JacekSzczytkofuwedupl
(Yatzek Schtchitko)
Faculty of Physics University of Warsaw
SPINTRONICS
2016-04-28 2
Google Jacek Szczytko
Login student
Hasło
Google Jacek Szczytko
Faculty of Physics University of Warsaw
2016-04-28 3
Hoża 69 1921-2014 r
The polariton laboratory
Kasia Lekenta
Mateusz Kroacutel Rafał Mirek
attocube CFM15-320K 00-90T700-1000nm420nm 532nm 633nmhellip
Dr Barbara Piętka
2016-04-28 5
The polariton laboratory
MBE growthRafał RudniewskiDr Wojciech PacuskiJean-Guy Rousset
Magneto-optical propertiesRafał MirekKatarzyna LekentaMateusz KroacutelDr Barbara Piętka
Appl Phys Lett 107 201109 (2015)
Laboratory of SQUID magnetometryAndrzej TwardowskiAndrzej MajhoferAnita GardiasJarosław RybusińskiMaciej Marchwiany (Monte Carlo)
2016-04-28 6
00-70T 15-8000K photomagnetism
2016-04-28
Magnetic nanoparticles
Magnetic Organic LCPiotr Kaszyński (Univ Vanderbilt USA The Centre of Molecular and Macromolecular Studies Lodz Poland)Ewa Goacuterecka (Faculty of Chemistry University of Warsaw)Damian Pociecha (Faculty of Chemistry University of Warsaw)
2016-04-28 8
Piotr Ewa
2016-04-28
Magnetic Organic LC
2016-04-28
SPINTRONICS1 Magnetic field and spin2 Exchange interactions3 Magnetism of matter4 Spintronics5 Organics spintronics
a Magnetismb Transportc Lightd Liquid crystals
S H
arri
s
Hamiltonian
2016-04-28 11
1
2119898Ƹ1199012 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
kinetic energy
119864119896 =1198981199072
119904=
1199012
2119898
potential energy time evolution
Homogenous magnetic field
2016-04-28 12
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Homogenous magnetic field
2016-04-28 13
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
Landau gauge magnetic field 119861 = 00 119861119911 rArr 119861119911 =120597119860119910
120597119909minus
120597119860119909
120597119910
Ԧ119860 = 0 119861119911119909 0 czyli 119860119910 = 119861119911119909 ≝ 119861119909
(unfortunately distinguishesdirection)
1
2119898minusℏ2
1205972
1205971199092+ minus119894ℏ
120597
120597119910+ 119890119861119909
2
minus ℏ21205972
1205971199112+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903
minusℏ2
21198981205712 minus
119894119890ℏ
119898119861119909
120597
120597119910+
119890119861119909 2
2119898+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903Which gives
The evidence of the Lorentz force Parabolic potential
We assume that in a plane 119909119910there is no other potential
119902 = minus119890
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Homogenous magnetic field
2016-04-28 14
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
Landau gauge magnetic field 119861 = 00 119861119911 rArr 119861119911 =120597119860119910
120597119909minus
120597119860119909
120597119910
Ԧ119860 = 0 119861119911119909 0 czyli 119860119910 = 119861119911119909 ≝ 119861119909
(unfortunately distinguishesdirection)
1
2119898minusℏ2
1205972
1205971199092+ minus119894ℏ
120597
120597119910+ 119890119861119909
2
minus ℏ21205972
1205971199112+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903
minusℏ2
21198981205712 minus
119894119890ℏ
119898119861119909
120597
120597119910+
119890119861119909 2
2119898+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903Which gives
The evidence of the Lorentz force Parabolic potential
We assume that in a plane 119909119910there is no other potential
119902 = minus119890
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Hamiltonian
2016-04-28 15
1
2119898Ƹ1199012 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
119880 119903 = minus1198902
41205871205761199031205760
1
119903
Coulomb potential
Coulomb potential
2016-04-28 16
FIRST Coulomb potential in 3D in the semiconductor of dielectric constant 120576119903 effective mass 119898lowast
119877119910 =1198902
41205871205760
2119898
2ℏ2=
ℏ2
21198981198861198612 =
1
2
1198902
41205871205760119886119861= 136 eV
119886119861 =41205871205760ℏ
2
11989801198902 = 05 Å
119880 119903 = minus1198902
41205871205761199031205760
1
119903
119864119899 = minus119898lowast
1198980
1
1205761199032 119877119910
1
1198992
119886119861lowast =
41205871205761199031205760ℏ2
11989801198902
1198980
119898lowast= 119886119861120576119903
1198980
119898lowast
119864119899 = minus1198771199101
1198992rArr | 119899 119897 119898119897
119897 = 012hellip
principal angular magnetic
clasically
thus
[Am2]
m
r
vBohr magneton 120583119861 =
ℏ119890
21198980
120583119861 = 9274009994(57)times10minus24 JT
2016-04-28 17
Magnetic field and spinMagnetic field
119867prime = minus119898119861
Here 119898 is magnetic moment
119898 = 119868 Ԧ119878 =119890
1198791205871199032 =
119890
21205871199031199071205871199032 =
119890
2119903119907
119898 = minus119890
21198980119871 = minus
120583119861ℏ119871
119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911119867prime = minus119898119861 =
120583119861ℏ119871119861
120583119861 =ℏ119890
21198980
circumference of a circle
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 18
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 19
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
2016-04-28 20
Magnetic field and spin
What is the bdquospinrdquo
bull What is bdquomassrdquo
Mariusz Pudzianowski httpwwwpudzianpl
2016-04-28 21
bull What is the bdquomomentumrdquo
What is the bdquospinrdquo
2016-04-28 22
bull What is the bdquoangular momentumrdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 23
bull What is the bdquochargerdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 24
bull Spin
DisneySebastian Muumlnster Cosmographia in 1544
htt
p
ww
wf
lori
dah
isto
ryc
om
us
15
70
htm
l
What is the bdquospinrdquo
2016-04-28 25
Pauli matrices 120590119909 120590119910 120590119911
Spinor
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
2016-04-28 26
Magnetic field and spinSpin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
2016-04-28 27
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc119892-factor for the agreement with experiments
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 28
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
119892 = minus200231930436182 plusmn 000000000000052
2016-04-28 29
QED ndash Quantum ElectroDynamics
119892 = minus200231930436182 plusmn 000000000000052
The consequences
2016-04-28 30
There is the bdquospinrdquo
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
Total magnetic moment 119872 = 119872119871 + 119872119878 = minus119892119871120583119861
ℏ119871 minus119892119878
120583119861
ℏመ119878
=1 =2
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 31
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
119872 ne መ119869 - magnetic anomaly of spin
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 32
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
119867119878119874 = 120582119871 መ119878 = 1205821
21198692 minus 1198712 minus 1198782 = 120582 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
120582 = ℎ119888 119860 =1198851205722
2
1
1199033
120572 =1198902
41205871205760ℏ119888asymp
1
137037
119864119878119874 = න120595lowast119867119878119874120595 119889119881 =119885
2 137 2න120595lowast119871 መ119878
1199033120595 119889119881
fine-structure constant119877119910 = ℎ119888119877infin
119877infin =119898119890119890
4
812057602ℎ3119888
119877infin = 1097 times 107m-1
eg for 120595210 we get1
1199033=
1
24
119885
1198860
3and for general 119899 (principal quantum number)
119864119878119874 =1198854
2 137 2119886031198993
119895 119895 + 1 minus 119897 119897 + 1 minus 119904(119904 + 1)
2119897(119897 + 12)(119897 + 1)
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 33
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
3
3
2
119871 = 1 መ119878 =1
2
211987532
211987512
shortly | ൿ119895 119898119895
the base | ൿ119899 119897 119904 119895 119898119895
ത119871 ҧ119878 =1
2ҧ1198692 minus ത1198712 minus ҧ1198782 = 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
Term symbol
an abbreviated description of the angular momentum quantum numbers in a multi-electron atom
Total wavefunction must be antisymmetric (under interchange of any pair of particle)
Orbital part Spin part
2016-04-28 34
Multi-electron atom2S+1 119871119869
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
120595 Ԧ1199031 hellip Ԧ119903119873 Ԧ1198781 hellip Ԧ119878119873 = 120595 Ԧ1199031 hellip Ԧ119903119873 120594 Ԧ1198781 hellip Ԧ119878119873
Multi-electron wavefunction
Antisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =Exchange interaction
Antisymmetric
Example
A
B
Two electrons localized on one centrum
2016-04-28 35
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Hundrsquos rules ET lt ES
Antisymmetric
2016-04-28 36
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28 2
Google Jacek Szczytko
Login student
Hasło
Google Jacek Szczytko
Faculty of Physics University of Warsaw
2016-04-28 3
Hoża 69 1921-2014 r
The polariton laboratory
Kasia Lekenta
Mateusz Kroacutel Rafał Mirek
attocube CFM15-320K 00-90T700-1000nm420nm 532nm 633nmhellip
Dr Barbara Piętka
2016-04-28 5
The polariton laboratory
MBE growthRafał RudniewskiDr Wojciech PacuskiJean-Guy Rousset
Magneto-optical propertiesRafał MirekKatarzyna LekentaMateusz KroacutelDr Barbara Piętka
Appl Phys Lett 107 201109 (2015)
Laboratory of SQUID magnetometryAndrzej TwardowskiAndrzej MajhoferAnita GardiasJarosław RybusińskiMaciej Marchwiany (Monte Carlo)
2016-04-28 6
00-70T 15-8000K photomagnetism
2016-04-28
Magnetic nanoparticles
Magnetic Organic LCPiotr Kaszyński (Univ Vanderbilt USA The Centre of Molecular and Macromolecular Studies Lodz Poland)Ewa Goacuterecka (Faculty of Chemistry University of Warsaw)Damian Pociecha (Faculty of Chemistry University of Warsaw)
2016-04-28 8
Piotr Ewa
2016-04-28
Magnetic Organic LC
2016-04-28
SPINTRONICS1 Magnetic field and spin2 Exchange interactions3 Magnetism of matter4 Spintronics5 Organics spintronics
a Magnetismb Transportc Lightd Liquid crystals
S H
arri
s
Hamiltonian
2016-04-28 11
1
2119898Ƹ1199012 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
kinetic energy
119864119896 =1198981199072
119904=
1199012
2119898
potential energy time evolution
Homogenous magnetic field
2016-04-28 12
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Homogenous magnetic field
2016-04-28 13
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
Landau gauge magnetic field 119861 = 00 119861119911 rArr 119861119911 =120597119860119910
120597119909minus
120597119860119909
120597119910
Ԧ119860 = 0 119861119911119909 0 czyli 119860119910 = 119861119911119909 ≝ 119861119909
(unfortunately distinguishesdirection)
1
2119898minusℏ2
1205972
1205971199092+ minus119894ℏ
120597
120597119910+ 119890119861119909
2
minus ℏ21205972
1205971199112+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903
minusℏ2
21198981205712 minus
119894119890ℏ
119898119861119909
120597
120597119910+
119890119861119909 2
2119898+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903Which gives
The evidence of the Lorentz force Parabolic potential
We assume that in a plane 119909119910there is no other potential
119902 = minus119890
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Homogenous magnetic field
2016-04-28 14
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
Landau gauge magnetic field 119861 = 00 119861119911 rArr 119861119911 =120597119860119910
120597119909minus
120597119860119909
120597119910
Ԧ119860 = 0 119861119911119909 0 czyli 119860119910 = 119861119911119909 ≝ 119861119909
(unfortunately distinguishesdirection)
1
2119898minusℏ2
1205972
1205971199092+ minus119894ℏ
120597
120597119910+ 119890119861119909
2
minus ℏ21205972
1205971199112+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903
minusℏ2
21198981205712 minus
119894119890ℏ
119898119861119909
120597
120597119910+
119890119861119909 2
2119898+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903Which gives
The evidence of the Lorentz force Parabolic potential
We assume that in a plane 119909119910there is no other potential
119902 = minus119890
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Hamiltonian
2016-04-28 15
1
2119898Ƹ1199012 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
119880 119903 = minus1198902
41205871205761199031205760
1
119903
Coulomb potential
Coulomb potential
2016-04-28 16
FIRST Coulomb potential in 3D in the semiconductor of dielectric constant 120576119903 effective mass 119898lowast
119877119910 =1198902
41205871205760
2119898
2ℏ2=
ℏ2
21198981198861198612 =
1
2
1198902
41205871205760119886119861= 136 eV
119886119861 =41205871205760ℏ
2
11989801198902 = 05 Å
119880 119903 = minus1198902
41205871205761199031205760
1
119903
119864119899 = minus119898lowast
1198980
1
1205761199032 119877119910
1
1198992
119886119861lowast =
41205871205761199031205760ℏ2
11989801198902
1198980
119898lowast= 119886119861120576119903
1198980
119898lowast
119864119899 = minus1198771199101
1198992rArr | 119899 119897 119898119897
119897 = 012hellip
principal angular magnetic
clasically
thus
[Am2]
m
r
vBohr magneton 120583119861 =
ℏ119890
21198980
120583119861 = 9274009994(57)times10minus24 JT
2016-04-28 17
Magnetic field and spinMagnetic field
119867prime = minus119898119861
Here 119898 is magnetic moment
119898 = 119868 Ԧ119878 =119890
1198791205871199032 =
119890
21205871199031199071205871199032 =
119890
2119903119907
119898 = minus119890
21198980119871 = minus
120583119861ℏ119871
119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911119867prime = minus119898119861 =
120583119861ℏ119871119861
120583119861 =ℏ119890
21198980
circumference of a circle
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 18
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 19
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
2016-04-28 20
Magnetic field and spin
What is the bdquospinrdquo
bull What is bdquomassrdquo
Mariusz Pudzianowski httpwwwpudzianpl
2016-04-28 21
bull What is the bdquomomentumrdquo
What is the bdquospinrdquo
2016-04-28 22
bull What is the bdquoangular momentumrdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 23
bull What is the bdquochargerdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 24
bull Spin
DisneySebastian Muumlnster Cosmographia in 1544
htt
p
ww
wf
lori
dah
isto
ryc
om
us
15
70
htm
l
What is the bdquospinrdquo
2016-04-28 25
Pauli matrices 120590119909 120590119910 120590119911
Spinor
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
2016-04-28 26
Magnetic field and spinSpin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
2016-04-28 27
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc119892-factor for the agreement with experiments
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 28
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
119892 = minus200231930436182 plusmn 000000000000052
2016-04-28 29
QED ndash Quantum ElectroDynamics
119892 = minus200231930436182 plusmn 000000000000052
The consequences
2016-04-28 30
There is the bdquospinrdquo
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
Total magnetic moment 119872 = 119872119871 + 119872119878 = minus119892119871120583119861
ℏ119871 minus119892119878
120583119861
ℏመ119878
=1 =2
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 31
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
119872 ne መ119869 - magnetic anomaly of spin
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 32
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
119867119878119874 = 120582119871 መ119878 = 1205821
21198692 minus 1198712 minus 1198782 = 120582 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
120582 = ℎ119888 119860 =1198851205722
2
1
1199033
120572 =1198902
41205871205760ℏ119888asymp
1
137037
119864119878119874 = න120595lowast119867119878119874120595 119889119881 =119885
2 137 2න120595lowast119871 መ119878
1199033120595 119889119881
fine-structure constant119877119910 = ℎ119888119877infin
119877infin =119898119890119890
4
812057602ℎ3119888
119877infin = 1097 times 107m-1
eg for 120595210 we get1
1199033=
1
24
119885
1198860
3and for general 119899 (principal quantum number)
119864119878119874 =1198854
2 137 2119886031198993
119895 119895 + 1 minus 119897 119897 + 1 minus 119904(119904 + 1)
2119897(119897 + 12)(119897 + 1)
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 33
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
3
3
2
119871 = 1 መ119878 =1
2
211987532
211987512
shortly | ൿ119895 119898119895
the base | ൿ119899 119897 119904 119895 119898119895
ത119871 ҧ119878 =1
2ҧ1198692 minus ത1198712 minus ҧ1198782 = 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
Term symbol
an abbreviated description of the angular momentum quantum numbers in a multi-electron atom
Total wavefunction must be antisymmetric (under interchange of any pair of particle)
Orbital part Spin part
2016-04-28 34
Multi-electron atom2S+1 119871119869
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
120595 Ԧ1199031 hellip Ԧ119903119873 Ԧ1198781 hellip Ԧ119878119873 = 120595 Ԧ1199031 hellip Ԧ119903119873 120594 Ԧ1198781 hellip Ԧ119878119873
Multi-electron wavefunction
Antisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =Exchange interaction
Antisymmetric
Example
A
B
Two electrons localized on one centrum
2016-04-28 35
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Hundrsquos rules ET lt ES
Antisymmetric
2016-04-28 36
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Faculty of Physics University of Warsaw
2016-04-28 3
Hoża 69 1921-2014 r
The polariton laboratory
Kasia Lekenta
Mateusz Kroacutel Rafał Mirek
attocube CFM15-320K 00-90T700-1000nm420nm 532nm 633nmhellip
Dr Barbara Piętka
2016-04-28 5
The polariton laboratory
MBE growthRafał RudniewskiDr Wojciech PacuskiJean-Guy Rousset
Magneto-optical propertiesRafał MirekKatarzyna LekentaMateusz KroacutelDr Barbara Piętka
Appl Phys Lett 107 201109 (2015)
Laboratory of SQUID magnetometryAndrzej TwardowskiAndrzej MajhoferAnita GardiasJarosław RybusińskiMaciej Marchwiany (Monte Carlo)
2016-04-28 6
00-70T 15-8000K photomagnetism
2016-04-28
Magnetic nanoparticles
Magnetic Organic LCPiotr Kaszyński (Univ Vanderbilt USA The Centre of Molecular and Macromolecular Studies Lodz Poland)Ewa Goacuterecka (Faculty of Chemistry University of Warsaw)Damian Pociecha (Faculty of Chemistry University of Warsaw)
2016-04-28 8
Piotr Ewa
2016-04-28
Magnetic Organic LC
2016-04-28
SPINTRONICS1 Magnetic field and spin2 Exchange interactions3 Magnetism of matter4 Spintronics5 Organics spintronics
a Magnetismb Transportc Lightd Liquid crystals
S H
arri
s
Hamiltonian
2016-04-28 11
1
2119898Ƹ1199012 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
kinetic energy
119864119896 =1198981199072
119904=
1199012
2119898
potential energy time evolution
Homogenous magnetic field
2016-04-28 12
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Homogenous magnetic field
2016-04-28 13
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
Landau gauge magnetic field 119861 = 00 119861119911 rArr 119861119911 =120597119860119910
120597119909minus
120597119860119909
120597119910
Ԧ119860 = 0 119861119911119909 0 czyli 119860119910 = 119861119911119909 ≝ 119861119909
(unfortunately distinguishesdirection)
1
2119898minusℏ2
1205972
1205971199092+ minus119894ℏ
120597
120597119910+ 119890119861119909
2
minus ℏ21205972
1205971199112+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903
minusℏ2
21198981205712 minus
119894119890ℏ
119898119861119909
120597
120597119910+
119890119861119909 2
2119898+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903Which gives
The evidence of the Lorentz force Parabolic potential
We assume that in a plane 119909119910there is no other potential
119902 = minus119890
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Homogenous magnetic field
2016-04-28 14
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
Landau gauge magnetic field 119861 = 00 119861119911 rArr 119861119911 =120597119860119910
120597119909minus
120597119860119909
120597119910
Ԧ119860 = 0 119861119911119909 0 czyli 119860119910 = 119861119911119909 ≝ 119861119909
(unfortunately distinguishesdirection)
1
2119898minusℏ2
1205972
1205971199092+ minus119894ℏ
120597
120597119910+ 119890119861119909
2
minus ℏ21205972
1205971199112+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903
minusℏ2
21198981205712 minus
119894119890ℏ
119898119861119909
120597
120597119910+
119890119861119909 2
2119898+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903Which gives
The evidence of the Lorentz force Parabolic potential
We assume that in a plane 119909119910there is no other potential
119902 = minus119890
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Hamiltonian
2016-04-28 15
1
2119898Ƹ1199012 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
119880 119903 = minus1198902
41205871205761199031205760
1
119903
Coulomb potential
Coulomb potential
2016-04-28 16
FIRST Coulomb potential in 3D in the semiconductor of dielectric constant 120576119903 effective mass 119898lowast
119877119910 =1198902
41205871205760
2119898
2ℏ2=
ℏ2
21198981198861198612 =
1
2
1198902
41205871205760119886119861= 136 eV
119886119861 =41205871205760ℏ
2
11989801198902 = 05 Å
119880 119903 = minus1198902
41205871205761199031205760
1
119903
119864119899 = minus119898lowast
1198980
1
1205761199032 119877119910
1
1198992
119886119861lowast =
41205871205761199031205760ℏ2
11989801198902
1198980
119898lowast= 119886119861120576119903
1198980
119898lowast
119864119899 = minus1198771199101
1198992rArr | 119899 119897 119898119897
119897 = 012hellip
principal angular magnetic
clasically
thus
[Am2]
m
r
vBohr magneton 120583119861 =
ℏ119890
21198980
120583119861 = 9274009994(57)times10minus24 JT
2016-04-28 17
Magnetic field and spinMagnetic field
119867prime = minus119898119861
Here 119898 is magnetic moment
119898 = 119868 Ԧ119878 =119890
1198791205871199032 =
119890
21205871199031199071205871199032 =
119890
2119903119907
119898 = minus119890
21198980119871 = minus
120583119861ℏ119871
119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911119867prime = minus119898119861 =
120583119861ℏ119871119861
120583119861 =ℏ119890
21198980
circumference of a circle
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 18
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 19
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
2016-04-28 20
Magnetic field and spin
What is the bdquospinrdquo
bull What is bdquomassrdquo
Mariusz Pudzianowski httpwwwpudzianpl
2016-04-28 21
bull What is the bdquomomentumrdquo
What is the bdquospinrdquo
2016-04-28 22
bull What is the bdquoangular momentumrdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 23
bull What is the bdquochargerdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 24
bull Spin
DisneySebastian Muumlnster Cosmographia in 1544
htt
p
ww
wf
lori
dah
isto
ryc
om
us
15
70
htm
l
What is the bdquospinrdquo
2016-04-28 25
Pauli matrices 120590119909 120590119910 120590119911
Spinor
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
2016-04-28 26
Magnetic field and spinSpin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
2016-04-28 27
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc119892-factor for the agreement with experiments
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 28
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
119892 = minus200231930436182 plusmn 000000000000052
2016-04-28 29
QED ndash Quantum ElectroDynamics
119892 = minus200231930436182 plusmn 000000000000052
The consequences
2016-04-28 30
There is the bdquospinrdquo
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
Total magnetic moment 119872 = 119872119871 + 119872119878 = minus119892119871120583119861
ℏ119871 minus119892119878
120583119861
ℏመ119878
=1 =2
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 31
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
119872 ne መ119869 - magnetic anomaly of spin
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 32
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
119867119878119874 = 120582119871 መ119878 = 1205821
21198692 minus 1198712 minus 1198782 = 120582 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
120582 = ℎ119888 119860 =1198851205722
2
1
1199033
120572 =1198902
41205871205760ℏ119888asymp
1
137037
119864119878119874 = න120595lowast119867119878119874120595 119889119881 =119885
2 137 2න120595lowast119871 መ119878
1199033120595 119889119881
fine-structure constant119877119910 = ℎ119888119877infin
119877infin =119898119890119890
4
812057602ℎ3119888
119877infin = 1097 times 107m-1
eg for 120595210 we get1
1199033=
1
24
119885
1198860
3and for general 119899 (principal quantum number)
119864119878119874 =1198854
2 137 2119886031198993
119895 119895 + 1 minus 119897 119897 + 1 minus 119904(119904 + 1)
2119897(119897 + 12)(119897 + 1)
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 33
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
3
3
2
119871 = 1 መ119878 =1
2
211987532
211987512
shortly | ൿ119895 119898119895
the base | ൿ119899 119897 119904 119895 119898119895
ത119871 ҧ119878 =1
2ҧ1198692 minus ത1198712 minus ҧ1198782 = 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
Term symbol
an abbreviated description of the angular momentum quantum numbers in a multi-electron atom
Total wavefunction must be antisymmetric (under interchange of any pair of particle)
Orbital part Spin part
2016-04-28 34
Multi-electron atom2S+1 119871119869
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
120595 Ԧ1199031 hellip Ԧ119903119873 Ԧ1198781 hellip Ԧ119878119873 = 120595 Ԧ1199031 hellip Ԧ119903119873 120594 Ԧ1198781 hellip Ԧ119878119873
Multi-electron wavefunction
Antisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =Exchange interaction
Antisymmetric
Example
A
B
Two electrons localized on one centrum
2016-04-28 35
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Hundrsquos rules ET lt ES
Antisymmetric
2016-04-28 36
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
The polariton laboratory
Kasia Lekenta
Mateusz Kroacutel Rafał Mirek
attocube CFM15-320K 00-90T700-1000nm420nm 532nm 633nmhellip
Dr Barbara Piętka
2016-04-28 5
The polariton laboratory
MBE growthRafał RudniewskiDr Wojciech PacuskiJean-Guy Rousset
Magneto-optical propertiesRafał MirekKatarzyna LekentaMateusz KroacutelDr Barbara Piętka
Appl Phys Lett 107 201109 (2015)
Laboratory of SQUID magnetometryAndrzej TwardowskiAndrzej MajhoferAnita GardiasJarosław RybusińskiMaciej Marchwiany (Monte Carlo)
2016-04-28 6
00-70T 15-8000K photomagnetism
2016-04-28
Magnetic nanoparticles
Magnetic Organic LCPiotr Kaszyński (Univ Vanderbilt USA The Centre of Molecular and Macromolecular Studies Lodz Poland)Ewa Goacuterecka (Faculty of Chemistry University of Warsaw)Damian Pociecha (Faculty of Chemistry University of Warsaw)
2016-04-28 8
Piotr Ewa
2016-04-28
Magnetic Organic LC
2016-04-28
SPINTRONICS1 Magnetic field and spin2 Exchange interactions3 Magnetism of matter4 Spintronics5 Organics spintronics
a Magnetismb Transportc Lightd Liquid crystals
S H
arri
s
Hamiltonian
2016-04-28 11
1
2119898Ƹ1199012 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
kinetic energy
119864119896 =1198981199072
119904=
1199012
2119898
potential energy time evolution
Homogenous magnetic field
2016-04-28 12
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Homogenous magnetic field
2016-04-28 13
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
Landau gauge magnetic field 119861 = 00 119861119911 rArr 119861119911 =120597119860119910
120597119909minus
120597119860119909
120597119910
Ԧ119860 = 0 119861119911119909 0 czyli 119860119910 = 119861119911119909 ≝ 119861119909
(unfortunately distinguishesdirection)
1
2119898minusℏ2
1205972
1205971199092+ minus119894ℏ
120597
120597119910+ 119890119861119909
2
minus ℏ21205972
1205971199112+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903
minusℏ2
21198981205712 minus
119894119890ℏ
119898119861119909
120597
120597119910+
119890119861119909 2
2119898+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903Which gives
The evidence of the Lorentz force Parabolic potential
We assume that in a plane 119909119910there is no other potential
119902 = minus119890
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Homogenous magnetic field
2016-04-28 14
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
Landau gauge magnetic field 119861 = 00 119861119911 rArr 119861119911 =120597119860119910
120597119909minus
120597119860119909
120597119910
Ԧ119860 = 0 119861119911119909 0 czyli 119860119910 = 119861119911119909 ≝ 119861119909
(unfortunately distinguishesdirection)
1
2119898minusℏ2
1205972
1205971199092+ minus119894ℏ
120597
120597119910+ 119890119861119909
2
minus ℏ21205972
1205971199112+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903
minusℏ2
21198981205712 minus
119894119890ℏ
119898119861119909
120597
120597119910+
119890119861119909 2
2119898+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903Which gives
The evidence of the Lorentz force Parabolic potential
We assume that in a plane 119909119910there is no other potential
119902 = minus119890
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Hamiltonian
2016-04-28 15
1
2119898Ƹ1199012 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
119880 119903 = minus1198902
41205871205761199031205760
1
119903
Coulomb potential
Coulomb potential
2016-04-28 16
FIRST Coulomb potential in 3D in the semiconductor of dielectric constant 120576119903 effective mass 119898lowast
119877119910 =1198902
41205871205760
2119898
2ℏ2=
ℏ2
21198981198861198612 =
1
2
1198902
41205871205760119886119861= 136 eV
119886119861 =41205871205760ℏ
2
11989801198902 = 05 Å
119880 119903 = minus1198902
41205871205761199031205760
1
119903
119864119899 = minus119898lowast
1198980
1
1205761199032 119877119910
1
1198992
119886119861lowast =
41205871205761199031205760ℏ2
11989801198902
1198980
119898lowast= 119886119861120576119903
1198980
119898lowast
119864119899 = minus1198771199101
1198992rArr | 119899 119897 119898119897
119897 = 012hellip
principal angular magnetic
clasically
thus
[Am2]
m
r
vBohr magneton 120583119861 =
ℏ119890
21198980
120583119861 = 9274009994(57)times10minus24 JT
2016-04-28 17
Magnetic field and spinMagnetic field
119867prime = minus119898119861
Here 119898 is magnetic moment
119898 = 119868 Ԧ119878 =119890
1198791205871199032 =
119890
21205871199031199071205871199032 =
119890
2119903119907
119898 = minus119890
21198980119871 = minus
120583119861ℏ119871
119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911119867prime = minus119898119861 =
120583119861ℏ119871119861
120583119861 =ℏ119890
21198980
circumference of a circle
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 18
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 19
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
2016-04-28 20
Magnetic field and spin
What is the bdquospinrdquo
bull What is bdquomassrdquo
Mariusz Pudzianowski httpwwwpudzianpl
2016-04-28 21
bull What is the bdquomomentumrdquo
What is the bdquospinrdquo
2016-04-28 22
bull What is the bdquoangular momentumrdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 23
bull What is the bdquochargerdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 24
bull Spin
DisneySebastian Muumlnster Cosmographia in 1544
htt
p
ww
wf
lori
dah
isto
ryc
om
us
15
70
htm
l
What is the bdquospinrdquo
2016-04-28 25
Pauli matrices 120590119909 120590119910 120590119911
Spinor
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
2016-04-28 26
Magnetic field and spinSpin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
2016-04-28 27
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc119892-factor for the agreement with experiments
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 28
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
119892 = minus200231930436182 plusmn 000000000000052
2016-04-28 29
QED ndash Quantum ElectroDynamics
119892 = minus200231930436182 plusmn 000000000000052
The consequences
2016-04-28 30
There is the bdquospinrdquo
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
Total magnetic moment 119872 = 119872119871 + 119872119878 = minus119892119871120583119861
ℏ119871 minus119892119878
120583119861
ℏመ119878
=1 =2
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 31
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
119872 ne መ119869 - magnetic anomaly of spin
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 32
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
119867119878119874 = 120582119871 መ119878 = 1205821
21198692 minus 1198712 minus 1198782 = 120582 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
120582 = ℎ119888 119860 =1198851205722
2
1
1199033
120572 =1198902
41205871205760ℏ119888asymp
1
137037
119864119878119874 = න120595lowast119867119878119874120595 119889119881 =119885
2 137 2න120595lowast119871 መ119878
1199033120595 119889119881
fine-structure constant119877119910 = ℎ119888119877infin
119877infin =119898119890119890
4
812057602ℎ3119888
119877infin = 1097 times 107m-1
eg for 120595210 we get1
1199033=
1
24
119885
1198860
3and for general 119899 (principal quantum number)
119864119878119874 =1198854
2 137 2119886031198993
119895 119895 + 1 minus 119897 119897 + 1 minus 119904(119904 + 1)
2119897(119897 + 12)(119897 + 1)
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 33
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
3
3
2
119871 = 1 መ119878 =1
2
211987532
211987512
shortly | ൿ119895 119898119895
the base | ൿ119899 119897 119904 119895 119898119895
ത119871 ҧ119878 =1
2ҧ1198692 minus ത1198712 minus ҧ1198782 = 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
Term symbol
an abbreviated description of the angular momentum quantum numbers in a multi-electron atom
Total wavefunction must be antisymmetric (under interchange of any pair of particle)
Orbital part Spin part
2016-04-28 34
Multi-electron atom2S+1 119871119869
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
120595 Ԧ1199031 hellip Ԧ119903119873 Ԧ1198781 hellip Ԧ119878119873 = 120595 Ԧ1199031 hellip Ԧ119903119873 120594 Ԧ1198781 hellip Ԧ119878119873
Multi-electron wavefunction
Antisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =Exchange interaction
Antisymmetric
Example
A
B
Two electrons localized on one centrum
2016-04-28 35
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Hundrsquos rules ET lt ES
Antisymmetric
2016-04-28 36
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28 5
The polariton laboratory
MBE growthRafał RudniewskiDr Wojciech PacuskiJean-Guy Rousset
Magneto-optical propertiesRafał MirekKatarzyna LekentaMateusz KroacutelDr Barbara Piętka
Appl Phys Lett 107 201109 (2015)
Laboratory of SQUID magnetometryAndrzej TwardowskiAndrzej MajhoferAnita GardiasJarosław RybusińskiMaciej Marchwiany (Monte Carlo)
2016-04-28 6
00-70T 15-8000K photomagnetism
2016-04-28
Magnetic nanoparticles
Magnetic Organic LCPiotr Kaszyński (Univ Vanderbilt USA The Centre of Molecular and Macromolecular Studies Lodz Poland)Ewa Goacuterecka (Faculty of Chemistry University of Warsaw)Damian Pociecha (Faculty of Chemistry University of Warsaw)
2016-04-28 8
Piotr Ewa
2016-04-28
Magnetic Organic LC
2016-04-28
SPINTRONICS1 Magnetic field and spin2 Exchange interactions3 Magnetism of matter4 Spintronics5 Organics spintronics
a Magnetismb Transportc Lightd Liquid crystals
S H
arri
s
Hamiltonian
2016-04-28 11
1
2119898Ƹ1199012 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
kinetic energy
119864119896 =1198981199072
119904=
1199012
2119898
potential energy time evolution
Homogenous magnetic field
2016-04-28 12
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Homogenous magnetic field
2016-04-28 13
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
Landau gauge magnetic field 119861 = 00 119861119911 rArr 119861119911 =120597119860119910
120597119909minus
120597119860119909
120597119910
Ԧ119860 = 0 119861119911119909 0 czyli 119860119910 = 119861119911119909 ≝ 119861119909
(unfortunately distinguishesdirection)
1
2119898minusℏ2
1205972
1205971199092+ minus119894ℏ
120597
120597119910+ 119890119861119909
2
minus ℏ21205972
1205971199112+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903
minusℏ2
21198981205712 minus
119894119890ℏ
119898119861119909
120597
120597119910+
119890119861119909 2
2119898+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903Which gives
The evidence of the Lorentz force Parabolic potential
We assume that in a plane 119909119910there is no other potential
119902 = minus119890
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Homogenous magnetic field
2016-04-28 14
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
Landau gauge magnetic field 119861 = 00 119861119911 rArr 119861119911 =120597119860119910
120597119909minus
120597119860119909
120597119910
Ԧ119860 = 0 119861119911119909 0 czyli 119860119910 = 119861119911119909 ≝ 119861119909
(unfortunately distinguishesdirection)
1
2119898minusℏ2
1205972
1205971199092+ minus119894ℏ
120597
120597119910+ 119890119861119909
2
minus ℏ21205972
1205971199112+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903
minusℏ2
21198981205712 minus
119894119890ℏ
119898119861119909
120597
120597119910+
119890119861119909 2
2119898+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903Which gives
The evidence of the Lorentz force Parabolic potential
We assume that in a plane 119909119910there is no other potential
119902 = minus119890
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Hamiltonian
2016-04-28 15
1
2119898Ƹ1199012 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
119880 119903 = minus1198902
41205871205761199031205760
1
119903
Coulomb potential
Coulomb potential
2016-04-28 16
FIRST Coulomb potential in 3D in the semiconductor of dielectric constant 120576119903 effective mass 119898lowast
119877119910 =1198902
41205871205760
2119898
2ℏ2=
ℏ2
21198981198861198612 =
1
2
1198902
41205871205760119886119861= 136 eV
119886119861 =41205871205760ℏ
2
11989801198902 = 05 Å
119880 119903 = minus1198902
41205871205761199031205760
1
119903
119864119899 = minus119898lowast
1198980
1
1205761199032 119877119910
1
1198992
119886119861lowast =
41205871205761199031205760ℏ2
11989801198902
1198980
119898lowast= 119886119861120576119903
1198980
119898lowast
119864119899 = minus1198771199101
1198992rArr | 119899 119897 119898119897
119897 = 012hellip
principal angular magnetic
clasically
thus
[Am2]
m
r
vBohr magneton 120583119861 =
ℏ119890
21198980
120583119861 = 9274009994(57)times10minus24 JT
2016-04-28 17
Magnetic field and spinMagnetic field
119867prime = minus119898119861
Here 119898 is magnetic moment
119898 = 119868 Ԧ119878 =119890
1198791205871199032 =
119890
21205871199031199071205871199032 =
119890
2119903119907
119898 = minus119890
21198980119871 = minus
120583119861ℏ119871
119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911119867prime = minus119898119861 =
120583119861ℏ119871119861
120583119861 =ℏ119890
21198980
circumference of a circle
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 18
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 19
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
2016-04-28 20
Magnetic field and spin
What is the bdquospinrdquo
bull What is bdquomassrdquo
Mariusz Pudzianowski httpwwwpudzianpl
2016-04-28 21
bull What is the bdquomomentumrdquo
What is the bdquospinrdquo
2016-04-28 22
bull What is the bdquoangular momentumrdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 23
bull What is the bdquochargerdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 24
bull Spin
DisneySebastian Muumlnster Cosmographia in 1544
htt
p
ww
wf
lori
dah
isto
ryc
om
us
15
70
htm
l
What is the bdquospinrdquo
2016-04-28 25
Pauli matrices 120590119909 120590119910 120590119911
Spinor
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
2016-04-28 26
Magnetic field and spinSpin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
2016-04-28 27
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc119892-factor for the agreement with experiments
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 28
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
119892 = minus200231930436182 plusmn 000000000000052
2016-04-28 29
QED ndash Quantum ElectroDynamics
119892 = minus200231930436182 plusmn 000000000000052
The consequences
2016-04-28 30
There is the bdquospinrdquo
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
Total magnetic moment 119872 = 119872119871 + 119872119878 = minus119892119871120583119861
ℏ119871 minus119892119878
120583119861
ℏመ119878
=1 =2
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 31
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
119872 ne መ119869 - magnetic anomaly of spin
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 32
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
119867119878119874 = 120582119871 መ119878 = 1205821
21198692 minus 1198712 minus 1198782 = 120582 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
120582 = ℎ119888 119860 =1198851205722
2
1
1199033
120572 =1198902
41205871205760ℏ119888asymp
1
137037
119864119878119874 = න120595lowast119867119878119874120595 119889119881 =119885
2 137 2න120595lowast119871 መ119878
1199033120595 119889119881
fine-structure constant119877119910 = ℎ119888119877infin
119877infin =119898119890119890
4
812057602ℎ3119888
119877infin = 1097 times 107m-1
eg for 120595210 we get1
1199033=
1
24
119885
1198860
3and for general 119899 (principal quantum number)
119864119878119874 =1198854
2 137 2119886031198993
119895 119895 + 1 minus 119897 119897 + 1 minus 119904(119904 + 1)
2119897(119897 + 12)(119897 + 1)
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 33
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
3
3
2
119871 = 1 መ119878 =1
2
211987532
211987512
shortly | ൿ119895 119898119895
the base | ൿ119899 119897 119904 119895 119898119895
ത119871 ҧ119878 =1
2ҧ1198692 minus ത1198712 minus ҧ1198782 = 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
Term symbol
an abbreviated description of the angular momentum quantum numbers in a multi-electron atom
Total wavefunction must be antisymmetric (under interchange of any pair of particle)
Orbital part Spin part
2016-04-28 34
Multi-electron atom2S+1 119871119869
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
120595 Ԧ1199031 hellip Ԧ119903119873 Ԧ1198781 hellip Ԧ119878119873 = 120595 Ԧ1199031 hellip Ԧ119903119873 120594 Ԧ1198781 hellip Ԧ119878119873
Multi-electron wavefunction
Antisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =Exchange interaction
Antisymmetric
Example
A
B
Two electrons localized on one centrum
2016-04-28 35
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Hundrsquos rules ET lt ES
Antisymmetric
2016-04-28 36
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Laboratory of SQUID magnetometryAndrzej TwardowskiAndrzej MajhoferAnita GardiasJarosław RybusińskiMaciej Marchwiany (Monte Carlo)
2016-04-28 6
00-70T 15-8000K photomagnetism
2016-04-28
Magnetic nanoparticles
Magnetic Organic LCPiotr Kaszyński (Univ Vanderbilt USA The Centre of Molecular and Macromolecular Studies Lodz Poland)Ewa Goacuterecka (Faculty of Chemistry University of Warsaw)Damian Pociecha (Faculty of Chemistry University of Warsaw)
2016-04-28 8
Piotr Ewa
2016-04-28
Magnetic Organic LC
2016-04-28
SPINTRONICS1 Magnetic field and spin2 Exchange interactions3 Magnetism of matter4 Spintronics5 Organics spintronics
a Magnetismb Transportc Lightd Liquid crystals
S H
arri
s
Hamiltonian
2016-04-28 11
1
2119898Ƹ1199012 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
kinetic energy
119864119896 =1198981199072
119904=
1199012
2119898
potential energy time evolution
Homogenous magnetic field
2016-04-28 12
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Homogenous magnetic field
2016-04-28 13
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
Landau gauge magnetic field 119861 = 00 119861119911 rArr 119861119911 =120597119860119910
120597119909minus
120597119860119909
120597119910
Ԧ119860 = 0 119861119911119909 0 czyli 119860119910 = 119861119911119909 ≝ 119861119909
(unfortunately distinguishesdirection)
1
2119898minusℏ2
1205972
1205971199092+ minus119894ℏ
120597
120597119910+ 119890119861119909
2
minus ℏ21205972
1205971199112+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903
minusℏ2
21198981205712 minus
119894119890ℏ
119898119861119909
120597
120597119910+
119890119861119909 2
2119898+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903Which gives
The evidence of the Lorentz force Parabolic potential
We assume that in a plane 119909119910there is no other potential
119902 = minus119890
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Homogenous magnetic field
2016-04-28 14
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
Landau gauge magnetic field 119861 = 00 119861119911 rArr 119861119911 =120597119860119910
120597119909minus
120597119860119909
120597119910
Ԧ119860 = 0 119861119911119909 0 czyli 119860119910 = 119861119911119909 ≝ 119861119909
(unfortunately distinguishesdirection)
1
2119898minusℏ2
1205972
1205971199092+ minus119894ℏ
120597
120597119910+ 119890119861119909
2
minus ℏ21205972
1205971199112+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903
minusℏ2
21198981205712 minus
119894119890ℏ
119898119861119909
120597
120597119910+
119890119861119909 2
2119898+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903Which gives
The evidence of the Lorentz force Parabolic potential
We assume that in a plane 119909119910there is no other potential
119902 = minus119890
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Hamiltonian
2016-04-28 15
1
2119898Ƹ1199012 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
119880 119903 = minus1198902
41205871205761199031205760
1
119903
Coulomb potential
Coulomb potential
2016-04-28 16
FIRST Coulomb potential in 3D in the semiconductor of dielectric constant 120576119903 effective mass 119898lowast
119877119910 =1198902
41205871205760
2119898
2ℏ2=
ℏ2
21198981198861198612 =
1
2
1198902
41205871205760119886119861= 136 eV
119886119861 =41205871205760ℏ
2
11989801198902 = 05 Å
119880 119903 = minus1198902
41205871205761199031205760
1
119903
119864119899 = minus119898lowast
1198980
1
1205761199032 119877119910
1
1198992
119886119861lowast =
41205871205761199031205760ℏ2
11989801198902
1198980
119898lowast= 119886119861120576119903
1198980
119898lowast
119864119899 = minus1198771199101
1198992rArr | 119899 119897 119898119897
119897 = 012hellip
principal angular magnetic
clasically
thus
[Am2]
m
r
vBohr magneton 120583119861 =
ℏ119890
21198980
120583119861 = 9274009994(57)times10minus24 JT
2016-04-28 17
Magnetic field and spinMagnetic field
119867prime = minus119898119861
Here 119898 is magnetic moment
119898 = 119868 Ԧ119878 =119890
1198791205871199032 =
119890
21205871199031199071205871199032 =
119890
2119903119907
119898 = minus119890
21198980119871 = minus
120583119861ℏ119871
119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911119867prime = minus119898119861 =
120583119861ℏ119871119861
120583119861 =ℏ119890
21198980
circumference of a circle
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 18
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 19
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
2016-04-28 20
Magnetic field and spin
What is the bdquospinrdquo
bull What is bdquomassrdquo
Mariusz Pudzianowski httpwwwpudzianpl
2016-04-28 21
bull What is the bdquomomentumrdquo
What is the bdquospinrdquo
2016-04-28 22
bull What is the bdquoangular momentumrdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 23
bull What is the bdquochargerdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 24
bull Spin
DisneySebastian Muumlnster Cosmographia in 1544
htt
p
ww
wf
lori
dah
isto
ryc
om
us
15
70
htm
l
What is the bdquospinrdquo
2016-04-28 25
Pauli matrices 120590119909 120590119910 120590119911
Spinor
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
2016-04-28 26
Magnetic field and spinSpin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
2016-04-28 27
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc119892-factor for the agreement with experiments
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 28
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
119892 = minus200231930436182 plusmn 000000000000052
2016-04-28 29
QED ndash Quantum ElectroDynamics
119892 = minus200231930436182 plusmn 000000000000052
The consequences
2016-04-28 30
There is the bdquospinrdquo
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
Total magnetic moment 119872 = 119872119871 + 119872119878 = minus119892119871120583119861
ℏ119871 minus119892119878
120583119861
ℏመ119878
=1 =2
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 31
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
119872 ne መ119869 - magnetic anomaly of spin
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 32
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
119867119878119874 = 120582119871 መ119878 = 1205821
21198692 minus 1198712 minus 1198782 = 120582 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
120582 = ℎ119888 119860 =1198851205722
2
1
1199033
120572 =1198902
41205871205760ℏ119888asymp
1
137037
119864119878119874 = න120595lowast119867119878119874120595 119889119881 =119885
2 137 2න120595lowast119871 መ119878
1199033120595 119889119881
fine-structure constant119877119910 = ℎ119888119877infin
119877infin =119898119890119890
4
812057602ℎ3119888
119877infin = 1097 times 107m-1
eg for 120595210 we get1
1199033=
1
24
119885
1198860
3and for general 119899 (principal quantum number)
119864119878119874 =1198854
2 137 2119886031198993
119895 119895 + 1 minus 119897 119897 + 1 minus 119904(119904 + 1)
2119897(119897 + 12)(119897 + 1)
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 33
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
3
3
2
119871 = 1 መ119878 =1
2
211987532
211987512
shortly | ൿ119895 119898119895
the base | ൿ119899 119897 119904 119895 119898119895
ത119871 ҧ119878 =1
2ҧ1198692 minus ത1198712 minus ҧ1198782 = 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
Term symbol
an abbreviated description of the angular momentum quantum numbers in a multi-electron atom
Total wavefunction must be antisymmetric (under interchange of any pair of particle)
Orbital part Spin part
2016-04-28 34
Multi-electron atom2S+1 119871119869
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
120595 Ԧ1199031 hellip Ԧ119903119873 Ԧ1198781 hellip Ԧ119878119873 = 120595 Ԧ1199031 hellip Ԧ119903119873 120594 Ԧ1198781 hellip Ԧ119878119873
Multi-electron wavefunction
Antisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =Exchange interaction
Antisymmetric
Example
A
B
Two electrons localized on one centrum
2016-04-28 35
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Hundrsquos rules ET lt ES
Antisymmetric
2016-04-28 36
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28
Magnetic nanoparticles
Magnetic Organic LCPiotr Kaszyński (Univ Vanderbilt USA The Centre of Molecular and Macromolecular Studies Lodz Poland)Ewa Goacuterecka (Faculty of Chemistry University of Warsaw)Damian Pociecha (Faculty of Chemistry University of Warsaw)
2016-04-28 8
Piotr Ewa
2016-04-28
Magnetic Organic LC
2016-04-28
SPINTRONICS1 Magnetic field and spin2 Exchange interactions3 Magnetism of matter4 Spintronics5 Organics spintronics
a Magnetismb Transportc Lightd Liquid crystals
S H
arri
s
Hamiltonian
2016-04-28 11
1
2119898Ƹ1199012 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
kinetic energy
119864119896 =1198981199072
119904=
1199012
2119898
potential energy time evolution
Homogenous magnetic field
2016-04-28 12
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Homogenous magnetic field
2016-04-28 13
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
Landau gauge magnetic field 119861 = 00 119861119911 rArr 119861119911 =120597119860119910
120597119909minus
120597119860119909
120597119910
Ԧ119860 = 0 119861119911119909 0 czyli 119860119910 = 119861119911119909 ≝ 119861119909
(unfortunately distinguishesdirection)
1
2119898minusℏ2
1205972
1205971199092+ minus119894ℏ
120597
120597119910+ 119890119861119909
2
minus ℏ21205972
1205971199112+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903
minusℏ2
21198981205712 minus
119894119890ℏ
119898119861119909
120597
120597119910+
119890119861119909 2
2119898+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903Which gives
The evidence of the Lorentz force Parabolic potential
We assume that in a plane 119909119910there is no other potential
119902 = minus119890
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Homogenous magnetic field
2016-04-28 14
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
Landau gauge magnetic field 119861 = 00 119861119911 rArr 119861119911 =120597119860119910
120597119909minus
120597119860119909
120597119910
Ԧ119860 = 0 119861119911119909 0 czyli 119860119910 = 119861119911119909 ≝ 119861119909
(unfortunately distinguishesdirection)
1
2119898minusℏ2
1205972
1205971199092+ minus119894ℏ
120597
120597119910+ 119890119861119909
2
minus ℏ21205972
1205971199112+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903
minusℏ2
21198981205712 minus
119894119890ℏ
119898119861119909
120597
120597119910+
119890119861119909 2
2119898+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903Which gives
The evidence of the Lorentz force Parabolic potential
We assume that in a plane 119909119910there is no other potential
119902 = minus119890
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Hamiltonian
2016-04-28 15
1
2119898Ƹ1199012 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
119880 119903 = minus1198902
41205871205761199031205760
1
119903
Coulomb potential
Coulomb potential
2016-04-28 16
FIRST Coulomb potential in 3D in the semiconductor of dielectric constant 120576119903 effective mass 119898lowast
119877119910 =1198902
41205871205760
2119898
2ℏ2=
ℏ2
21198981198861198612 =
1
2
1198902
41205871205760119886119861= 136 eV
119886119861 =41205871205760ℏ
2
11989801198902 = 05 Å
119880 119903 = minus1198902
41205871205761199031205760
1
119903
119864119899 = minus119898lowast
1198980
1
1205761199032 119877119910
1
1198992
119886119861lowast =
41205871205761199031205760ℏ2
11989801198902
1198980
119898lowast= 119886119861120576119903
1198980
119898lowast
119864119899 = minus1198771199101
1198992rArr | 119899 119897 119898119897
119897 = 012hellip
principal angular magnetic
clasically
thus
[Am2]
m
r
vBohr magneton 120583119861 =
ℏ119890
21198980
120583119861 = 9274009994(57)times10minus24 JT
2016-04-28 17
Magnetic field and spinMagnetic field
119867prime = minus119898119861
Here 119898 is magnetic moment
119898 = 119868 Ԧ119878 =119890
1198791205871199032 =
119890
21205871199031199071205871199032 =
119890
2119903119907
119898 = minus119890
21198980119871 = minus
120583119861ℏ119871
119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911119867prime = minus119898119861 =
120583119861ℏ119871119861
120583119861 =ℏ119890
21198980
circumference of a circle
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 18
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 19
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
2016-04-28 20
Magnetic field and spin
What is the bdquospinrdquo
bull What is bdquomassrdquo
Mariusz Pudzianowski httpwwwpudzianpl
2016-04-28 21
bull What is the bdquomomentumrdquo
What is the bdquospinrdquo
2016-04-28 22
bull What is the bdquoangular momentumrdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 23
bull What is the bdquochargerdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 24
bull Spin
DisneySebastian Muumlnster Cosmographia in 1544
htt
p
ww
wf
lori
dah
isto
ryc
om
us
15
70
htm
l
What is the bdquospinrdquo
2016-04-28 25
Pauli matrices 120590119909 120590119910 120590119911
Spinor
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
2016-04-28 26
Magnetic field and spinSpin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
2016-04-28 27
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc119892-factor for the agreement with experiments
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 28
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
119892 = minus200231930436182 plusmn 000000000000052
2016-04-28 29
QED ndash Quantum ElectroDynamics
119892 = minus200231930436182 plusmn 000000000000052
The consequences
2016-04-28 30
There is the bdquospinrdquo
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
Total magnetic moment 119872 = 119872119871 + 119872119878 = minus119892119871120583119861
ℏ119871 minus119892119878
120583119861
ℏመ119878
=1 =2
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 31
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
119872 ne መ119869 - magnetic anomaly of spin
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 32
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
119867119878119874 = 120582119871 መ119878 = 1205821
21198692 minus 1198712 minus 1198782 = 120582 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
120582 = ℎ119888 119860 =1198851205722
2
1
1199033
120572 =1198902
41205871205760ℏ119888asymp
1
137037
119864119878119874 = න120595lowast119867119878119874120595 119889119881 =119885
2 137 2න120595lowast119871 መ119878
1199033120595 119889119881
fine-structure constant119877119910 = ℎ119888119877infin
119877infin =119898119890119890
4
812057602ℎ3119888
119877infin = 1097 times 107m-1
eg for 120595210 we get1
1199033=
1
24
119885
1198860
3and for general 119899 (principal quantum number)
119864119878119874 =1198854
2 137 2119886031198993
119895 119895 + 1 minus 119897 119897 + 1 minus 119904(119904 + 1)
2119897(119897 + 12)(119897 + 1)
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 33
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
3
3
2
119871 = 1 መ119878 =1
2
211987532
211987512
shortly | ൿ119895 119898119895
the base | ൿ119899 119897 119904 119895 119898119895
ത119871 ҧ119878 =1
2ҧ1198692 minus ത1198712 minus ҧ1198782 = 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
Term symbol
an abbreviated description of the angular momentum quantum numbers in a multi-electron atom
Total wavefunction must be antisymmetric (under interchange of any pair of particle)
Orbital part Spin part
2016-04-28 34
Multi-electron atom2S+1 119871119869
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
120595 Ԧ1199031 hellip Ԧ119903119873 Ԧ1198781 hellip Ԧ119878119873 = 120595 Ԧ1199031 hellip Ԧ119903119873 120594 Ԧ1198781 hellip Ԧ119878119873
Multi-electron wavefunction
Antisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =Exchange interaction
Antisymmetric
Example
A
B
Two electrons localized on one centrum
2016-04-28 35
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Hundrsquos rules ET lt ES
Antisymmetric
2016-04-28 36
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Magnetic Organic LCPiotr Kaszyński (Univ Vanderbilt USA The Centre of Molecular and Macromolecular Studies Lodz Poland)Ewa Goacuterecka (Faculty of Chemistry University of Warsaw)Damian Pociecha (Faculty of Chemistry University of Warsaw)
2016-04-28 8
Piotr Ewa
2016-04-28
Magnetic Organic LC
2016-04-28
SPINTRONICS1 Magnetic field and spin2 Exchange interactions3 Magnetism of matter4 Spintronics5 Organics spintronics
a Magnetismb Transportc Lightd Liquid crystals
S H
arri
s
Hamiltonian
2016-04-28 11
1
2119898Ƹ1199012 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
kinetic energy
119864119896 =1198981199072
119904=
1199012
2119898
potential energy time evolution
Homogenous magnetic field
2016-04-28 12
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Homogenous magnetic field
2016-04-28 13
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
Landau gauge magnetic field 119861 = 00 119861119911 rArr 119861119911 =120597119860119910
120597119909minus
120597119860119909
120597119910
Ԧ119860 = 0 119861119911119909 0 czyli 119860119910 = 119861119911119909 ≝ 119861119909
(unfortunately distinguishesdirection)
1
2119898minusℏ2
1205972
1205971199092+ minus119894ℏ
120597
120597119910+ 119890119861119909
2
minus ℏ21205972
1205971199112+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903
minusℏ2
21198981205712 minus
119894119890ℏ
119898119861119909
120597
120597119910+
119890119861119909 2
2119898+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903Which gives
The evidence of the Lorentz force Parabolic potential
We assume that in a plane 119909119910there is no other potential
119902 = minus119890
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Homogenous magnetic field
2016-04-28 14
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
Landau gauge magnetic field 119861 = 00 119861119911 rArr 119861119911 =120597119860119910
120597119909minus
120597119860119909
120597119910
Ԧ119860 = 0 119861119911119909 0 czyli 119860119910 = 119861119911119909 ≝ 119861119909
(unfortunately distinguishesdirection)
1
2119898minusℏ2
1205972
1205971199092+ minus119894ℏ
120597
120597119910+ 119890119861119909
2
minus ℏ21205972
1205971199112+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903
minusℏ2
21198981205712 minus
119894119890ℏ
119898119861119909
120597
120597119910+
119890119861119909 2
2119898+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903Which gives
The evidence of the Lorentz force Parabolic potential
We assume that in a plane 119909119910there is no other potential
119902 = minus119890
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Hamiltonian
2016-04-28 15
1
2119898Ƹ1199012 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
119880 119903 = minus1198902
41205871205761199031205760
1
119903
Coulomb potential
Coulomb potential
2016-04-28 16
FIRST Coulomb potential in 3D in the semiconductor of dielectric constant 120576119903 effective mass 119898lowast
119877119910 =1198902
41205871205760
2119898
2ℏ2=
ℏ2
21198981198861198612 =
1
2
1198902
41205871205760119886119861= 136 eV
119886119861 =41205871205760ℏ
2
11989801198902 = 05 Å
119880 119903 = minus1198902
41205871205761199031205760
1
119903
119864119899 = minus119898lowast
1198980
1
1205761199032 119877119910
1
1198992
119886119861lowast =
41205871205761199031205760ℏ2
11989801198902
1198980
119898lowast= 119886119861120576119903
1198980
119898lowast
119864119899 = minus1198771199101
1198992rArr | 119899 119897 119898119897
119897 = 012hellip
principal angular magnetic
clasically
thus
[Am2]
m
r
vBohr magneton 120583119861 =
ℏ119890
21198980
120583119861 = 9274009994(57)times10minus24 JT
2016-04-28 17
Magnetic field and spinMagnetic field
119867prime = minus119898119861
Here 119898 is magnetic moment
119898 = 119868 Ԧ119878 =119890
1198791205871199032 =
119890
21205871199031199071205871199032 =
119890
2119903119907
119898 = minus119890
21198980119871 = minus
120583119861ℏ119871
119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911119867prime = minus119898119861 =
120583119861ℏ119871119861
120583119861 =ℏ119890
21198980
circumference of a circle
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 18
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 19
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
2016-04-28 20
Magnetic field and spin
What is the bdquospinrdquo
bull What is bdquomassrdquo
Mariusz Pudzianowski httpwwwpudzianpl
2016-04-28 21
bull What is the bdquomomentumrdquo
What is the bdquospinrdquo
2016-04-28 22
bull What is the bdquoangular momentumrdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 23
bull What is the bdquochargerdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 24
bull Spin
DisneySebastian Muumlnster Cosmographia in 1544
htt
p
ww
wf
lori
dah
isto
ryc
om
us
15
70
htm
l
What is the bdquospinrdquo
2016-04-28 25
Pauli matrices 120590119909 120590119910 120590119911
Spinor
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
2016-04-28 26
Magnetic field and spinSpin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
2016-04-28 27
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc119892-factor for the agreement with experiments
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 28
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
119892 = minus200231930436182 plusmn 000000000000052
2016-04-28 29
QED ndash Quantum ElectroDynamics
119892 = minus200231930436182 plusmn 000000000000052
The consequences
2016-04-28 30
There is the bdquospinrdquo
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
Total magnetic moment 119872 = 119872119871 + 119872119878 = minus119892119871120583119861
ℏ119871 minus119892119878
120583119861
ℏመ119878
=1 =2
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 31
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
119872 ne መ119869 - magnetic anomaly of spin
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 32
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
119867119878119874 = 120582119871 መ119878 = 1205821
21198692 minus 1198712 minus 1198782 = 120582 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
120582 = ℎ119888 119860 =1198851205722
2
1
1199033
120572 =1198902
41205871205760ℏ119888asymp
1
137037
119864119878119874 = න120595lowast119867119878119874120595 119889119881 =119885
2 137 2න120595lowast119871 መ119878
1199033120595 119889119881
fine-structure constant119877119910 = ℎ119888119877infin
119877infin =119898119890119890
4
812057602ℎ3119888
119877infin = 1097 times 107m-1
eg for 120595210 we get1
1199033=
1
24
119885
1198860
3and for general 119899 (principal quantum number)
119864119878119874 =1198854
2 137 2119886031198993
119895 119895 + 1 minus 119897 119897 + 1 minus 119904(119904 + 1)
2119897(119897 + 12)(119897 + 1)
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 33
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
3
3
2
119871 = 1 መ119878 =1
2
211987532
211987512
shortly | ൿ119895 119898119895
the base | ൿ119899 119897 119904 119895 119898119895
ത119871 ҧ119878 =1
2ҧ1198692 minus ത1198712 minus ҧ1198782 = 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
Term symbol
an abbreviated description of the angular momentum quantum numbers in a multi-electron atom
Total wavefunction must be antisymmetric (under interchange of any pair of particle)
Orbital part Spin part
2016-04-28 34
Multi-electron atom2S+1 119871119869
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
120595 Ԧ1199031 hellip Ԧ119903119873 Ԧ1198781 hellip Ԧ119878119873 = 120595 Ԧ1199031 hellip Ԧ119903119873 120594 Ԧ1198781 hellip Ԧ119878119873
Multi-electron wavefunction
Antisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =Exchange interaction
Antisymmetric
Example
A
B
Two electrons localized on one centrum
2016-04-28 35
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Hundrsquos rules ET lt ES
Antisymmetric
2016-04-28 36
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28
Magnetic Organic LC
2016-04-28
SPINTRONICS1 Magnetic field and spin2 Exchange interactions3 Magnetism of matter4 Spintronics5 Organics spintronics
a Magnetismb Transportc Lightd Liquid crystals
S H
arri
s
Hamiltonian
2016-04-28 11
1
2119898Ƹ1199012 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
kinetic energy
119864119896 =1198981199072
119904=
1199012
2119898
potential energy time evolution
Homogenous magnetic field
2016-04-28 12
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Homogenous magnetic field
2016-04-28 13
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
Landau gauge magnetic field 119861 = 00 119861119911 rArr 119861119911 =120597119860119910
120597119909minus
120597119860119909
120597119910
Ԧ119860 = 0 119861119911119909 0 czyli 119860119910 = 119861119911119909 ≝ 119861119909
(unfortunately distinguishesdirection)
1
2119898minusℏ2
1205972
1205971199092+ minus119894ℏ
120597
120597119910+ 119890119861119909
2
minus ℏ21205972
1205971199112+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903
minusℏ2
21198981205712 minus
119894119890ℏ
119898119861119909
120597
120597119910+
119890119861119909 2
2119898+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903Which gives
The evidence of the Lorentz force Parabolic potential
We assume that in a plane 119909119910there is no other potential
119902 = minus119890
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Homogenous magnetic field
2016-04-28 14
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
Landau gauge magnetic field 119861 = 00 119861119911 rArr 119861119911 =120597119860119910
120597119909minus
120597119860119909
120597119910
Ԧ119860 = 0 119861119911119909 0 czyli 119860119910 = 119861119911119909 ≝ 119861119909
(unfortunately distinguishesdirection)
1
2119898minusℏ2
1205972
1205971199092+ minus119894ℏ
120597
120597119910+ 119890119861119909
2
minus ℏ21205972
1205971199112+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903
minusℏ2
21198981205712 minus
119894119890ℏ
119898119861119909
120597
120597119910+
119890119861119909 2
2119898+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903Which gives
The evidence of the Lorentz force Parabolic potential
We assume that in a plane 119909119910there is no other potential
119902 = minus119890
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Hamiltonian
2016-04-28 15
1
2119898Ƹ1199012 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
119880 119903 = minus1198902
41205871205761199031205760
1
119903
Coulomb potential
Coulomb potential
2016-04-28 16
FIRST Coulomb potential in 3D in the semiconductor of dielectric constant 120576119903 effective mass 119898lowast
119877119910 =1198902
41205871205760
2119898
2ℏ2=
ℏ2
21198981198861198612 =
1
2
1198902
41205871205760119886119861= 136 eV
119886119861 =41205871205760ℏ
2
11989801198902 = 05 Å
119880 119903 = minus1198902
41205871205761199031205760
1
119903
119864119899 = minus119898lowast
1198980
1
1205761199032 119877119910
1
1198992
119886119861lowast =
41205871205761199031205760ℏ2
11989801198902
1198980
119898lowast= 119886119861120576119903
1198980
119898lowast
119864119899 = minus1198771199101
1198992rArr | 119899 119897 119898119897
119897 = 012hellip
principal angular magnetic
clasically
thus
[Am2]
m
r
vBohr magneton 120583119861 =
ℏ119890
21198980
120583119861 = 9274009994(57)times10minus24 JT
2016-04-28 17
Magnetic field and spinMagnetic field
119867prime = minus119898119861
Here 119898 is magnetic moment
119898 = 119868 Ԧ119878 =119890
1198791205871199032 =
119890
21205871199031199071205871199032 =
119890
2119903119907
119898 = minus119890
21198980119871 = minus
120583119861ℏ119871
119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911119867prime = minus119898119861 =
120583119861ℏ119871119861
120583119861 =ℏ119890
21198980
circumference of a circle
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 18
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 19
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
2016-04-28 20
Magnetic field and spin
What is the bdquospinrdquo
bull What is bdquomassrdquo
Mariusz Pudzianowski httpwwwpudzianpl
2016-04-28 21
bull What is the bdquomomentumrdquo
What is the bdquospinrdquo
2016-04-28 22
bull What is the bdquoangular momentumrdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 23
bull What is the bdquochargerdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 24
bull Spin
DisneySebastian Muumlnster Cosmographia in 1544
htt
p
ww
wf
lori
dah
isto
ryc
om
us
15
70
htm
l
What is the bdquospinrdquo
2016-04-28 25
Pauli matrices 120590119909 120590119910 120590119911
Spinor
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
2016-04-28 26
Magnetic field and spinSpin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
2016-04-28 27
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc119892-factor for the agreement with experiments
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 28
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
119892 = minus200231930436182 plusmn 000000000000052
2016-04-28 29
QED ndash Quantum ElectroDynamics
119892 = minus200231930436182 plusmn 000000000000052
The consequences
2016-04-28 30
There is the bdquospinrdquo
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
Total magnetic moment 119872 = 119872119871 + 119872119878 = minus119892119871120583119861
ℏ119871 minus119892119878
120583119861
ℏመ119878
=1 =2
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 31
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
119872 ne መ119869 - magnetic anomaly of spin
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 32
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
119867119878119874 = 120582119871 መ119878 = 1205821
21198692 minus 1198712 minus 1198782 = 120582 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
120582 = ℎ119888 119860 =1198851205722
2
1
1199033
120572 =1198902
41205871205760ℏ119888asymp
1
137037
119864119878119874 = න120595lowast119867119878119874120595 119889119881 =119885
2 137 2න120595lowast119871 መ119878
1199033120595 119889119881
fine-structure constant119877119910 = ℎ119888119877infin
119877infin =119898119890119890
4
812057602ℎ3119888
119877infin = 1097 times 107m-1
eg for 120595210 we get1
1199033=
1
24
119885
1198860
3and for general 119899 (principal quantum number)
119864119878119874 =1198854
2 137 2119886031198993
119895 119895 + 1 minus 119897 119897 + 1 minus 119904(119904 + 1)
2119897(119897 + 12)(119897 + 1)
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 33
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
3
3
2
119871 = 1 መ119878 =1
2
211987532
211987512
shortly | ൿ119895 119898119895
the base | ൿ119899 119897 119904 119895 119898119895
ത119871 ҧ119878 =1
2ҧ1198692 minus ത1198712 minus ҧ1198782 = 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
Term symbol
an abbreviated description of the angular momentum quantum numbers in a multi-electron atom
Total wavefunction must be antisymmetric (under interchange of any pair of particle)
Orbital part Spin part
2016-04-28 34
Multi-electron atom2S+1 119871119869
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
120595 Ԧ1199031 hellip Ԧ119903119873 Ԧ1198781 hellip Ԧ119878119873 = 120595 Ԧ1199031 hellip Ԧ119903119873 120594 Ԧ1198781 hellip Ԧ119878119873
Multi-electron wavefunction
Antisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =Exchange interaction
Antisymmetric
Example
A
B
Two electrons localized on one centrum
2016-04-28 35
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Hundrsquos rules ET lt ES
Antisymmetric
2016-04-28 36
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28
SPINTRONICS1 Magnetic field and spin2 Exchange interactions3 Magnetism of matter4 Spintronics5 Organics spintronics
a Magnetismb Transportc Lightd Liquid crystals
S H
arri
s
Hamiltonian
2016-04-28 11
1
2119898Ƹ1199012 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
kinetic energy
119864119896 =1198981199072
119904=
1199012
2119898
potential energy time evolution
Homogenous magnetic field
2016-04-28 12
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Homogenous magnetic field
2016-04-28 13
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
Landau gauge magnetic field 119861 = 00 119861119911 rArr 119861119911 =120597119860119910
120597119909minus
120597119860119909
120597119910
Ԧ119860 = 0 119861119911119909 0 czyli 119860119910 = 119861119911119909 ≝ 119861119909
(unfortunately distinguishesdirection)
1
2119898minusℏ2
1205972
1205971199092+ minus119894ℏ
120597
120597119910+ 119890119861119909
2
minus ℏ21205972
1205971199112+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903
minusℏ2
21198981205712 minus
119894119890ℏ
119898119861119909
120597
120597119910+
119890119861119909 2
2119898+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903Which gives
The evidence of the Lorentz force Parabolic potential
We assume that in a plane 119909119910there is no other potential
119902 = minus119890
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Homogenous magnetic field
2016-04-28 14
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
Landau gauge magnetic field 119861 = 00 119861119911 rArr 119861119911 =120597119860119910
120597119909minus
120597119860119909
120597119910
Ԧ119860 = 0 119861119911119909 0 czyli 119860119910 = 119861119911119909 ≝ 119861119909
(unfortunately distinguishesdirection)
1
2119898minusℏ2
1205972
1205971199092+ minus119894ℏ
120597
120597119910+ 119890119861119909
2
minus ℏ21205972
1205971199112+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903
minusℏ2
21198981205712 minus
119894119890ℏ
119898119861119909
120597
120597119910+
119890119861119909 2
2119898+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903Which gives
The evidence of the Lorentz force Parabolic potential
We assume that in a plane 119909119910there is no other potential
119902 = minus119890
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Hamiltonian
2016-04-28 15
1
2119898Ƹ1199012 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
119880 119903 = minus1198902
41205871205761199031205760
1
119903
Coulomb potential
Coulomb potential
2016-04-28 16
FIRST Coulomb potential in 3D in the semiconductor of dielectric constant 120576119903 effective mass 119898lowast
119877119910 =1198902
41205871205760
2119898
2ℏ2=
ℏ2
21198981198861198612 =
1
2
1198902
41205871205760119886119861= 136 eV
119886119861 =41205871205760ℏ
2
11989801198902 = 05 Å
119880 119903 = minus1198902
41205871205761199031205760
1
119903
119864119899 = minus119898lowast
1198980
1
1205761199032 119877119910
1
1198992
119886119861lowast =
41205871205761199031205760ℏ2
11989801198902
1198980
119898lowast= 119886119861120576119903
1198980
119898lowast
119864119899 = minus1198771199101
1198992rArr | 119899 119897 119898119897
119897 = 012hellip
principal angular magnetic
clasically
thus
[Am2]
m
r
vBohr magneton 120583119861 =
ℏ119890
21198980
120583119861 = 9274009994(57)times10minus24 JT
2016-04-28 17
Magnetic field and spinMagnetic field
119867prime = minus119898119861
Here 119898 is magnetic moment
119898 = 119868 Ԧ119878 =119890
1198791205871199032 =
119890
21205871199031199071205871199032 =
119890
2119903119907
119898 = minus119890
21198980119871 = minus
120583119861ℏ119871
119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911119867prime = minus119898119861 =
120583119861ℏ119871119861
120583119861 =ℏ119890
21198980
circumference of a circle
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 18
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 19
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
2016-04-28 20
Magnetic field and spin
What is the bdquospinrdquo
bull What is bdquomassrdquo
Mariusz Pudzianowski httpwwwpudzianpl
2016-04-28 21
bull What is the bdquomomentumrdquo
What is the bdquospinrdquo
2016-04-28 22
bull What is the bdquoangular momentumrdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 23
bull What is the bdquochargerdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 24
bull Spin
DisneySebastian Muumlnster Cosmographia in 1544
htt
p
ww
wf
lori
dah
isto
ryc
om
us
15
70
htm
l
What is the bdquospinrdquo
2016-04-28 25
Pauli matrices 120590119909 120590119910 120590119911
Spinor
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
2016-04-28 26
Magnetic field and spinSpin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
2016-04-28 27
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc119892-factor for the agreement with experiments
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 28
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
119892 = minus200231930436182 plusmn 000000000000052
2016-04-28 29
QED ndash Quantum ElectroDynamics
119892 = minus200231930436182 plusmn 000000000000052
The consequences
2016-04-28 30
There is the bdquospinrdquo
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
Total magnetic moment 119872 = 119872119871 + 119872119878 = minus119892119871120583119861
ℏ119871 minus119892119878
120583119861
ℏመ119878
=1 =2
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 31
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
119872 ne መ119869 - magnetic anomaly of spin
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 32
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
119867119878119874 = 120582119871 መ119878 = 1205821
21198692 minus 1198712 minus 1198782 = 120582 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
120582 = ℎ119888 119860 =1198851205722
2
1
1199033
120572 =1198902
41205871205760ℏ119888asymp
1
137037
119864119878119874 = න120595lowast119867119878119874120595 119889119881 =119885
2 137 2න120595lowast119871 መ119878
1199033120595 119889119881
fine-structure constant119877119910 = ℎ119888119877infin
119877infin =119898119890119890
4
812057602ℎ3119888
119877infin = 1097 times 107m-1
eg for 120595210 we get1
1199033=
1
24
119885
1198860
3and for general 119899 (principal quantum number)
119864119878119874 =1198854
2 137 2119886031198993
119895 119895 + 1 minus 119897 119897 + 1 minus 119904(119904 + 1)
2119897(119897 + 12)(119897 + 1)
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 33
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
3
3
2
119871 = 1 መ119878 =1
2
211987532
211987512
shortly | ൿ119895 119898119895
the base | ൿ119899 119897 119904 119895 119898119895
ത119871 ҧ119878 =1
2ҧ1198692 minus ത1198712 minus ҧ1198782 = 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
Term symbol
an abbreviated description of the angular momentum quantum numbers in a multi-electron atom
Total wavefunction must be antisymmetric (under interchange of any pair of particle)
Orbital part Spin part
2016-04-28 34
Multi-electron atom2S+1 119871119869
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
120595 Ԧ1199031 hellip Ԧ119903119873 Ԧ1198781 hellip Ԧ119878119873 = 120595 Ԧ1199031 hellip Ԧ119903119873 120594 Ԧ1198781 hellip Ԧ119878119873
Multi-electron wavefunction
Antisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =Exchange interaction
Antisymmetric
Example
A
B
Two electrons localized on one centrum
2016-04-28 35
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Hundrsquos rules ET lt ES
Antisymmetric
2016-04-28 36
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Hamiltonian
2016-04-28 11
1
2119898Ƹ1199012 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
kinetic energy
119864119896 =1198981199072
119904=
1199012
2119898
potential energy time evolution
Homogenous magnetic field
2016-04-28 12
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Homogenous magnetic field
2016-04-28 13
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
Landau gauge magnetic field 119861 = 00 119861119911 rArr 119861119911 =120597119860119910
120597119909minus
120597119860119909
120597119910
Ԧ119860 = 0 119861119911119909 0 czyli 119860119910 = 119861119911119909 ≝ 119861119909
(unfortunately distinguishesdirection)
1
2119898minusℏ2
1205972
1205971199092+ minus119894ℏ
120597
120597119910+ 119890119861119909
2
minus ℏ21205972
1205971199112+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903
minusℏ2
21198981205712 minus
119894119890ℏ
119898119861119909
120597
120597119910+
119890119861119909 2
2119898+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903Which gives
The evidence of the Lorentz force Parabolic potential
We assume that in a plane 119909119910there is no other potential
119902 = minus119890
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Homogenous magnetic field
2016-04-28 14
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
Landau gauge magnetic field 119861 = 00 119861119911 rArr 119861119911 =120597119860119910
120597119909minus
120597119860119909
120597119910
Ԧ119860 = 0 119861119911119909 0 czyli 119860119910 = 119861119911119909 ≝ 119861119909
(unfortunately distinguishesdirection)
1
2119898minusℏ2
1205972
1205971199092+ minus119894ℏ
120597
120597119910+ 119890119861119909
2
minus ℏ21205972
1205971199112+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903
minusℏ2
21198981205712 minus
119894119890ℏ
119898119861119909
120597
120597119910+
119890119861119909 2
2119898+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903Which gives
The evidence of the Lorentz force Parabolic potential
We assume that in a plane 119909119910there is no other potential
119902 = minus119890
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Hamiltonian
2016-04-28 15
1
2119898Ƹ1199012 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
119880 119903 = minus1198902
41205871205761199031205760
1
119903
Coulomb potential
Coulomb potential
2016-04-28 16
FIRST Coulomb potential in 3D in the semiconductor of dielectric constant 120576119903 effective mass 119898lowast
119877119910 =1198902
41205871205760
2119898
2ℏ2=
ℏ2
21198981198861198612 =
1
2
1198902
41205871205760119886119861= 136 eV
119886119861 =41205871205760ℏ
2
11989801198902 = 05 Å
119880 119903 = minus1198902
41205871205761199031205760
1
119903
119864119899 = minus119898lowast
1198980
1
1205761199032 119877119910
1
1198992
119886119861lowast =
41205871205761199031205760ℏ2
11989801198902
1198980
119898lowast= 119886119861120576119903
1198980
119898lowast
119864119899 = minus1198771199101
1198992rArr | 119899 119897 119898119897
119897 = 012hellip
principal angular magnetic
clasically
thus
[Am2]
m
r
vBohr magneton 120583119861 =
ℏ119890
21198980
120583119861 = 9274009994(57)times10minus24 JT
2016-04-28 17
Magnetic field and spinMagnetic field
119867prime = minus119898119861
Here 119898 is magnetic moment
119898 = 119868 Ԧ119878 =119890
1198791205871199032 =
119890
21205871199031199071205871199032 =
119890
2119903119907
119898 = minus119890
21198980119871 = minus
120583119861ℏ119871
119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911119867prime = minus119898119861 =
120583119861ℏ119871119861
120583119861 =ℏ119890
21198980
circumference of a circle
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 18
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 19
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
2016-04-28 20
Magnetic field and spin
What is the bdquospinrdquo
bull What is bdquomassrdquo
Mariusz Pudzianowski httpwwwpudzianpl
2016-04-28 21
bull What is the bdquomomentumrdquo
What is the bdquospinrdquo
2016-04-28 22
bull What is the bdquoangular momentumrdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 23
bull What is the bdquochargerdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 24
bull Spin
DisneySebastian Muumlnster Cosmographia in 1544
htt
p
ww
wf
lori
dah
isto
ryc
om
us
15
70
htm
l
What is the bdquospinrdquo
2016-04-28 25
Pauli matrices 120590119909 120590119910 120590119911
Spinor
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
2016-04-28 26
Magnetic field and spinSpin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
2016-04-28 27
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc119892-factor for the agreement with experiments
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 28
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
119892 = minus200231930436182 plusmn 000000000000052
2016-04-28 29
QED ndash Quantum ElectroDynamics
119892 = minus200231930436182 plusmn 000000000000052
The consequences
2016-04-28 30
There is the bdquospinrdquo
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
Total magnetic moment 119872 = 119872119871 + 119872119878 = minus119892119871120583119861
ℏ119871 minus119892119878
120583119861
ℏመ119878
=1 =2
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 31
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
119872 ne መ119869 - magnetic anomaly of spin
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 32
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
119867119878119874 = 120582119871 መ119878 = 1205821
21198692 minus 1198712 minus 1198782 = 120582 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
120582 = ℎ119888 119860 =1198851205722
2
1
1199033
120572 =1198902
41205871205760ℏ119888asymp
1
137037
119864119878119874 = න120595lowast119867119878119874120595 119889119881 =119885
2 137 2න120595lowast119871 መ119878
1199033120595 119889119881
fine-structure constant119877119910 = ℎ119888119877infin
119877infin =119898119890119890
4
812057602ℎ3119888
119877infin = 1097 times 107m-1
eg for 120595210 we get1
1199033=
1
24
119885
1198860
3and for general 119899 (principal quantum number)
119864119878119874 =1198854
2 137 2119886031198993
119895 119895 + 1 minus 119897 119897 + 1 minus 119904(119904 + 1)
2119897(119897 + 12)(119897 + 1)
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 33
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
3
3
2
119871 = 1 መ119878 =1
2
211987532
211987512
shortly | ൿ119895 119898119895
the base | ൿ119899 119897 119904 119895 119898119895
ത119871 ҧ119878 =1
2ҧ1198692 minus ത1198712 minus ҧ1198782 = 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
Term symbol
an abbreviated description of the angular momentum quantum numbers in a multi-electron atom
Total wavefunction must be antisymmetric (under interchange of any pair of particle)
Orbital part Spin part
2016-04-28 34
Multi-electron atom2S+1 119871119869
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
120595 Ԧ1199031 hellip Ԧ119903119873 Ԧ1198781 hellip Ԧ119878119873 = 120595 Ԧ1199031 hellip Ԧ119903119873 120594 Ԧ1198781 hellip Ԧ119878119873
Multi-electron wavefunction
Antisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =Exchange interaction
Antisymmetric
Example
A
B
Two electrons localized on one centrum
2016-04-28 35
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Hundrsquos rules ET lt ES
Antisymmetric
2016-04-28 36
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Homogenous magnetic field
2016-04-28 12
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Homogenous magnetic field
2016-04-28 13
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
Landau gauge magnetic field 119861 = 00 119861119911 rArr 119861119911 =120597119860119910
120597119909minus
120597119860119909
120597119910
Ԧ119860 = 0 119861119911119909 0 czyli 119860119910 = 119861119911119909 ≝ 119861119909
(unfortunately distinguishesdirection)
1
2119898minusℏ2
1205972
1205971199092+ minus119894ℏ
120597
120597119910+ 119890119861119909
2
minus ℏ21205972
1205971199112+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903
minusℏ2
21198981205712 minus
119894119890ℏ
119898119861119909
120597
120597119910+
119890119861119909 2
2119898+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903Which gives
The evidence of the Lorentz force Parabolic potential
We assume that in a plane 119909119910there is no other potential
119902 = minus119890
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Homogenous magnetic field
2016-04-28 14
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
Landau gauge magnetic field 119861 = 00 119861119911 rArr 119861119911 =120597119860119910
120597119909minus
120597119860119909
120597119910
Ԧ119860 = 0 119861119911119909 0 czyli 119860119910 = 119861119911119909 ≝ 119861119909
(unfortunately distinguishesdirection)
1
2119898minusℏ2
1205972
1205971199092+ minus119894ℏ
120597
120597119910+ 119890119861119909
2
minus ℏ21205972
1205971199112+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903
minusℏ2
21198981205712 minus
119894119890ℏ
119898119861119909
120597
120597119910+
119890119861119909 2
2119898+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903Which gives
The evidence of the Lorentz force Parabolic potential
We assume that in a plane 119909119910there is no other potential
119902 = minus119890
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Hamiltonian
2016-04-28 15
1
2119898Ƹ1199012 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
119880 119903 = minus1198902
41205871205761199031205760
1
119903
Coulomb potential
Coulomb potential
2016-04-28 16
FIRST Coulomb potential in 3D in the semiconductor of dielectric constant 120576119903 effective mass 119898lowast
119877119910 =1198902
41205871205760
2119898
2ℏ2=
ℏ2
21198981198861198612 =
1
2
1198902
41205871205760119886119861= 136 eV
119886119861 =41205871205760ℏ
2
11989801198902 = 05 Å
119880 119903 = minus1198902
41205871205761199031205760
1
119903
119864119899 = minus119898lowast
1198980
1
1205761199032 119877119910
1
1198992
119886119861lowast =
41205871205761199031205760ℏ2
11989801198902
1198980
119898lowast= 119886119861120576119903
1198980
119898lowast
119864119899 = minus1198771199101
1198992rArr | 119899 119897 119898119897
119897 = 012hellip
principal angular magnetic
clasically
thus
[Am2]
m
r
vBohr magneton 120583119861 =
ℏ119890
21198980
120583119861 = 9274009994(57)times10minus24 JT
2016-04-28 17
Magnetic field and spinMagnetic field
119867prime = minus119898119861
Here 119898 is magnetic moment
119898 = 119868 Ԧ119878 =119890
1198791205871199032 =
119890
21205871199031199071205871199032 =
119890
2119903119907
119898 = minus119890
21198980119871 = minus
120583119861ℏ119871
119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911119867prime = minus119898119861 =
120583119861ℏ119871119861
120583119861 =ℏ119890
21198980
circumference of a circle
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 18
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 19
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
2016-04-28 20
Magnetic field and spin
What is the bdquospinrdquo
bull What is bdquomassrdquo
Mariusz Pudzianowski httpwwwpudzianpl
2016-04-28 21
bull What is the bdquomomentumrdquo
What is the bdquospinrdquo
2016-04-28 22
bull What is the bdquoangular momentumrdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 23
bull What is the bdquochargerdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 24
bull Spin
DisneySebastian Muumlnster Cosmographia in 1544
htt
p
ww
wf
lori
dah
isto
ryc
om
us
15
70
htm
l
What is the bdquospinrdquo
2016-04-28 25
Pauli matrices 120590119909 120590119910 120590119911
Spinor
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
2016-04-28 26
Magnetic field and spinSpin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
2016-04-28 27
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc119892-factor for the agreement with experiments
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 28
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
119892 = minus200231930436182 plusmn 000000000000052
2016-04-28 29
QED ndash Quantum ElectroDynamics
119892 = minus200231930436182 plusmn 000000000000052
The consequences
2016-04-28 30
There is the bdquospinrdquo
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
Total magnetic moment 119872 = 119872119871 + 119872119878 = minus119892119871120583119861
ℏ119871 minus119892119878
120583119861
ℏመ119878
=1 =2
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 31
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
119872 ne መ119869 - magnetic anomaly of spin
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 32
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
119867119878119874 = 120582119871 መ119878 = 1205821
21198692 minus 1198712 minus 1198782 = 120582 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
120582 = ℎ119888 119860 =1198851205722
2
1
1199033
120572 =1198902
41205871205760ℏ119888asymp
1
137037
119864119878119874 = න120595lowast119867119878119874120595 119889119881 =119885
2 137 2න120595lowast119871 መ119878
1199033120595 119889119881
fine-structure constant119877119910 = ℎ119888119877infin
119877infin =119898119890119890
4
812057602ℎ3119888
119877infin = 1097 times 107m-1
eg for 120595210 we get1
1199033=
1
24
119885
1198860
3and for general 119899 (principal quantum number)
119864119878119874 =1198854
2 137 2119886031198993
119895 119895 + 1 minus 119897 119897 + 1 minus 119904(119904 + 1)
2119897(119897 + 12)(119897 + 1)
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 33
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
3
3
2
119871 = 1 መ119878 =1
2
211987532
211987512
shortly | ൿ119895 119898119895
the base | ൿ119899 119897 119904 119895 119898119895
ത119871 ҧ119878 =1
2ҧ1198692 minus ത1198712 minus ҧ1198782 = 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
Term symbol
an abbreviated description of the angular momentum quantum numbers in a multi-electron atom
Total wavefunction must be antisymmetric (under interchange of any pair of particle)
Orbital part Spin part
2016-04-28 34
Multi-electron atom2S+1 119871119869
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
120595 Ԧ1199031 hellip Ԧ119903119873 Ԧ1198781 hellip Ԧ119878119873 = 120595 Ԧ1199031 hellip Ԧ119903119873 120594 Ԧ1198781 hellip Ԧ119878119873
Multi-electron wavefunction
Antisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =Exchange interaction
Antisymmetric
Example
A
B
Two electrons localized on one centrum
2016-04-28 35
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Hundrsquos rules ET lt ES
Antisymmetric
2016-04-28 36
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Homogenous magnetic field
2016-04-28 13
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
Landau gauge magnetic field 119861 = 00 119861119911 rArr 119861119911 =120597119860119910
120597119909minus
120597119860119909
120597119910
Ԧ119860 = 0 119861119911119909 0 czyli 119860119910 = 119861119911119909 ≝ 119861119909
(unfortunately distinguishesdirection)
1
2119898minusℏ2
1205972
1205971199092+ minus119894ℏ
120597
120597119910+ 119890119861119909
2
minus ℏ21205972
1205971199112+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903
minusℏ2
21198981205712 minus
119894119890ℏ
119898119861119909
120597
120597119910+
119890119861119909 2
2119898+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903Which gives
The evidence of the Lorentz force Parabolic potential
We assume that in a plane 119909119910there is no other potential
119902 = minus119890
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Homogenous magnetic field
2016-04-28 14
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
Landau gauge magnetic field 119861 = 00 119861119911 rArr 119861119911 =120597119860119910
120597119909minus
120597119860119909
120597119910
Ԧ119860 = 0 119861119911119909 0 czyli 119860119910 = 119861119911119909 ≝ 119861119909
(unfortunately distinguishesdirection)
1
2119898minusℏ2
1205972
1205971199092+ minus119894ℏ
120597
120597119910+ 119890119861119909
2
minus ℏ21205972
1205971199112+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903
minusℏ2
21198981205712 minus
119894119890ℏ
119898119861119909
120597
120597119910+
119890119861119909 2
2119898+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903Which gives
The evidence of the Lorentz force Parabolic potential
We assume that in a plane 119909119910there is no other potential
119902 = minus119890
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Hamiltonian
2016-04-28 15
1
2119898Ƹ1199012 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
119880 119903 = minus1198902
41205871205761199031205760
1
119903
Coulomb potential
Coulomb potential
2016-04-28 16
FIRST Coulomb potential in 3D in the semiconductor of dielectric constant 120576119903 effective mass 119898lowast
119877119910 =1198902
41205871205760
2119898
2ℏ2=
ℏ2
21198981198861198612 =
1
2
1198902
41205871205760119886119861= 136 eV
119886119861 =41205871205760ℏ
2
11989801198902 = 05 Å
119880 119903 = minus1198902
41205871205761199031205760
1
119903
119864119899 = minus119898lowast
1198980
1
1205761199032 119877119910
1
1198992
119886119861lowast =
41205871205761199031205760ℏ2
11989801198902
1198980
119898lowast= 119886119861120576119903
1198980
119898lowast
119864119899 = minus1198771199101
1198992rArr | 119899 119897 119898119897
119897 = 012hellip
principal angular magnetic
clasically
thus
[Am2]
m
r
vBohr magneton 120583119861 =
ℏ119890
21198980
120583119861 = 9274009994(57)times10minus24 JT
2016-04-28 17
Magnetic field and spinMagnetic field
119867prime = minus119898119861
Here 119898 is magnetic moment
119898 = 119868 Ԧ119878 =119890
1198791205871199032 =
119890
21205871199031199071205871199032 =
119890
2119903119907
119898 = minus119890
21198980119871 = minus
120583119861ℏ119871
119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911119867prime = minus119898119861 =
120583119861ℏ119871119861
120583119861 =ℏ119890
21198980
circumference of a circle
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 18
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 19
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
2016-04-28 20
Magnetic field and spin
What is the bdquospinrdquo
bull What is bdquomassrdquo
Mariusz Pudzianowski httpwwwpudzianpl
2016-04-28 21
bull What is the bdquomomentumrdquo
What is the bdquospinrdquo
2016-04-28 22
bull What is the bdquoangular momentumrdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 23
bull What is the bdquochargerdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 24
bull Spin
DisneySebastian Muumlnster Cosmographia in 1544
htt
p
ww
wf
lori
dah
isto
ryc
om
us
15
70
htm
l
What is the bdquospinrdquo
2016-04-28 25
Pauli matrices 120590119909 120590119910 120590119911
Spinor
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
2016-04-28 26
Magnetic field and spinSpin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
2016-04-28 27
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc119892-factor for the agreement with experiments
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 28
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
119892 = minus200231930436182 plusmn 000000000000052
2016-04-28 29
QED ndash Quantum ElectroDynamics
119892 = minus200231930436182 plusmn 000000000000052
The consequences
2016-04-28 30
There is the bdquospinrdquo
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
Total magnetic moment 119872 = 119872119871 + 119872119878 = minus119892119871120583119861
ℏ119871 minus119892119878
120583119861
ℏመ119878
=1 =2
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 31
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
119872 ne መ119869 - magnetic anomaly of spin
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 32
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
119867119878119874 = 120582119871 መ119878 = 1205821
21198692 minus 1198712 minus 1198782 = 120582 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
120582 = ℎ119888 119860 =1198851205722
2
1
1199033
120572 =1198902
41205871205760ℏ119888asymp
1
137037
119864119878119874 = න120595lowast119867119878119874120595 119889119881 =119885
2 137 2න120595lowast119871 መ119878
1199033120595 119889119881
fine-structure constant119877119910 = ℎ119888119877infin
119877infin =119898119890119890
4
812057602ℎ3119888
119877infin = 1097 times 107m-1
eg for 120595210 we get1
1199033=
1
24
119885
1198860
3and for general 119899 (principal quantum number)
119864119878119874 =1198854
2 137 2119886031198993
119895 119895 + 1 minus 119897 119897 + 1 minus 119904(119904 + 1)
2119897(119897 + 12)(119897 + 1)
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 33
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
3
3
2
119871 = 1 መ119878 =1
2
211987532
211987512
shortly | ൿ119895 119898119895
the base | ൿ119899 119897 119904 119895 119898119895
ത119871 ҧ119878 =1
2ҧ1198692 minus ത1198712 minus ҧ1198782 = 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
Term symbol
an abbreviated description of the angular momentum quantum numbers in a multi-electron atom
Total wavefunction must be antisymmetric (under interchange of any pair of particle)
Orbital part Spin part
2016-04-28 34
Multi-electron atom2S+1 119871119869
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
120595 Ԧ1199031 hellip Ԧ119903119873 Ԧ1198781 hellip Ԧ119878119873 = 120595 Ԧ1199031 hellip Ԧ119903119873 120594 Ԧ1198781 hellip Ԧ119878119873
Multi-electron wavefunction
Antisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =Exchange interaction
Antisymmetric
Example
A
B
Two electrons localized on one centrum
2016-04-28 35
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Hundrsquos rules ET lt ES
Antisymmetric
2016-04-28 36
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Homogenous magnetic field
2016-04-28 14
The Landau gauge solution
1
2119898Ƹ119901 minus 119902 Ԧ119860 Ԧ119903 119905
2+ 119902120593 Ԧ119903 119905 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
Landau gauge magnetic field 119861 = 00 119861119911 rArr 119861119911 =120597119860119910
120597119909minus
120597119860119909
120597119910
Ԧ119860 = 0 119861119911119909 0 czyli 119860119910 = 119861119911119909 ≝ 119861119909
(unfortunately distinguishesdirection)
1
2119898minusℏ2
1205972
1205971199092+ minus119894ℏ
120597
120597119910+ 119890119861119909
2
minus ℏ21205972
1205971199112+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903
minusℏ2
21198981205712 minus
119894119890ℏ
119898119861119909
120597
120597119910+
119890119861119909 2
2119898+ 119880 119911 120595 Ԧ119903 = 119864120595 Ԧ119903Which gives
The evidence of the Lorentz force Parabolic potential
We assume that in a plane 119909119910there is no other potential
119902 = minus119890
bdquofree electronrdquo (119880 119909 119910 119911 = 119880(119911)) rArr Landau levels
Hamiltonian
2016-04-28 15
1
2119898Ƹ1199012 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
119880 119903 = minus1198902
41205871205761199031205760
1
119903
Coulomb potential
Coulomb potential
2016-04-28 16
FIRST Coulomb potential in 3D in the semiconductor of dielectric constant 120576119903 effective mass 119898lowast
119877119910 =1198902
41205871205760
2119898
2ℏ2=
ℏ2
21198981198861198612 =
1
2
1198902
41205871205760119886119861= 136 eV
119886119861 =41205871205760ℏ
2
11989801198902 = 05 Å
119880 119903 = minus1198902
41205871205761199031205760
1
119903
119864119899 = minus119898lowast
1198980
1
1205761199032 119877119910
1
1198992
119886119861lowast =
41205871205761199031205760ℏ2
11989801198902
1198980
119898lowast= 119886119861120576119903
1198980
119898lowast
119864119899 = minus1198771199101
1198992rArr | 119899 119897 119898119897
119897 = 012hellip
principal angular magnetic
clasically
thus
[Am2]
m
r
vBohr magneton 120583119861 =
ℏ119890
21198980
120583119861 = 9274009994(57)times10minus24 JT
2016-04-28 17
Magnetic field and spinMagnetic field
119867prime = minus119898119861
Here 119898 is magnetic moment
119898 = 119868 Ԧ119878 =119890
1198791205871199032 =
119890
21205871199031199071205871199032 =
119890
2119903119907
119898 = minus119890
21198980119871 = minus
120583119861ℏ119871
119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911119867prime = minus119898119861 =
120583119861ℏ119871119861
120583119861 =ℏ119890
21198980
circumference of a circle
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 18
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 19
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
2016-04-28 20
Magnetic field and spin
What is the bdquospinrdquo
bull What is bdquomassrdquo
Mariusz Pudzianowski httpwwwpudzianpl
2016-04-28 21
bull What is the bdquomomentumrdquo
What is the bdquospinrdquo
2016-04-28 22
bull What is the bdquoangular momentumrdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 23
bull What is the bdquochargerdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 24
bull Spin
DisneySebastian Muumlnster Cosmographia in 1544
htt
p
ww
wf
lori
dah
isto
ryc
om
us
15
70
htm
l
What is the bdquospinrdquo
2016-04-28 25
Pauli matrices 120590119909 120590119910 120590119911
Spinor
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
2016-04-28 26
Magnetic field and spinSpin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
2016-04-28 27
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc119892-factor for the agreement with experiments
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 28
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
119892 = minus200231930436182 plusmn 000000000000052
2016-04-28 29
QED ndash Quantum ElectroDynamics
119892 = minus200231930436182 plusmn 000000000000052
The consequences
2016-04-28 30
There is the bdquospinrdquo
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
Total magnetic moment 119872 = 119872119871 + 119872119878 = minus119892119871120583119861
ℏ119871 minus119892119878
120583119861
ℏመ119878
=1 =2
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 31
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
119872 ne መ119869 - magnetic anomaly of spin
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 32
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
119867119878119874 = 120582119871 መ119878 = 1205821
21198692 minus 1198712 minus 1198782 = 120582 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
120582 = ℎ119888 119860 =1198851205722
2
1
1199033
120572 =1198902
41205871205760ℏ119888asymp
1
137037
119864119878119874 = න120595lowast119867119878119874120595 119889119881 =119885
2 137 2න120595lowast119871 መ119878
1199033120595 119889119881
fine-structure constant119877119910 = ℎ119888119877infin
119877infin =119898119890119890
4
812057602ℎ3119888
119877infin = 1097 times 107m-1
eg for 120595210 we get1
1199033=
1
24
119885
1198860
3and for general 119899 (principal quantum number)
119864119878119874 =1198854
2 137 2119886031198993
119895 119895 + 1 minus 119897 119897 + 1 minus 119904(119904 + 1)
2119897(119897 + 12)(119897 + 1)
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 33
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
3
3
2
119871 = 1 መ119878 =1
2
211987532
211987512
shortly | ൿ119895 119898119895
the base | ൿ119899 119897 119904 119895 119898119895
ത119871 ҧ119878 =1
2ҧ1198692 minus ത1198712 minus ҧ1198782 = 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
Term symbol
an abbreviated description of the angular momentum quantum numbers in a multi-electron atom
Total wavefunction must be antisymmetric (under interchange of any pair of particle)
Orbital part Spin part
2016-04-28 34
Multi-electron atom2S+1 119871119869
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
120595 Ԧ1199031 hellip Ԧ119903119873 Ԧ1198781 hellip Ԧ119878119873 = 120595 Ԧ1199031 hellip Ԧ119903119873 120594 Ԧ1198781 hellip Ԧ119878119873
Multi-electron wavefunction
Antisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =Exchange interaction
Antisymmetric
Example
A
B
Two electrons localized on one centrum
2016-04-28 35
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Hundrsquos rules ET lt ES
Antisymmetric
2016-04-28 36
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Hamiltonian
2016-04-28 15
1
2119898Ƹ1199012 + 119880 Ԧ119903 119905 120595 Ԧ119903 119905 = 119894ℏ
119889
119889119905120595 Ԧ119903 119905
119880 119903 = minus1198902
41205871205761199031205760
1
119903
Coulomb potential
Coulomb potential
2016-04-28 16
FIRST Coulomb potential in 3D in the semiconductor of dielectric constant 120576119903 effective mass 119898lowast
119877119910 =1198902
41205871205760
2119898
2ℏ2=
ℏ2
21198981198861198612 =
1
2
1198902
41205871205760119886119861= 136 eV
119886119861 =41205871205760ℏ
2
11989801198902 = 05 Å
119880 119903 = minus1198902
41205871205761199031205760
1
119903
119864119899 = minus119898lowast
1198980
1
1205761199032 119877119910
1
1198992
119886119861lowast =
41205871205761199031205760ℏ2
11989801198902
1198980
119898lowast= 119886119861120576119903
1198980
119898lowast
119864119899 = minus1198771199101
1198992rArr | 119899 119897 119898119897
119897 = 012hellip
principal angular magnetic
clasically
thus
[Am2]
m
r
vBohr magneton 120583119861 =
ℏ119890
21198980
120583119861 = 9274009994(57)times10minus24 JT
2016-04-28 17
Magnetic field and spinMagnetic field
119867prime = minus119898119861
Here 119898 is magnetic moment
119898 = 119868 Ԧ119878 =119890
1198791205871199032 =
119890
21205871199031199071205871199032 =
119890
2119903119907
119898 = minus119890
21198980119871 = minus
120583119861ℏ119871
119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911119867prime = minus119898119861 =
120583119861ℏ119871119861
120583119861 =ℏ119890
21198980
circumference of a circle
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 18
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 19
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
2016-04-28 20
Magnetic field and spin
What is the bdquospinrdquo
bull What is bdquomassrdquo
Mariusz Pudzianowski httpwwwpudzianpl
2016-04-28 21
bull What is the bdquomomentumrdquo
What is the bdquospinrdquo
2016-04-28 22
bull What is the bdquoangular momentumrdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 23
bull What is the bdquochargerdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 24
bull Spin
DisneySebastian Muumlnster Cosmographia in 1544
htt
p
ww
wf
lori
dah
isto
ryc
om
us
15
70
htm
l
What is the bdquospinrdquo
2016-04-28 25
Pauli matrices 120590119909 120590119910 120590119911
Spinor
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
2016-04-28 26
Magnetic field and spinSpin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
2016-04-28 27
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc119892-factor for the agreement with experiments
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 28
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
119892 = minus200231930436182 plusmn 000000000000052
2016-04-28 29
QED ndash Quantum ElectroDynamics
119892 = minus200231930436182 plusmn 000000000000052
The consequences
2016-04-28 30
There is the bdquospinrdquo
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
Total magnetic moment 119872 = 119872119871 + 119872119878 = minus119892119871120583119861
ℏ119871 minus119892119878
120583119861
ℏመ119878
=1 =2
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 31
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
119872 ne መ119869 - magnetic anomaly of spin
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 32
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
119867119878119874 = 120582119871 መ119878 = 1205821
21198692 minus 1198712 minus 1198782 = 120582 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
120582 = ℎ119888 119860 =1198851205722
2
1
1199033
120572 =1198902
41205871205760ℏ119888asymp
1
137037
119864119878119874 = න120595lowast119867119878119874120595 119889119881 =119885
2 137 2න120595lowast119871 መ119878
1199033120595 119889119881
fine-structure constant119877119910 = ℎ119888119877infin
119877infin =119898119890119890
4
812057602ℎ3119888
119877infin = 1097 times 107m-1
eg for 120595210 we get1
1199033=
1
24
119885
1198860
3and for general 119899 (principal quantum number)
119864119878119874 =1198854
2 137 2119886031198993
119895 119895 + 1 minus 119897 119897 + 1 minus 119904(119904 + 1)
2119897(119897 + 12)(119897 + 1)
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 33
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
3
3
2
119871 = 1 መ119878 =1
2
211987532
211987512
shortly | ൿ119895 119898119895
the base | ൿ119899 119897 119904 119895 119898119895
ത119871 ҧ119878 =1
2ҧ1198692 minus ത1198712 minus ҧ1198782 = 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
Term symbol
an abbreviated description of the angular momentum quantum numbers in a multi-electron atom
Total wavefunction must be antisymmetric (under interchange of any pair of particle)
Orbital part Spin part
2016-04-28 34
Multi-electron atom2S+1 119871119869
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
120595 Ԧ1199031 hellip Ԧ119903119873 Ԧ1198781 hellip Ԧ119878119873 = 120595 Ԧ1199031 hellip Ԧ119903119873 120594 Ԧ1198781 hellip Ԧ119878119873
Multi-electron wavefunction
Antisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =Exchange interaction
Antisymmetric
Example
A
B
Two electrons localized on one centrum
2016-04-28 35
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Hundrsquos rules ET lt ES
Antisymmetric
2016-04-28 36
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Coulomb potential
2016-04-28 16
FIRST Coulomb potential in 3D in the semiconductor of dielectric constant 120576119903 effective mass 119898lowast
119877119910 =1198902
41205871205760
2119898
2ℏ2=
ℏ2
21198981198861198612 =
1
2
1198902
41205871205760119886119861= 136 eV
119886119861 =41205871205760ℏ
2
11989801198902 = 05 Å
119880 119903 = minus1198902
41205871205761199031205760
1
119903
119864119899 = minus119898lowast
1198980
1
1205761199032 119877119910
1
1198992
119886119861lowast =
41205871205761199031205760ℏ2
11989801198902
1198980
119898lowast= 119886119861120576119903
1198980
119898lowast
119864119899 = minus1198771199101
1198992rArr | 119899 119897 119898119897
119897 = 012hellip
principal angular magnetic
clasically
thus
[Am2]
m
r
vBohr magneton 120583119861 =
ℏ119890
21198980
120583119861 = 9274009994(57)times10minus24 JT
2016-04-28 17
Magnetic field and spinMagnetic field
119867prime = minus119898119861
Here 119898 is magnetic moment
119898 = 119868 Ԧ119878 =119890
1198791205871199032 =
119890
21205871199031199071205871199032 =
119890
2119903119907
119898 = minus119890
21198980119871 = minus
120583119861ℏ119871
119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911119867prime = minus119898119861 =
120583119861ℏ119871119861
120583119861 =ℏ119890
21198980
circumference of a circle
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 18
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 19
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
2016-04-28 20
Magnetic field and spin
What is the bdquospinrdquo
bull What is bdquomassrdquo
Mariusz Pudzianowski httpwwwpudzianpl
2016-04-28 21
bull What is the bdquomomentumrdquo
What is the bdquospinrdquo
2016-04-28 22
bull What is the bdquoangular momentumrdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 23
bull What is the bdquochargerdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 24
bull Spin
DisneySebastian Muumlnster Cosmographia in 1544
htt
p
ww
wf
lori
dah
isto
ryc
om
us
15
70
htm
l
What is the bdquospinrdquo
2016-04-28 25
Pauli matrices 120590119909 120590119910 120590119911
Spinor
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
2016-04-28 26
Magnetic field and spinSpin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
2016-04-28 27
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc119892-factor for the agreement with experiments
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 28
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
119892 = minus200231930436182 plusmn 000000000000052
2016-04-28 29
QED ndash Quantum ElectroDynamics
119892 = minus200231930436182 plusmn 000000000000052
The consequences
2016-04-28 30
There is the bdquospinrdquo
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
Total magnetic moment 119872 = 119872119871 + 119872119878 = minus119892119871120583119861
ℏ119871 minus119892119878
120583119861
ℏመ119878
=1 =2
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 31
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
119872 ne መ119869 - magnetic anomaly of spin
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 32
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
119867119878119874 = 120582119871 መ119878 = 1205821
21198692 minus 1198712 minus 1198782 = 120582 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
120582 = ℎ119888 119860 =1198851205722
2
1
1199033
120572 =1198902
41205871205760ℏ119888asymp
1
137037
119864119878119874 = න120595lowast119867119878119874120595 119889119881 =119885
2 137 2න120595lowast119871 መ119878
1199033120595 119889119881
fine-structure constant119877119910 = ℎ119888119877infin
119877infin =119898119890119890
4
812057602ℎ3119888
119877infin = 1097 times 107m-1
eg for 120595210 we get1
1199033=
1
24
119885
1198860
3and for general 119899 (principal quantum number)
119864119878119874 =1198854
2 137 2119886031198993
119895 119895 + 1 minus 119897 119897 + 1 minus 119904(119904 + 1)
2119897(119897 + 12)(119897 + 1)
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 33
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
3
3
2
119871 = 1 መ119878 =1
2
211987532
211987512
shortly | ൿ119895 119898119895
the base | ൿ119899 119897 119904 119895 119898119895
ത119871 ҧ119878 =1
2ҧ1198692 minus ത1198712 minus ҧ1198782 = 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
Term symbol
an abbreviated description of the angular momentum quantum numbers in a multi-electron atom
Total wavefunction must be antisymmetric (under interchange of any pair of particle)
Orbital part Spin part
2016-04-28 34
Multi-electron atom2S+1 119871119869
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
120595 Ԧ1199031 hellip Ԧ119903119873 Ԧ1198781 hellip Ԧ119878119873 = 120595 Ԧ1199031 hellip Ԧ119903119873 120594 Ԧ1198781 hellip Ԧ119878119873
Multi-electron wavefunction
Antisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =Exchange interaction
Antisymmetric
Example
A
B
Two electrons localized on one centrum
2016-04-28 35
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Hundrsquos rules ET lt ES
Antisymmetric
2016-04-28 36
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
clasically
thus
[Am2]
m
r
vBohr magneton 120583119861 =
ℏ119890
21198980
120583119861 = 9274009994(57)times10minus24 JT
2016-04-28 17
Magnetic field and spinMagnetic field
119867prime = minus119898119861
Here 119898 is magnetic moment
119898 = 119868 Ԧ119878 =119890
1198791205871199032 =
119890
21205871199031199071205871199032 =
119890
2119903119907
119898 = minus119890
21198980119871 = minus
120583119861ℏ119871
119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911119867prime = minus119898119861 =
120583119861ℏ119871119861
120583119861 =ℏ119890
21198980
circumference of a circle
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 18
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 19
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
2016-04-28 20
Magnetic field and spin
What is the bdquospinrdquo
bull What is bdquomassrdquo
Mariusz Pudzianowski httpwwwpudzianpl
2016-04-28 21
bull What is the bdquomomentumrdquo
What is the bdquospinrdquo
2016-04-28 22
bull What is the bdquoangular momentumrdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 23
bull What is the bdquochargerdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 24
bull Spin
DisneySebastian Muumlnster Cosmographia in 1544
htt
p
ww
wf
lori
dah
isto
ryc
om
us
15
70
htm
l
What is the bdquospinrdquo
2016-04-28 25
Pauli matrices 120590119909 120590119910 120590119911
Spinor
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
2016-04-28 26
Magnetic field and spinSpin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
2016-04-28 27
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc119892-factor for the agreement with experiments
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 28
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
119892 = minus200231930436182 plusmn 000000000000052
2016-04-28 29
QED ndash Quantum ElectroDynamics
119892 = minus200231930436182 plusmn 000000000000052
The consequences
2016-04-28 30
There is the bdquospinrdquo
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
Total magnetic moment 119872 = 119872119871 + 119872119878 = minus119892119871120583119861
ℏ119871 minus119892119878
120583119861
ℏመ119878
=1 =2
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 31
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
119872 ne መ119869 - magnetic anomaly of spin
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 32
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
119867119878119874 = 120582119871 መ119878 = 1205821
21198692 minus 1198712 minus 1198782 = 120582 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
120582 = ℎ119888 119860 =1198851205722
2
1
1199033
120572 =1198902
41205871205760ℏ119888asymp
1
137037
119864119878119874 = න120595lowast119867119878119874120595 119889119881 =119885
2 137 2න120595lowast119871 መ119878
1199033120595 119889119881
fine-structure constant119877119910 = ℎ119888119877infin
119877infin =119898119890119890
4
812057602ℎ3119888
119877infin = 1097 times 107m-1
eg for 120595210 we get1
1199033=
1
24
119885
1198860
3and for general 119899 (principal quantum number)
119864119878119874 =1198854
2 137 2119886031198993
119895 119895 + 1 minus 119897 119897 + 1 minus 119904(119904 + 1)
2119897(119897 + 12)(119897 + 1)
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 33
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
3
3
2
119871 = 1 መ119878 =1
2
211987532
211987512
shortly | ൿ119895 119898119895
the base | ൿ119899 119897 119904 119895 119898119895
ത119871 ҧ119878 =1
2ҧ1198692 minus ത1198712 minus ҧ1198782 = 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
Term symbol
an abbreviated description of the angular momentum quantum numbers in a multi-electron atom
Total wavefunction must be antisymmetric (under interchange of any pair of particle)
Orbital part Spin part
2016-04-28 34
Multi-electron atom2S+1 119871119869
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
120595 Ԧ1199031 hellip Ԧ119903119873 Ԧ1198781 hellip Ԧ119878119873 = 120595 Ԧ1199031 hellip Ԧ119903119873 120594 Ԧ1198781 hellip Ԧ119878119873
Multi-electron wavefunction
Antisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =Exchange interaction
Antisymmetric
Example
A
B
Two electrons localized on one centrum
2016-04-28 35
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Hundrsquos rules ET lt ES
Antisymmetric
2016-04-28 36
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 18
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 19
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
2016-04-28 20
Magnetic field and spin
What is the bdquospinrdquo
bull What is bdquomassrdquo
Mariusz Pudzianowski httpwwwpudzianpl
2016-04-28 21
bull What is the bdquomomentumrdquo
What is the bdquospinrdquo
2016-04-28 22
bull What is the bdquoangular momentumrdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 23
bull What is the bdquochargerdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 24
bull Spin
DisneySebastian Muumlnster Cosmographia in 1544
htt
p
ww
wf
lori
dah
isto
ryc
om
us
15
70
htm
l
What is the bdquospinrdquo
2016-04-28 25
Pauli matrices 120590119909 120590119910 120590119911
Spinor
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
2016-04-28 26
Magnetic field and spinSpin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
2016-04-28 27
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc119892-factor for the agreement with experiments
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 28
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
119892 = minus200231930436182 plusmn 000000000000052
2016-04-28 29
QED ndash Quantum ElectroDynamics
119892 = minus200231930436182 plusmn 000000000000052
The consequences
2016-04-28 30
There is the bdquospinrdquo
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
Total magnetic moment 119872 = 119872119871 + 119872119878 = minus119892119871120583119861
ℏ119871 minus119892119878
120583119861
ℏመ119878
=1 =2
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 31
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
119872 ne መ119869 - magnetic anomaly of spin
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 32
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
119867119878119874 = 120582119871 መ119878 = 1205821
21198692 minus 1198712 minus 1198782 = 120582 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
120582 = ℎ119888 119860 =1198851205722
2
1
1199033
120572 =1198902
41205871205760ℏ119888asymp
1
137037
119864119878119874 = න120595lowast119867119878119874120595 119889119881 =119885
2 137 2න120595lowast119871 መ119878
1199033120595 119889119881
fine-structure constant119877119910 = ℎ119888119877infin
119877infin =119898119890119890
4
812057602ℎ3119888
119877infin = 1097 times 107m-1
eg for 120595210 we get1
1199033=
1
24
119885
1198860
3and for general 119899 (principal quantum number)
119864119878119874 =1198854
2 137 2119886031198993
119895 119895 + 1 minus 119897 119897 + 1 minus 119904(119904 + 1)
2119897(119897 + 12)(119897 + 1)
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 33
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
3
3
2
119871 = 1 መ119878 =1
2
211987532
211987512
shortly | ൿ119895 119898119895
the base | ൿ119899 119897 119904 119895 119898119895
ത119871 ҧ119878 =1
2ҧ1198692 minus ത1198712 minus ҧ1198782 = 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
Term symbol
an abbreviated description of the angular momentum quantum numbers in a multi-electron atom
Total wavefunction must be antisymmetric (under interchange of any pair of particle)
Orbital part Spin part
2016-04-28 34
Multi-electron atom2S+1 119871119869
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
120595 Ԧ1199031 hellip Ԧ119903119873 Ԧ1198781 hellip Ԧ119878119873 = 120595 Ԧ1199031 hellip Ԧ119903119873 120594 Ԧ1198781 hellip Ԧ119878119873
Multi-electron wavefunction
Antisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =Exchange interaction
Antisymmetric
Example
A
B
Two electrons localized on one centrum
2016-04-28 35
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Hundrsquos rules ET lt ES
Antisymmetric
2016-04-28 36
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Magnetic field
for 119861 = 00 119861119911
we have 119867prime =120583119861
ℏ119871119911119861119911 = 120583119861119861119911119898
where 119898 = minus119897 minus119897 + 1hellip 119897 minus 1 119897
the base
2016-04-28 19
Magnetic field and spin
119867prime = minus119898119861 =120583119861ℏ119871119861
Here 119898 is magnetic moment
119898 = 1
119898 = 0
119898 = minus1
119897 = 1
119861 = 0 119861 ne 0
| 119897 119898
m
r
v119871 = Ԧ119903 times 1198980 Ԧ119907
119871 = 119871119909 119871119910 119871119911
Here 119898 is NOT a magnetic moment(it is a magnetic quantum number)
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
2016-04-28 20
Magnetic field and spin
What is the bdquospinrdquo
bull What is bdquomassrdquo
Mariusz Pudzianowski httpwwwpudzianpl
2016-04-28 21
bull What is the bdquomomentumrdquo
What is the bdquospinrdquo
2016-04-28 22
bull What is the bdquoangular momentumrdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 23
bull What is the bdquochargerdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 24
bull Spin
DisneySebastian Muumlnster Cosmographia in 1544
htt
p
ww
wf
lori
dah
isto
ryc
om
us
15
70
htm
l
What is the bdquospinrdquo
2016-04-28 25
Pauli matrices 120590119909 120590119910 120590119911
Spinor
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
2016-04-28 26
Magnetic field and spinSpin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
2016-04-28 27
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc119892-factor for the agreement with experiments
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 28
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
119892 = minus200231930436182 plusmn 000000000000052
2016-04-28 29
QED ndash Quantum ElectroDynamics
119892 = minus200231930436182 plusmn 000000000000052
The consequences
2016-04-28 30
There is the bdquospinrdquo
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
Total magnetic moment 119872 = 119872119871 + 119872119878 = minus119892119871120583119861
ℏ119871 minus119892119878
120583119861
ℏመ119878
=1 =2
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 31
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
119872 ne መ119869 - magnetic anomaly of spin
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 32
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
119867119878119874 = 120582119871 መ119878 = 1205821
21198692 minus 1198712 minus 1198782 = 120582 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
120582 = ℎ119888 119860 =1198851205722
2
1
1199033
120572 =1198902
41205871205760ℏ119888asymp
1
137037
119864119878119874 = න120595lowast119867119878119874120595 119889119881 =119885
2 137 2න120595lowast119871 መ119878
1199033120595 119889119881
fine-structure constant119877119910 = ℎ119888119877infin
119877infin =119898119890119890
4
812057602ℎ3119888
119877infin = 1097 times 107m-1
eg for 120595210 we get1
1199033=
1
24
119885
1198860
3and for general 119899 (principal quantum number)
119864119878119874 =1198854
2 137 2119886031198993
119895 119895 + 1 minus 119897 119897 + 1 minus 119904(119904 + 1)
2119897(119897 + 12)(119897 + 1)
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 33
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
3
3
2
119871 = 1 መ119878 =1
2
211987532
211987512
shortly | ൿ119895 119898119895
the base | ൿ119899 119897 119904 119895 119898119895
ത119871 ҧ119878 =1
2ҧ1198692 minus ത1198712 minus ҧ1198782 = 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
Term symbol
an abbreviated description of the angular momentum quantum numbers in a multi-electron atom
Total wavefunction must be antisymmetric (under interchange of any pair of particle)
Orbital part Spin part
2016-04-28 34
Multi-electron atom2S+1 119871119869
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
120595 Ԧ1199031 hellip Ԧ119903119873 Ԧ1198781 hellip Ԧ119878119873 = 120595 Ԧ1199031 hellip Ԧ119903119873 120594 Ԧ1198781 hellip Ԧ119878119873
Multi-electron wavefunction
Antisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =Exchange interaction
Antisymmetric
Example
A
B
Two electrons localized on one centrum
2016-04-28 35
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Hundrsquos rules ET lt ES
Antisymmetric
2016-04-28 36
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
2016-04-28 20
Magnetic field and spin
What is the bdquospinrdquo
bull What is bdquomassrdquo
Mariusz Pudzianowski httpwwwpudzianpl
2016-04-28 21
bull What is the bdquomomentumrdquo
What is the bdquospinrdquo
2016-04-28 22
bull What is the bdquoangular momentumrdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 23
bull What is the bdquochargerdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 24
bull Spin
DisneySebastian Muumlnster Cosmographia in 1544
htt
p
ww
wf
lori
dah
isto
ryc
om
us
15
70
htm
l
What is the bdquospinrdquo
2016-04-28 25
Pauli matrices 120590119909 120590119910 120590119911
Spinor
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
2016-04-28 26
Magnetic field and spinSpin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
2016-04-28 27
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc119892-factor for the agreement with experiments
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 28
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
119892 = minus200231930436182 plusmn 000000000000052
2016-04-28 29
QED ndash Quantum ElectroDynamics
119892 = minus200231930436182 plusmn 000000000000052
The consequences
2016-04-28 30
There is the bdquospinrdquo
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
Total magnetic moment 119872 = 119872119871 + 119872119878 = minus119892119871120583119861
ℏ119871 minus119892119878
120583119861
ℏመ119878
=1 =2
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 31
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
119872 ne መ119869 - magnetic anomaly of spin
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 32
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
119867119878119874 = 120582119871 መ119878 = 1205821
21198692 minus 1198712 minus 1198782 = 120582 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
120582 = ℎ119888 119860 =1198851205722
2
1
1199033
120572 =1198902
41205871205760ℏ119888asymp
1
137037
119864119878119874 = න120595lowast119867119878119874120595 119889119881 =119885
2 137 2න120595lowast119871 መ119878
1199033120595 119889119881
fine-structure constant119877119910 = ℎ119888119877infin
119877infin =119898119890119890
4
812057602ℎ3119888
119877infin = 1097 times 107m-1
eg for 120595210 we get1
1199033=
1
24
119885
1198860
3and for general 119899 (principal quantum number)
119864119878119874 =1198854
2 137 2119886031198993
119895 119895 + 1 minus 119897 119897 + 1 minus 119904(119904 + 1)
2119897(119897 + 12)(119897 + 1)
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 33
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
3
3
2
119871 = 1 መ119878 =1
2
211987532
211987512
shortly | ൿ119895 119898119895
the base | ൿ119899 119897 119904 119895 119898119895
ത119871 ҧ119878 =1
2ҧ1198692 minus ത1198712 minus ҧ1198782 = 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
Term symbol
an abbreviated description of the angular momentum quantum numbers in a multi-electron atom
Total wavefunction must be antisymmetric (under interchange of any pair of particle)
Orbital part Spin part
2016-04-28 34
Multi-electron atom2S+1 119871119869
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
120595 Ԧ1199031 hellip Ԧ119903119873 Ԧ1198781 hellip Ԧ119878119873 = 120595 Ԧ1199031 hellip Ԧ119903119873 120594 Ԧ1198781 hellip Ԧ119878119873
Multi-electron wavefunction
Antisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =Exchange interaction
Antisymmetric
Example
A
B
Two electrons localized on one centrum
2016-04-28 35
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Hundrsquos rules ET lt ES
Antisymmetric
2016-04-28 36
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
What is the bdquospinrdquo
bull What is bdquomassrdquo
Mariusz Pudzianowski httpwwwpudzianpl
2016-04-28 21
bull What is the bdquomomentumrdquo
What is the bdquospinrdquo
2016-04-28 22
bull What is the bdquoangular momentumrdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 23
bull What is the bdquochargerdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 24
bull Spin
DisneySebastian Muumlnster Cosmographia in 1544
htt
p
ww
wf
lori
dah
isto
ryc
om
us
15
70
htm
l
What is the bdquospinrdquo
2016-04-28 25
Pauli matrices 120590119909 120590119910 120590119911
Spinor
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
2016-04-28 26
Magnetic field and spinSpin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
2016-04-28 27
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc119892-factor for the agreement with experiments
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 28
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
119892 = minus200231930436182 plusmn 000000000000052
2016-04-28 29
QED ndash Quantum ElectroDynamics
119892 = minus200231930436182 plusmn 000000000000052
The consequences
2016-04-28 30
There is the bdquospinrdquo
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
Total magnetic moment 119872 = 119872119871 + 119872119878 = minus119892119871120583119861
ℏ119871 minus119892119878
120583119861
ℏመ119878
=1 =2
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 31
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
119872 ne መ119869 - magnetic anomaly of spin
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 32
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
119867119878119874 = 120582119871 መ119878 = 1205821
21198692 minus 1198712 minus 1198782 = 120582 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
120582 = ℎ119888 119860 =1198851205722
2
1
1199033
120572 =1198902
41205871205760ℏ119888asymp
1
137037
119864119878119874 = න120595lowast119867119878119874120595 119889119881 =119885
2 137 2න120595lowast119871 መ119878
1199033120595 119889119881
fine-structure constant119877119910 = ℎ119888119877infin
119877infin =119898119890119890
4
812057602ℎ3119888
119877infin = 1097 times 107m-1
eg for 120595210 we get1
1199033=
1
24
119885
1198860
3and for general 119899 (principal quantum number)
119864119878119874 =1198854
2 137 2119886031198993
119895 119895 + 1 minus 119897 119897 + 1 minus 119904(119904 + 1)
2119897(119897 + 12)(119897 + 1)
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 33
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
3
3
2
119871 = 1 መ119878 =1
2
211987532
211987512
shortly | ൿ119895 119898119895
the base | ൿ119899 119897 119904 119895 119898119895
ത119871 ҧ119878 =1
2ҧ1198692 minus ത1198712 minus ҧ1198782 = 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
Term symbol
an abbreviated description of the angular momentum quantum numbers in a multi-electron atom
Total wavefunction must be antisymmetric (under interchange of any pair of particle)
Orbital part Spin part
2016-04-28 34
Multi-electron atom2S+1 119871119869
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
120595 Ԧ1199031 hellip Ԧ119903119873 Ԧ1198781 hellip Ԧ119878119873 = 120595 Ԧ1199031 hellip Ԧ119903119873 120594 Ԧ1198781 hellip Ԧ119878119873
Multi-electron wavefunction
Antisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =Exchange interaction
Antisymmetric
Example
A
B
Two electrons localized on one centrum
2016-04-28 35
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Hundrsquos rules ET lt ES
Antisymmetric
2016-04-28 36
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
bull What is the bdquomomentumrdquo
What is the bdquospinrdquo
2016-04-28 22
bull What is the bdquoangular momentumrdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 23
bull What is the bdquochargerdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 24
bull Spin
DisneySebastian Muumlnster Cosmographia in 1544
htt
p
ww
wf
lori
dah
isto
ryc
om
us
15
70
htm
l
What is the bdquospinrdquo
2016-04-28 25
Pauli matrices 120590119909 120590119910 120590119911
Spinor
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
2016-04-28 26
Magnetic field and spinSpin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
2016-04-28 27
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc119892-factor for the agreement with experiments
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 28
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
119892 = minus200231930436182 plusmn 000000000000052
2016-04-28 29
QED ndash Quantum ElectroDynamics
119892 = minus200231930436182 plusmn 000000000000052
The consequences
2016-04-28 30
There is the bdquospinrdquo
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
Total magnetic moment 119872 = 119872119871 + 119872119878 = minus119892119871120583119861
ℏ119871 minus119892119878
120583119861
ℏመ119878
=1 =2
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 31
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
119872 ne መ119869 - magnetic anomaly of spin
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 32
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
119867119878119874 = 120582119871 መ119878 = 1205821
21198692 minus 1198712 minus 1198782 = 120582 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
120582 = ℎ119888 119860 =1198851205722
2
1
1199033
120572 =1198902
41205871205760ℏ119888asymp
1
137037
119864119878119874 = න120595lowast119867119878119874120595 119889119881 =119885
2 137 2න120595lowast119871 መ119878
1199033120595 119889119881
fine-structure constant119877119910 = ℎ119888119877infin
119877infin =119898119890119890
4
812057602ℎ3119888
119877infin = 1097 times 107m-1
eg for 120595210 we get1
1199033=
1
24
119885
1198860
3and for general 119899 (principal quantum number)
119864119878119874 =1198854
2 137 2119886031198993
119895 119895 + 1 minus 119897 119897 + 1 minus 119904(119904 + 1)
2119897(119897 + 12)(119897 + 1)
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 33
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
3
3
2
119871 = 1 መ119878 =1
2
211987532
211987512
shortly | ൿ119895 119898119895
the base | ൿ119899 119897 119904 119895 119898119895
ത119871 ҧ119878 =1
2ҧ1198692 minus ത1198712 minus ҧ1198782 = 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
Term symbol
an abbreviated description of the angular momentum quantum numbers in a multi-electron atom
Total wavefunction must be antisymmetric (under interchange of any pair of particle)
Orbital part Spin part
2016-04-28 34
Multi-electron atom2S+1 119871119869
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
120595 Ԧ1199031 hellip Ԧ119903119873 Ԧ1198781 hellip Ԧ119878119873 = 120595 Ԧ1199031 hellip Ԧ119903119873 120594 Ԧ1198781 hellip Ԧ119878119873
Multi-electron wavefunction
Antisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =Exchange interaction
Antisymmetric
Example
A
B
Two electrons localized on one centrum
2016-04-28 35
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Hundrsquos rules ET lt ES
Antisymmetric
2016-04-28 36
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
bull What is the bdquoangular momentumrdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 23
bull What is the bdquochargerdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 24
bull Spin
DisneySebastian Muumlnster Cosmographia in 1544
htt
p
ww
wf
lori
dah
isto
ryc
om
us
15
70
htm
l
What is the bdquospinrdquo
2016-04-28 25
Pauli matrices 120590119909 120590119910 120590119911
Spinor
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
2016-04-28 26
Magnetic field and spinSpin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
2016-04-28 27
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc119892-factor for the agreement with experiments
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 28
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
119892 = minus200231930436182 plusmn 000000000000052
2016-04-28 29
QED ndash Quantum ElectroDynamics
119892 = minus200231930436182 plusmn 000000000000052
The consequences
2016-04-28 30
There is the bdquospinrdquo
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
Total magnetic moment 119872 = 119872119871 + 119872119878 = minus119892119871120583119861
ℏ119871 minus119892119878
120583119861
ℏመ119878
=1 =2
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 31
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
119872 ne መ119869 - magnetic anomaly of spin
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 32
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
119867119878119874 = 120582119871 መ119878 = 1205821
21198692 minus 1198712 minus 1198782 = 120582 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
120582 = ℎ119888 119860 =1198851205722
2
1
1199033
120572 =1198902
41205871205760ℏ119888asymp
1
137037
119864119878119874 = න120595lowast119867119878119874120595 119889119881 =119885
2 137 2න120595lowast119871 መ119878
1199033120595 119889119881
fine-structure constant119877119910 = ℎ119888119877infin
119877infin =119898119890119890
4
812057602ℎ3119888
119877infin = 1097 times 107m-1
eg for 120595210 we get1
1199033=
1
24
119885
1198860
3and for general 119899 (principal quantum number)
119864119878119874 =1198854
2 137 2119886031198993
119895 119895 + 1 minus 119897 119897 + 1 minus 119904(119904 + 1)
2119897(119897 + 12)(119897 + 1)
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 33
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
3
3
2
119871 = 1 መ119878 =1
2
211987532
211987512
shortly | ൿ119895 119898119895
the base | ൿ119899 119897 119904 119895 119898119895
ത119871 ҧ119878 =1
2ҧ1198692 minus ത1198712 minus ҧ1198782 = 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
Term symbol
an abbreviated description of the angular momentum quantum numbers in a multi-electron atom
Total wavefunction must be antisymmetric (under interchange of any pair of particle)
Orbital part Spin part
2016-04-28 34
Multi-electron atom2S+1 119871119869
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
120595 Ԧ1199031 hellip Ԧ119903119873 Ԧ1198781 hellip Ԧ119878119873 = 120595 Ԧ1199031 hellip Ԧ119903119873 120594 Ԧ1198781 hellip Ԧ119878119873
Multi-electron wavefunction
Antisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =Exchange interaction
Antisymmetric
Example
A
B
Two electrons localized on one centrum
2016-04-28 35
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Hundrsquos rules ET lt ES
Antisymmetric
2016-04-28 36
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
bull What is the bdquochargerdquo
httpwwwchasedaycom
What is the bdquospinrdquo
2016-04-28 24
bull Spin
DisneySebastian Muumlnster Cosmographia in 1544
htt
p
ww
wf
lori
dah
isto
ryc
om
us
15
70
htm
l
What is the bdquospinrdquo
2016-04-28 25
Pauli matrices 120590119909 120590119910 120590119911
Spinor
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
2016-04-28 26
Magnetic field and spinSpin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
2016-04-28 27
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc119892-factor for the agreement with experiments
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 28
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
119892 = minus200231930436182 plusmn 000000000000052
2016-04-28 29
QED ndash Quantum ElectroDynamics
119892 = minus200231930436182 plusmn 000000000000052
The consequences
2016-04-28 30
There is the bdquospinrdquo
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
Total magnetic moment 119872 = 119872119871 + 119872119878 = minus119892119871120583119861
ℏ119871 minus119892119878
120583119861
ℏመ119878
=1 =2
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 31
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
119872 ne መ119869 - magnetic anomaly of spin
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 32
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
119867119878119874 = 120582119871 መ119878 = 1205821
21198692 minus 1198712 minus 1198782 = 120582 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
120582 = ℎ119888 119860 =1198851205722
2
1
1199033
120572 =1198902
41205871205760ℏ119888asymp
1
137037
119864119878119874 = න120595lowast119867119878119874120595 119889119881 =119885
2 137 2න120595lowast119871 መ119878
1199033120595 119889119881
fine-structure constant119877119910 = ℎ119888119877infin
119877infin =119898119890119890
4
812057602ℎ3119888
119877infin = 1097 times 107m-1
eg for 120595210 we get1
1199033=
1
24
119885
1198860
3and for general 119899 (principal quantum number)
119864119878119874 =1198854
2 137 2119886031198993
119895 119895 + 1 minus 119897 119897 + 1 minus 119904(119904 + 1)
2119897(119897 + 12)(119897 + 1)
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 33
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
3
3
2
119871 = 1 መ119878 =1
2
211987532
211987512
shortly | ൿ119895 119898119895
the base | ൿ119899 119897 119904 119895 119898119895
ത119871 ҧ119878 =1
2ҧ1198692 minus ത1198712 minus ҧ1198782 = 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
Term symbol
an abbreviated description of the angular momentum quantum numbers in a multi-electron atom
Total wavefunction must be antisymmetric (under interchange of any pair of particle)
Orbital part Spin part
2016-04-28 34
Multi-electron atom2S+1 119871119869
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
120595 Ԧ1199031 hellip Ԧ119903119873 Ԧ1198781 hellip Ԧ119878119873 = 120595 Ԧ1199031 hellip Ԧ119903119873 120594 Ԧ1198781 hellip Ԧ119878119873
Multi-electron wavefunction
Antisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =Exchange interaction
Antisymmetric
Example
A
B
Two electrons localized on one centrum
2016-04-28 35
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Hundrsquos rules ET lt ES
Antisymmetric
2016-04-28 36
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
bull Spin
DisneySebastian Muumlnster Cosmographia in 1544
htt
p
ww
wf
lori
dah
isto
ryc
om
us
15
70
htm
l
What is the bdquospinrdquo
2016-04-28 25
Pauli matrices 120590119909 120590119910 120590119911
Spinor
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
2016-04-28 26
Magnetic field and spinSpin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
2016-04-28 27
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc119892-factor for the agreement with experiments
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 28
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
119892 = minus200231930436182 plusmn 000000000000052
2016-04-28 29
QED ndash Quantum ElectroDynamics
119892 = minus200231930436182 plusmn 000000000000052
The consequences
2016-04-28 30
There is the bdquospinrdquo
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
Total magnetic moment 119872 = 119872119871 + 119872119878 = minus119892119871120583119861
ℏ119871 minus119892119878
120583119861
ℏመ119878
=1 =2
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 31
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
119872 ne መ119869 - magnetic anomaly of spin
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 32
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
119867119878119874 = 120582119871 መ119878 = 1205821
21198692 minus 1198712 minus 1198782 = 120582 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
120582 = ℎ119888 119860 =1198851205722
2
1
1199033
120572 =1198902
41205871205760ℏ119888asymp
1
137037
119864119878119874 = න120595lowast119867119878119874120595 119889119881 =119885
2 137 2න120595lowast119871 መ119878
1199033120595 119889119881
fine-structure constant119877119910 = ℎ119888119877infin
119877infin =119898119890119890
4
812057602ℎ3119888
119877infin = 1097 times 107m-1
eg for 120595210 we get1
1199033=
1
24
119885
1198860
3and for general 119899 (principal quantum number)
119864119878119874 =1198854
2 137 2119886031198993
119895 119895 + 1 minus 119897 119897 + 1 minus 119904(119904 + 1)
2119897(119897 + 12)(119897 + 1)
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 33
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
3
3
2
119871 = 1 መ119878 =1
2
211987532
211987512
shortly | ൿ119895 119898119895
the base | ൿ119899 119897 119904 119895 119898119895
ത119871 ҧ119878 =1
2ҧ1198692 minus ത1198712 minus ҧ1198782 = 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
Term symbol
an abbreviated description of the angular momentum quantum numbers in a multi-electron atom
Total wavefunction must be antisymmetric (under interchange of any pair of particle)
Orbital part Spin part
2016-04-28 34
Multi-electron atom2S+1 119871119869
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
120595 Ԧ1199031 hellip Ԧ119903119873 Ԧ1198781 hellip Ԧ119878119873 = 120595 Ԧ1199031 hellip Ԧ119903119873 120594 Ԧ1198781 hellip Ԧ119878119873
Multi-electron wavefunction
Antisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =Exchange interaction
Antisymmetric
Example
A
B
Two electrons localized on one centrum
2016-04-28 35
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Hundrsquos rules ET lt ES
Antisymmetric
2016-04-28 36
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Pauli matrices 120590119909 120590119910 120590119911
Spinor
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
2016-04-28 26
Magnetic field and spinSpin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
2016-04-28 27
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc119892-factor for the agreement with experiments
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 28
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
119892 = minus200231930436182 plusmn 000000000000052
2016-04-28 29
QED ndash Quantum ElectroDynamics
119892 = minus200231930436182 plusmn 000000000000052
The consequences
2016-04-28 30
There is the bdquospinrdquo
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
Total magnetic moment 119872 = 119872119871 + 119872119878 = minus119892119871120583119861
ℏ119871 minus119892119878
120583119861
ℏመ119878
=1 =2
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 31
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
119872 ne መ119869 - magnetic anomaly of spin
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 32
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
119867119878119874 = 120582119871 መ119878 = 1205821
21198692 minus 1198712 minus 1198782 = 120582 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
120582 = ℎ119888 119860 =1198851205722
2
1
1199033
120572 =1198902
41205871205760ℏ119888asymp
1
137037
119864119878119874 = න120595lowast119867119878119874120595 119889119881 =119885
2 137 2න120595lowast119871 መ119878
1199033120595 119889119881
fine-structure constant119877119910 = ℎ119888119877infin
119877infin =119898119890119890
4
812057602ℎ3119888
119877infin = 1097 times 107m-1
eg for 120595210 we get1
1199033=
1
24
119885
1198860
3and for general 119899 (principal quantum number)
119864119878119874 =1198854
2 137 2119886031198993
119895 119895 + 1 minus 119897 119897 + 1 minus 119904(119904 + 1)
2119897(119897 + 12)(119897 + 1)
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 33
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
3
3
2
119871 = 1 መ119878 =1
2
211987532
211987512
shortly | ൿ119895 119898119895
the base | ൿ119899 119897 119904 119895 119898119895
ത119871 ҧ119878 =1
2ҧ1198692 minus ത1198712 minus ҧ1198782 = 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
Term symbol
an abbreviated description of the angular momentum quantum numbers in a multi-electron atom
Total wavefunction must be antisymmetric (under interchange of any pair of particle)
Orbital part Spin part
2016-04-28 34
Multi-electron atom2S+1 119871119869
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
120595 Ԧ1199031 hellip Ԧ119903119873 Ԧ1198781 hellip Ԧ119878119873 = 120595 Ԧ1199031 hellip Ԧ119903119873 120594 Ԧ1198781 hellip Ԧ119878119873
Multi-electron wavefunction
Antisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =Exchange interaction
Antisymmetric
Example
A
B
Two electrons localized on one centrum
2016-04-28 35
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Hundrsquos rules ET lt ES
Antisymmetric
2016-04-28 36
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
2016-04-28 27
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc119892-factor for the agreement with experiments
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 28
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
119892 = minus200231930436182 plusmn 000000000000052
2016-04-28 29
QED ndash Quantum ElectroDynamics
119892 = minus200231930436182 plusmn 000000000000052
The consequences
2016-04-28 30
There is the bdquospinrdquo
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
Total magnetic moment 119872 = 119872119871 + 119872119878 = minus119892119871120583119861
ℏ119871 minus119892119878
120583119861
ℏመ119878
=1 =2
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 31
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
119872 ne መ119869 - magnetic anomaly of spin
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 32
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
119867119878119874 = 120582119871 መ119878 = 1205821
21198692 minus 1198712 minus 1198782 = 120582 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
120582 = ℎ119888 119860 =1198851205722
2
1
1199033
120572 =1198902
41205871205760ℏ119888asymp
1
137037
119864119878119874 = න120595lowast119867119878119874120595 119889119881 =119885
2 137 2න120595lowast119871 መ119878
1199033120595 119889119881
fine-structure constant119877119910 = ℎ119888119877infin
119877infin =119898119890119890
4
812057602ℎ3119888
119877infin = 1097 times 107m-1
eg for 120595210 we get1
1199033=
1
24
119885
1198860
3and for general 119899 (principal quantum number)
119864119878119874 =1198854
2 137 2119886031198993
119895 119895 + 1 minus 119897 119897 + 1 minus 119904(119904 + 1)
2119897(119897 + 12)(119897 + 1)
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 33
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
3
3
2
119871 = 1 መ119878 =1
2
211987532
211987512
shortly | ൿ119895 119898119895
the base | ൿ119899 119897 119904 119895 119898119895
ത119871 ҧ119878 =1
2ҧ1198692 minus ത1198712 minus ҧ1198782 = 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
Term symbol
an abbreviated description of the angular momentum quantum numbers in a multi-electron atom
Total wavefunction must be antisymmetric (under interchange of any pair of particle)
Orbital part Spin part
2016-04-28 34
Multi-electron atom2S+1 119871119869
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
120595 Ԧ1199031 hellip Ԧ119903119873 Ԧ1198781 hellip Ԧ119878119873 = 120595 Ԧ1199031 hellip Ԧ119903119873 120594 Ԧ1198781 hellip Ԧ119878119873
Multi-electron wavefunction
Antisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =Exchange interaction
Antisymmetric
Example
A
B
Two electrons localized on one centrum
2016-04-28 35
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Hundrsquos rules ET lt ES
Antisymmetric
2016-04-28 36
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 28
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
Pauli matrices 120590119909 120590119910 120590119911
መ119878119909 =1
2ℏ120590119909 =
1
2ℏ0 11 0
መ119878119910 =1
2ℏ120590119910 =
1
2ℏ0 minus119894119894 0
መ119878119909 =1
2ℏ120590119911 =
1
2ℏ1 00 minus1
projections of the spin on the axis 119911
120594uarr =10
120594darr =01
መ119878119909 መ119878119910 = 119894ℏ መ119878119911 etc
119892 = minus200231930436182 plusmn 000000000000052
2016-04-28 29
QED ndash Quantum ElectroDynamics
119892 = minus200231930436182 plusmn 000000000000052
The consequences
2016-04-28 30
There is the bdquospinrdquo
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
Total magnetic moment 119872 = 119872119871 + 119872119878 = minus119892119871120583119861
ℏ119871 minus119892119878
120583119861
ℏመ119878
=1 =2
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 31
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
119872 ne መ119869 - magnetic anomaly of spin
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 32
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
119867119878119874 = 120582119871 መ119878 = 1205821
21198692 minus 1198712 minus 1198782 = 120582 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
120582 = ℎ119888 119860 =1198851205722
2
1
1199033
120572 =1198902
41205871205760ℏ119888asymp
1
137037
119864119878119874 = න120595lowast119867119878119874120595 119889119881 =119885
2 137 2න120595lowast119871 መ119878
1199033120595 119889119881
fine-structure constant119877119910 = ℎ119888119877infin
119877infin =119898119890119890
4
812057602ℎ3119888
119877infin = 1097 times 107m-1
eg for 120595210 we get1
1199033=
1
24
119885
1198860
3and for general 119899 (principal quantum number)
119864119878119874 =1198854
2 137 2119886031198993
119895 119895 + 1 minus 119897 119897 + 1 minus 119904(119904 + 1)
2119897(119897 + 12)(119897 + 1)
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 33
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
3
3
2
119871 = 1 መ119878 =1
2
211987532
211987512
shortly | ൿ119895 119898119895
the base | ൿ119899 119897 119904 119895 119898119895
ത119871 ҧ119878 =1
2ҧ1198692 minus ത1198712 minus ҧ1198782 = 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
Term symbol
an abbreviated description of the angular momentum quantum numbers in a multi-electron atom
Total wavefunction must be antisymmetric (under interchange of any pair of particle)
Orbital part Spin part
2016-04-28 34
Multi-electron atom2S+1 119871119869
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
120595 Ԧ1199031 hellip Ԧ119903119873 Ԧ1198781 hellip Ԧ119878119873 = 120595 Ԧ1199031 hellip Ԧ119903119873 120594 Ԧ1198781 hellip Ԧ119878119873
Multi-electron wavefunction
Antisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =Exchange interaction
Antisymmetric
Example
A
B
Two electrons localized on one centrum
2016-04-28 35
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Hundrsquos rules ET lt ES
Antisymmetric
2016-04-28 36
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28 29
QED ndash Quantum ElectroDynamics
119892 = minus200231930436182 plusmn 000000000000052
The consequences
2016-04-28 30
There is the bdquospinrdquo
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
Total magnetic moment 119872 = 119872119871 + 119872119878 = minus119892119871120583119861
ℏ119871 minus119892119878
120583119861
ℏመ119878
=1 =2
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 31
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
119872 ne መ119869 - magnetic anomaly of spin
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 32
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
119867119878119874 = 120582119871 መ119878 = 1205821
21198692 minus 1198712 minus 1198782 = 120582 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
120582 = ℎ119888 119860 =1198851205722
2
1
1199033
120572 =1198902
41205871205760ℏ119888asymp
1
137037
119864119878119874 = න120595lowast119867119878119874120595 119889119881 =119885
2 137 2න120595lowast119871 መ119878
1199033120595 119889119881
fine-structure constant119877119910 = ℎ119888119877infin
119877infin =119898119890119890
4
812057602ℎ3119888
119877infin = 1097 times 107m-1
eg for 120595210 we get1
1199033=
1
24
119885
1198860
3and for general 119899 (principal quantum number)
119864119878119874 =1198854
2 137 2119886031198993
119895 119895 + 1 minus 119897 119897 + 1 minus 119904(119904 + 1)
2119897(119897 + 12)(119897 + 1)
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 33
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
3
3
2
119871 = 1 መ119878 =1
2
211987532
211987512
shortly | ൿ119895 119898119895
the base | ൿ119899 119897 119904 119895 119898119895
ത119871 ҧ119878 =1
2ҧ1198692 minus ത1198712 minus ҧ1198782 = 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
Term symbol
an abbreviated description of the angular momentum quantum numbers in a multi-electron atom
Total wavefunction must be antisymmetric (under interchange of any pair of particle)
Orbital part Spin part
2016-04-28 34
Multi-electron atom2S+1 119871119869
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
120595 Ԧ1199031 hellip Ԧ119903119873 Ԧ1198781 hellip Ԧ119878119873 = 120595 Ԧ1199031 hellip Ԧ119903119873 120594 Ԧ1198781 hellip Ԧ119878119873
Multi-electron wavefunction
Antisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =Exchange interaction
Antisymmetric
Example
A
B
Two electrons localized on one centrum
2016-04-28 35
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Hundrsquos rules ET lt ES
Antisymmetric
2016-04-28 36
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
The consequences
2016-04-28 30
There is the bdquospinrdquo
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
Total magnetic moment 119872 = 119872119871 + 119872119878 = minus119892119871120583119861
ℏ119871 minus119892119878
120583119861
ℏመ119878
=1 =2
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 31
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
119872 ne መ119869 - magnetic anomaly of spin
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 32
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
119867119878119874 = 120582119871 መ119878 = 1205821
21198692 minus 1198712 minus 1198782 = 120582 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
120582 = ℎ119888 119860 =1198851205722
2
1
1199033
120572 =1198902
41205871205760ℏ119888asymp
1
137037
119864119878119874 = න120595lowast119867119878119874120595 119889119881 =119885
2 137 2න120595lowast119871 መ119878
1199033120595 119889119881
fine-structure constant119877119910 = ℎ119888119877infin
119877infin =119898119890119890
4
812057602ℎ3119888
119877infin = 1097 times 107m-1
eg for 120595210 we get1
1199033=
1
24
119885
1198860
3and for general 119899 (principal quantum number)
119864119878119874 =1198854
2 137 2119886031198993
119895 119895 + 1 minus 119897 119897 + 1 minus 119904(119904 + 1)
2119897(119897 + 12)(119897 + 1)
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 33
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
3
3
2
119871 = 1 መ119878 =1
2
211987532
211987512
shortly | ൿ119895 119898119895
the base | ൿ119899 119897 119904 119895 119898119895
ത119871 ҧ119878 =1
2ҧ1198692 minus ത1198712 minus ҧ1198782 = 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
Term symbol
an abbreviated description of the angular momentum quantum numbers in a multi-electron atom
Total wavefunction must be antisymmetric (under interchange of any pair of particle)
Orbital part Spin part
2016-04-28 34
Multi-electron atom2S+1 119871119869
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
120595 Ԧ1199031 hellip Ԧ119903119873 Ԧ1198781 hellip Ԧ119878119873 = 120595 Ԧ1199031 hellip Ԧ119903119873 120594 Ԧ1198781 hellip Ԧ119878119873
Multi-electron wavefunction
Antisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =Exchange interaction
Antisymmetric
Example
A
B
Two electrons localized on one centrum
2016-04-28 35
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Hundrsquos rules ET lt ES
Antisymmetric
2016-04-28 36
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
Total magnetic moment 119872 = 119872119871 + 119872119878 = minus119892119871120583119861
ℏ119871 minus119892119878
120583119861
ℏመ119878
=1 =2
Spin spin-orbit interaction
Spin operators መ119878119909 መ119878119910 መ119878119911 መ1198782
119892-factor for the agreement with experiments
2016-04-28 31
Magnetic field and spin
119867prime =120583119861ℏ
119871 + 119892 መ119878 119861
119872 ne መ119869 - magnetic anomaly of spin
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 32
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
119867119878119874 = 120582119871 መ119878 = 1205821
21198692 minus 1198712 minus 1198782 = 120582 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
120582 = ℎ119888 119860 =1198851205722
2
1
1199033
120572 =1198902
41205871205760ℏ119888asymp
1
137037
119864119878119874 = න120595lowast119867119878119874120595 119889119881 =119885
2 137 2න120595lowast119871 መ119878
1199033120595 119889119881
fine-structure constant119877119910 = ℎ119888119877infin
119877infin =119898119890119890
4
812057602ℎ3119888
119877infin = 1097 times 107m-1
eg for 120595210 we get1
1199033=
1
24
119885
1198860
3and for general 119899 (principal quantum number)
119864119878119874 =1198854
2 137 2119886031198993
119895 119895 + 1 minus 119897 119897 + 1 minus 119904(119904 + 1)
2119897(119897 + 12)(119897 + 1)
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 33
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
3
3
2
119871 = 1 መ119878 =1
2
211987532
211987512
shortly | ൿ119895 119898119895
the base | ൿ119899 119897 119904 119895 119898119895
ത119871 ҧ119878 =1
2ҧ1198692 minus ത1198712 minus ҧ1198782 = 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
Term symbol
an abbreviated description of the angular momentum quantum numbers in a multi-electron atom
Total wavefunction must be antisymmetric (under interchange of any pair of particle)
Orbital part Spin part
2016-04-28 34
Multi-electron atom2S+1 119871119869
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
120595 Ԧ1199031 hellip Ԧ119903119873 Ԧ1198781 hellip Ԧ119878119873 = 120595 Ԧ1199031 hellip Ԧ119903119873 120594 Ԧ1198781 hellip Ԧ119878119873
Multi-electron wavefunction
Antisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =Exchange interaction
Antisymmetric
Example
A
B
Two electrons localized on one centrum
2016-04-28 35
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Hundrsquos rules ET lt ES
Antisymmetric
2016-04-28 36
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 32
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
119867119878119874 = 120582119871 መ119878 = 1205821
21198692 minus 1198712 minus 1198782 = 120582 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
120582 = ℎ119888 119860 =1198851205722
2
1
1199033
120572 =1198902
41205871205760ℏ119888asymp
1
137037
119864119878119874 = න120595lowast119867119878119874120595 119889119881 =119885
2 137 2න120595lowast119871 መ119878
1199033120595 119889119881
fine-structure constant119877119910 = ℎ119888119877infin
119877infin =119898119890119890
4
812057602ℎ3119888
119877infin = 1097 times 107m-1
eg for 120595210 we get1
1199033=
1
24
119885
1198860
3and for general 119899 (principal quantum number)
119864119878119874 =1198854
2 137 2119886031198993
119895 119895 + 1 minus 119897 119897 + 1 minus 119904(119904 + 1)
2119897(119897 + 12)(119897 + 1)
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 33
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
3
3
2
119871 = 1 መ119878 =1
2
211987532
211987512
shortly | ൿ119895 119898119895
the base | ൿ119899 119897 119904 119895 119898119895
ത119871 ҧ119878 =1
2ҧ1198692 minus ത1198712 minus ҧ1198782 = 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
Term symbol
an abbreviated description of the angular momentum quantum numbers in a multi-electron atom
Total wavefunction must be antisymmetric (under interchange of any pair of particle)
Orbital part Spin part
2016-04-28 34
Multi-electron atom2S+1 119871119869
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
120595 Ԧ1199031 hellip Ԧ119903119873 Ԧ1198781 hellip Ԧ119878119873 = 120595 Ԧ1199031 hellip Ԧ119903119873 120594 Ԧ1198781 hellip Ԧ119878119873
Multi-electron wavefunction
Antisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =Exchange interaction
Antisymmetric
Example
A
B
Two electrons localized on one centrum
2016-04-28 35
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Hundrsquos rules ET lt ES
Antisymmetric
2016-04-28 36
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Spin-orbit interaction 119867119878119874 = 120582119871 መ119878 with the base | 119899 119897 119904119898119897 119898119904
For 119904-states 119871 = 0 rArr 119871 መ119878 = 0
2016-04-28 33
Magnetic field and spin
Total angular momentum operator መ119869 = 119871 + መ119878 the base | ൿ119895 119898119895
3
3
2
119871 = 1 መ119878 =1
2
211987532
211987512
shortly | ൿ119895 119898119895
the base | ൿ119899 119897 119904 119895 119898119895
ത119871 ҧ119878 =1
2ҧ1198692 minus ത1198712 minus ҧ1198782 = 119871119911119878119911 +
1
2119871+119878minus + 119871minus119878+
Term symbol
an abbreviated description of the angular momentum quantum numbers in a multi-electron atom
Total wavefunction must be antisymmetric (under interchange of any pair of particle)
Orbital part Spin part
2016-04-28 34
Multi-electron atom2S+1 119871119869
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
120595 Ԧ1199031 hellip Ԧ119903119873 Ԧ1198781 hellip Ԧ119878119873 = 120595 Ԧ1199031 hellip Ԧ119903119873 120594 Ԧ1198781 hellip Ԧ119878119873
Multi-electron wavefunction
Antisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =Exchange interaction
Antisymmetric
Example
A
B
Two electrons localized on one centrum
2016-04-28 35
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Hundrsquos rules ET lt ES
Antisymmetric
2016-04-28 36
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Term symbol
an abbreviated description of the angular momentum quantum numbers in a multi-electron atom
Total wavefunction must be antisymmetric (under interchange of any pair of particle)
Orbital part Spin part
2016-04-28 34
Multi-electron atom2S+1 119871119869
120595 Ԧ119903 119878119911 = 120595 Ԧ119903 120594 119878119911
120595 Ԧ1199031 hellip Ԧ119903119873 Ԧ1198781 hellip Ԧ119878119873 = 120595 Ԧ1199031 hellip Ԧ119903119873 120594 Ԧ1198781 hellip Ԧ119878119873
Multi-electron wavefunction
Antisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =Exchange interaction
Antisymmetric
Example
A
B
Two electrons localized on one centrum
2016-04-28 35
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Hundrsquos rules ET lt ES
Antisymmetric
2016-04-28 36
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Antisymmetric
Example
A
B
Two electrons localized on one centrum
2016-04-28 35
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Hundrsquos rules ET lt ES
Antisymmetric
2016-04-28 36
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
times
Hundrsquos rules ET lt ES
Antisymmetric
2016-04-28 36
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
A B Two electrons localized on two centres
Antisymmetric
2016-04-28 37
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Example
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
times
Chemical bonds ES lt ET
2016-04-28 38
Exchange interactionAntisymmetric wavefunction + Pauli exclusion principle + Coulomb interaction =
Exchange interaction
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Exchange interaction = Coulomb interaction + Pauli principle
Antisymmetric
Heisenberg Hamiltonian
Orbital motion depends on the mutual orientation of the spinsThe effect is purely electrostatic
J gt 0
J lt 0
ferro
antiferro
Exchange interactions
2016-04-28 39
Ψ = 120593119900119903119887119894119905119886119897 times 120594119904119901119894119899
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Kinetic exchange
Exchange interactions
2016-04-28 40
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 41
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 42
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
triplet singlet
Kinetic exchange
Exchange interactions
2016-04-28 43
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
ground state
ground state
excited state
ground state
A B
S = 0 S = 1
Kinetic exchange
Exchange interactions
2016-04-28 44
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
S = 0 S = 1S = 0 S = 1
S = 0
E
Singlet is the ground state
Kinetic exchange
Exchange interactions
2016-04-28 45
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 46
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
No excited states for both spins
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 47
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 48
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
| J1| gt | J2| gt | J3| gt
The superexchange is antiferromagnetic even over long distances
A specal case ndash superexchange
Kinetic exchange
Exchange interactions
2016-04-28 49
There are an excited state for BOTH spinsJ lt 0 (antiferromagnetic exchange)
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Exchange interactions
2016-04-28 50
Mn3+ (d4)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 51
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892
Empty orbitals
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Double exchange (in mixed vallence compounds)
Exchange interactions
2016-04-28 52
Mn3+ (d4) Mn4+ (d3)O(2p)
1199052119892 1199052119892
119890119892 119890119892Mn4+ (d3) Mn3+ (d4)
e119892lowast
t2119892lowast
e119892lowast
t2119892lowast
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Lattice energy Carrier energy
(Zener model RKKY)Indirect exchange
Ferromagnetism
2016-04-28 53
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Lattice energy Carrier energy
(Zener model RKKY)
Ferromagnetism
2016-04-28 54
Indirect exchange
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28 55
Spin density of states
SCIENCE VOL 282 1660 (1998)
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Magnetism of the matter
ndash J
0
0
-gmBH
gmBH
ES
ET
S = 0
S = 1
Example 2 ions of spin S = frac12 J lt 0
119872 =σ119899minus
120597119864119899120597119867
exp minus119864119899119896119861119879
σ119899 exp minus119864119899119896119861119879
120594 =2119873119860119892
2120583119861
119896119861119879 3 + exp minus119869
119896119861119879
2016-04-28 56
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
0 1 2 3 4 5 60
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
20 K
0 1 2 3 4 5 60
500
1000
1500
2000
2500
3000
3500
4000
4500
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
100 K
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
3000 K
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 57
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
0 5 10 15 200
2000
4000
6000
8000
10000
12000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
J= 0 meV
J= -1 meV
ndash J
T = 20 K
0
0
-gmBH
gmBH
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 58
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
0 50 100 150 200 250 3000
500
1000
1500
Temperature (K)
Magnetz
ation (
em
um
ol)
J= 0 meV
J=-01 meV
J=-05 meV
J=-1 meV
J=-10 meV
B = 10 T
0 50 100 1500
20
40
60
80
100
120
140
160
180
Temperature (K)
Magnetz
ation (
em
um
ol)
J = -30 meV
J = -35 meV
J = -40 meV
J = -45 meV
J = -5 meV
Magnetism of the matterExample 2 ions of spin S = frac12 J lt 0
2016-04-28 59
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Experiment
Ewa Goacuterecka Adam Kroacutewczyński Jadwiga Szydłowska Jacek Szczytko
students Paweł Majewski
Department of Chemistry University of Warsaw
Structural Research Laboratory
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Samples
H17C8O
Cu
H17C8O N
N
O
O
OC6H13
OC10H21
OC10H21
OC6H13
H21C10O
H13C6O
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
2016-04-28 61
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
coordinate bonds with lone pairs of electrons
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
M = Ni Cu
Cu
H23C11
Cu
N
N
O
O
N
N
O
O
C11H23
H23C11
C11H231344 2 times Cu2+ biphenyl n = 8
Samples
2016-04-28 62
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
OC8H17
OC8H17
H17C8O
O N OC8H17
OC8H17N
ON
NO
NH17C8O
H17C8O N O
OC8H17
OC8H17
H17C8O
Cu
Cu
2 times Cu2+ pyrazine N = 42955
Samples
2016-04-28 63
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu 2 times Cu2+ oxamide n = 32567
Samples
2016-04-28 64
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
OC8H17
H17C8O
2 times Cu2+ oxamide n = 32356
Samples
2016-04-28 65
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
2 times Cu2+ oxamide n = 32356
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2 times Cu2+ pyrimidine n = 32975
Samples
2016-04-28 66
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
2 times Cu2+ pyrazine n = 42955
2 times Cu2+ oxamide n = 32567
2 times Cu2+ oxamide n = 32356
2 times Cu2+ pyirimidyne n = 32975
74
20 K
100 K
Samples
2016-04-28 67
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ biphenyl n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100
100 K
Samples
2016-04-28 68
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
0 1 2 3 4 5 60
5000
10000
15000
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment
theory J = 0
theory J = - 011294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 69
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
0 1 2 3 4 5 60
20
40
60
80
100
120
140
160
180
200
Magnetic Field (T)
Magnetz
ation (
em
um
ol)
experiment 20 K
theory J = - 45
theory J = - 12
experiment 100 K
theory J = - 45
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
20 K
100 K
100
Samples
2016-04-28 70
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ biphenyl
2 times Cu2+ pyrazine
2 times Cu2+ oxamide
2 times Cu2+ oxamide
2 times Cu2+ pyirimidyne
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30 1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 2 times Cu2+ bifenyl n = 8
2 times Cu2+ pirazyna n = 42955
2 times Cu2+ oksamid n = 32567
2 times Cu2+ oksamid n = 32356
2 times Cu2+ pirymidyna n = 3297510 T
AF + P
Samples
2016-04-28 71
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 50 100 150 200 250 3000
5
10
15
20
25
30
35
40
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment-M(25)
experiment-M(35)
experiment-M(45)
experiment
theory J = -45 meV
theory J = -25 meV
10 T
Samples
2016-04-28 72
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
0 10 20 30 40 50 60 70 80 90 100 1100
10
20
30
40
50
60
70
80
90
100
110
Temperature (K)
Magnetization (
em
um
ol)
experiment
theory J = -53 meV
difference
AF + P
Samples
2016-04-28 73
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
0 1 2 3 4 5 60
100
200
300
400
500
600
700
Magnetic Field (T)
Magnetization (
em
um
ol)
Cu 2975
300K
50K
10K1294 1 times Cu2+
Cu2+ndash n ndash Cu2+
1344 n = 8
n = 42955
n = 32567
n = 32356
n = 32975
J = - 53 meV
Samples
2016-04-28 74
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2 times Cu2+ bifenyl
2 times Cu2+ pirazyna
2 times Cu2+ oksamid
2 times Cu2+ oksamid
2 times Cu2+ pirymidyna
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetz
ation (
em
um
ol)
experiment
theory J = - 30
0 50 100 150 200 250 300 35010
20
30
40
50
60
70
80
90
100
Temperature (1K)
Susceptibili
ty (
em
um
olT
)
01T
1T
30 100
Results
2016-04-28 75
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
C9H19
H17C8O
O
N
N
O
O
Cu
H9C19
OC8H17
N
N
O
Cu
2567
OC8H17
H17C8O
N
N
O
N N
N
O
OC8H17
OC8H17
N
O
H17C8O
H17C8O
OC8H17
O
OC8H17
OC8H17
OC8H17
Cu Cu
2975
212 SSJH
AFJJ 3 FAF JJJ 3
superexchange
indirect
exchange
lt0
lt0 gt0
Hypothesis
2016-04-28 76
Cu2+ndash 3 ndash Cu2+ Cu2+ndash 3 ndash Cu2+
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
OC8H17H17C8O
NN
OO
Ni
N
N
O
O
O
N
O
N
H19C9
C9H19 H19C9
C9H19
2763 agata
Samples
2016-04-28 77
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O
Cu
H17C8O N
N
O
O
OC8H17
OC8H17
OC8H17
OC8H17
H17C8O
H17C8O
Ni
Samples
2016-04-28 78
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 6-20
0
20
40
60
80
100
120
140
Magnetic Field (T)
Magnetization (
em
um
ol)
Nano Ni 2763 Agata Bis
10K Bis
300K Bis
10K
Samples
2016-04-28 79
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
5
10
15
20
25
30
Temperature (K)
Magnetization (
em
um
ol)
010 T
MFA
0 05 1 15 2 250
10
20
30
40
50
60
70
80
90
100
110
Magnetic field (T)
Magnetization (
em
um
ol)
100 K
Samples
2016-04-28 80
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
H17C8O OC8H17
NN
O
NN
O
O
O
NN
O
ONi
H19C9
C9H19 H19C9
C9H19
Szydłowska Szczytko et alCHEMPHYSCHEM 11 1735-1741 (2010 )
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Samples
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 10 20 30 40 50 60 70 80 90 1000
001
002
003
004
005
006
Temperature (T)
Magnetization (
M)
0001 T
0001 T
0005 T
002 T
005 T
01 T
10 T
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 1 2 3 4 5 60
1
2
3
4
5
6
7
Magnetic Field (T)
Magnetization (
em
ug
)
Ni 2763
300K
10K
Samples
2016-04-28 83
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
005
01
015
02
025
Temperature (K)
Magnetization (
em
ug
)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 84
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Isomeric bimetallic copper(II) Cu2+ and nickel(II) Ni2+ complexes
2763 1 times Ni2+
Ni2+ndash n ndash Ni2+
1421 1 times Ni2+
0 50 100 150 200 250 3000
10
20
30
40
50
60
Temperature (K)
1S
usceptibili
ty (
em
ug
T)
Ni 2763
01T 10-300K
01T 300-10K
Samples
2016-04-28 85
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Spintronic devices
2016-04-28 86
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
httphyperphysicsphy-astrgsuedu
Stern-Gerlach experiment (1922 r)
Spintronic devices
2016-04-28 87
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Spintronic devices
2016-04-28 88
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Spintronic devices
2016-04-28 89
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Spintronic devices
2016-04-28 90
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Spin filter
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spintronic devices
2016-04-28 91
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Spin-filter
2016-04-28 92
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Spin-filter
2016-04-28 93
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Spin-filter
2016-04-28 94
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Spin-filter
2016-04-28 95
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Spin-filter
2016-04-28 96
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Spin-filter
2016-04-28 97
httpwwwupscaleutorontocaGeneralInterestHarrisonSternGerlachSternGerlachhtml
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28 98
Giant Magnetoresistance
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
(Zener model RKKY)
Ferromagnetism
2016-04-28 99
Indirect exchange
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28 100
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28 101
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28 102
(in)organic spintronics
SCIENCE VOL 282 1660 (1998)
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28 103
(in)organic spintronics ndash spin valve
J Phys D Appl Phys 33 (2000) 2911ndash2920
The spin-valve transistor
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Diluted Magnetic Semiconductors
2016-04-28 104
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28 105
(in)organics spintronics ndash spin valve
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Magnetic tunnel junction (MTJ)
Ferromag (soft)
Insulator (barrier)
Ferromag (hard)
Ferromag Co Py FeCo etc
BarrierAl2O3 MgO etc
TMR()=(RAP-RP)RP 100
Takahiro Moriyama httpwwweceudeledu~appelbauspintronics
Spintronics
2016-04-28 106
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28 107
Giant Magnetoresistance
MgO
Spin-dependent tunneling conductance of Fe|MgO|Fe sandwichesW H Butler X-G Zhang T C Schulthess and J M MacLarenPhys Rev B 63 054416 (2001)
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28 108
Organic Spintronics ndash spin valve
2004
Molecular spin valves
Alq3 hydroxy-quinoline aluminium
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28 109
Organic SpintronicsS Sanvito Nature Physics 6 562 (2010)
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28 110
Organic Spintronics
Nicolae Atodiresei and Karthik V Raman
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28 111
Organic Spintronics
Nicolae Atodiresei et al Phys Rev Lett 105 066601 (2010)
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28 112
Organic Spintronics
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28 113
Organic Spintronics
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28 114
Fe2+ (d6)
Crystal field (CF) splitting
119889119899
Crystal field splitting (the presence of the ligants)rArr quenching of the orbital momentum
Organic Spintronics
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28 115
Organic Spintronics
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28 116
Organic Spintronics
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28 117
Organic Spintronics
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Organic SpintronicsRare-earth complexes
Spin qbits
E Coronado
HoW10
Ground state 119898119869 = plusmn4
LnW30
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28 119
Organic Spintronics
Long spin relaxation time due to the small spin-orbit couplin and small hyperfineinteraaction rArr spin qbits
M Shiddiq D Komijani Y Duan A Gaita-Arino E Coronado S Hill ldquoEnhancing coherence in molecular spinqubits via atomic clock transitionsrdquo Nature 531 348 (2016)
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28 120
Light
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28 121
bdquoStandardrdquo spintronicsbull There is a need for new materials (spin filters spin transistors ndash Diluted Magnetic
Semiconductors Ferromagnetic Semiconductors etc)
bull There is a hope for new phenomena
GaMnAs
(light polarization swithing magnetization on and off etc)
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Magnetic Semiconductors
2016-04-28 122
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28 123
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28 124
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28 125
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
E Coronado
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28 126
Organic SpintronicsElectroluminescence control using Magnetic field(Magneto-Electro Luminescence (MEL) effect)
Injection of chargeacute (e- h+) in the EL deviceleads to the formation of two types of excitons
Singlet Triplet
25 75
Bright Dark
In a spin valve the current is spin polarized rArr by applying an external magnetic field the ratio single-triplet (and thus electroluminescence EL) should be controlled
E Coronado
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28 127
Organic Spintronics
E Coronado et al Nature Chemistry 2 1031ndash1036
(2010) doi101038nchem898
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28 128
Organic Liquid Crystals Spintronics
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28 129
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28 130
Organic Spintronics
Piotr Kaszyński Jacek Szczytko et alJACS 134 (5) 2465-2468 (2012)CHEM COMMUN 48 7064-7066 (2012)JACS 136 (42) pp 14658-14661 (2014)LIQUID CRYSTALS 41 1653-1660 (2014) LIQUID CRYSTALS 41 385-392 (2014) J OF MATERIALS CHEMISTRY C 2 319-324 (2014)
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28 131
Organic Spintronics
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28 132
Organic Spintronics
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28 133
Organic Spintronics
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
2016-04-28 134
Organic Spintronics
supercooled liquid
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Spintronics
High-speed high-density nonvolatile memory
Reconfigurable logic devices
Integrated magneto-optical devices
Quantum information processing with spin
Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Magnetic Devices
Non-volatile memory
Storage (HDD floppy streamer)
Magneto-optical devices
Optical isolators (Faraday rotation)
2016-04-28 135
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS
Organic SpintronicsOrganic Semiconductor DevicesTransistors
IC LSI porcessors
Diodes (LED Lasers)
Memory (RAM EPROM FLASH)
Optical Devices
Telecomunication (fibres amplifiers)
Diodes (LED Lasers)
Photo detectors
Organic Magnetic Devices
2016-04-28 136
SPINTRONICS