Faculty of Physics and Applied Computer Science, AGH University of Science and Technology, Krakow, Poland email: [email protected]Janusz Tobola Electronic structure and transport properties (II) complex multi-atom systems with metal-semiconductor transition G = G 0 + G 0 VG GDR-Thermoelectricite, 5-9 may 2008, Carcans-Maubuisson
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Electronic structure and transport properties (II)
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Faculty of Physics and Applied Computer Science, AGH University of Science and Technology,
Electronic structure and transport properties (II)
complex multi-atom systems with
metal-semiconductor transition
G = G0 + G0VG
GDR-Thermoelectricite, 5-9 may 2008, Carcans-Maubuisson
CollaborationT. Stopa, B. Wiendlocha, S. Kaprzyk Faculty of Physics and Applied Computer Science AGH, Kraków, Poland
D. Fruchart, E. K. HlilInstitut Neel CNRS, Grenoble, France
B. Malaman, G. VenturiniLCSM Université H. Poincaré, Nancy, France
L. Chaput, C. Candolfi, B. Lenoir, P. Pecheur, H. Scherrer Laboratoire de Physique des Materiaux, Ecole des Mines, Nancy, France
A. Bansil Northeastern University, Boston , USA
GDR-Thermoelectricite, 5-9 may 2008, Carcans-Maubuisson
PLANBasic thermoelectric effects in solids
Double goal of ab initio electronic structure investigations :- fundamental (computations of electron transport from „first principles”)- practical (search for optimal thermoelectrics with maximum of ZT)
View on TE materials vs. Fermi surface peculiarities Thermoelectric „tetragon” – Onsager coefficients.Boltzmann transport equation (relaxation time approximation),Formulas for transport coefficients (electrical conductivity, thermopower, Hall coefficient,
Lorentz factor).Used methods to study electronic structure and electron scattering in
ordered systems (FLAPW, rigid band app + constant relax. time) disordered alloys (KKR-CPA, complex bands, kinetic parameters of electrons).Illustrative examples of theoretical results vs. experimental measurements
Skutterudites (normal and partly filled),Heusler and half-Heusler alloys,Zintl phases (3-3-4 type)
Chevrel phases.
GDR-Thermoelectricite, 5-9 may 2008, Carcans-Maubuisson
Investigations of electronic states near the Fermi surface E(k)=EF
mkkk
kE zyx
2)(
)(2222 ++
=
Thermoelectric properties Resitivity
Thermopower
Thermal conductivity
ZTFigure of
merit
ρ
S
κ
ZT
INS SC M
A. Joffe
COOLING ELEMENTSη = (TH-TC)(γ−1)(TC+ γTH)−1
POWER GENERATORSη = (γTC-TH)[(TH -TC+ (γ+1)]−1
γ = (1+ΖΤ)1/2
Thermoelectric “tetragon”
LEE LET
LTE LTT
j
q
E
-∇T
Π = S T (Kelvin-Onsager) LET=LTE/ T
κ/σ ≈ L0 T (Wiedemann-Franz, L0 liczba Lorentza) κ ≈ -LTT
∇−
=
T
ELL
LL
qj
TT
ET
TE
EE
Electrical current
Heat current
Electric field
temperature gradient
Ohm, 1826
Fourier, 1822
Seebeck, 1821Peltier, 1834
Volta (1800) - battery, Ampere (1820) – two conductors with currents,Faraday (1831), Gauss (1832), …
Seebeck effect (1821)
∇−
=
T
ELL
LL
qj
TT
ET
TE
EE
Temperature gradientElectric field E= S ∇ T
thermopower
1770 Tallin1854 Berlin
S = LEE-1LET
Explanation : thermomagnetism - „magnetic” polarisation of metals and alloys due to the difference of temperature !!
Vivid personality of the Romaticism
- new theory of colours (with Goethe) opposite to the theory of Newton,
- temperature gradient causes changes of magnetic field of Earth !!,- Oersted’s experiments (1820) „blind” scientists.
Fourier relation (1822)
∇−
=
T
ELL
LL
qj
TT
ET
TE
EE
Heat current Temperature gradientq= -κ ∇ T
Thermal conductivity κ = LTELEE-1LET - LTT
∇q = qgen- du/dtdu/dt =ρ c dT/dt
∇(-κ ∇ T)+ ∂T/ ∂t =qgen
∇2T+ (ρc/k) ∂T/∂t = 0
when qgen=0
Heat conducted(balance)
= Heat generated in system
- Heat accumulated
in system
1768 Auxerre1830 Paris
T k mn
23
B τ=κ
Ohm law (1826)
Ohm’s study inspired by works of Fourier and Seebeck
Co : 8c (1/4,1/4,1/4)Sb : 24g (0,u,v)void: 2a (0,0,0)
u=0.335, v=0.159
Filled skutterudites RT4X12 (e.g. LaFe4Sb12)
Fe : 8c (1/4,1/4,1/4)Sb : 24g (0,u,v)La: 2a (0,0,0)
Name from Skutterud (place in Norway), important resource of cobalt-The most extended investigations in the world (last 15 years) within the thermoelectric materials (USA, Japan, France, Germany, Poland, ...) Systems close to realize the concept of Slack (1995) :
PGEC =„phonon-glass electron crystal”GOOD electrical conductivity like in metals
(by doping/substitution), HIGH thermopower – position of the Fermi level near the energy gap on the DOS slope, LOW thermal conductivity like in amorphous – due to specific scattering of phonons „rattling”
Doping in skutterudite CoSb3
Im-3 space group No. 204 (bcc)
Co : 8c (1/4,1/4,1/4)Sb : 24g (0,u,v)void: 2a (0,0,0)
u=0.335, v=0.159
Filled skutterudites RT4X12 (e.g. LaFe4Sb12)
Fe : 8c (1/4,1/4,1/4)Sb : 24g (0,u,v)La: 2a (0,0,0)
n & p types: Co site (Fe,Ni) lub vacancy site (La, Nd)
CoSb3 (density of states)
- narrow energy gap at EF ,
- strong hybridisation between p-states of Sb and d-states of Co,
- the theoretical value of gap strongly depends on the structural parameters, mostly Sb positions, Sofo et al., PRB ’98
- present KKR results support this conclusion, Eg=0.17 eV (0.2 eV)(a=8.94 A, u=0.3328, v=0.1599)
Eg =60-70 meV ) this work(a=9.034 A, u=335, v=0.158
close to results of Akai et al. ICT ’97Wojciechowski, JT et al., JALCOM (2003)
DOS vs. transport function σ(E)
Small substitution/doping 0.01-0.05 el. per Co4Sb12 → ∆EF≈1-2 mRy
Chaput, … JT, PRB (2005)
Doped CoSb3 : FS vs. Hall concentration (rigid band)Chaput, … JT, PRB (2005)
Constant relaxation time (only one free parameter selected in order to gain the best fits to experimental resitivity curves, includes also lattice contribution) (τ ~ 10-14 s)
Experiment (literature) FLAPW calculations
Constant relaxation time – NOT important, since Seebeck coefficient Does not depend on this parameter – Excellent test for theory !!
Doped CoSb3 : thermopower
Experiment (literature) FLAPW calculations
S(T) = e(3Tσ)-1 ∫ dE N(E) v2(E) E τ(E,T) [-∂f(E)/∂E ]
Doped CoSb3: Lorentz factor& effect of band gap on thermopower S
Chaput, … JT, PRB (2005)
C
ATTENTION: one must be careful when estimating lattice contribution to thermal conductivity using Wiedemann-Franz law & total thermal conductivity measurements – it can appear NEGATIVE !
FLAPW calculations
Band gap effect on S:Eg=0.05 eV (green)Eg=0.22 eV (red)
Validity of rigid band approximation in Ni(Ti,Hf)Sn
FLAPW (ordered)
Close agreement between different codes well justifies using a rigid shift of the Fermi level when simulating different size of doping.
Chaput, JT, et al., PRB (2007)
Thermopower computations in Ni(Ti,Hf)SnS – nH correlation
Chaput, JT, ...., PRB (2007)
Calculated thermopower in Ni(Ti,Hf)Sn
Different approximations: - constant relaxation time,- constant mean-path,- free electron.
Chaput, JT, ...., PRB (2007)
Transport properties in disordered systems (KKR-CPA methodology)
The idea of Butler (1980-82) of complex energy bands applied to study metallic alloys as Ag-Pd, Ag-Cu, etc.
In alloys (solid state systems containing chemical disorder) the electronic energy bands are „fat-fuzzy” related to finite life-time of excited carriers.
Mattheissen rules (contributions to total resistivity coming from different relaxation/scattering mechanisms are additive quantities:
At low temperature electrical conductivity is in general dominated by various types of disorder.
Information on the Fermi surface (with complex energy) from the KKR-CPA computations allows for finding kinetic parameters of electrons (velocities and life-times depending on k-vector). It permits next determining transport coefficients (residual resitivity, thermopower)
...ef
+++=321
1111ττττ
Multiple Scattering Theory (1) Dyson equations
Crystal potential
Free-electron Green function
Path-scattering operator (for many potentials)
Scattering operator t for single potential v
Multiple Scattering Theory (2)
KKR-constants matrix
Expression of full GF
Korringa-Kohn-Rostoker method
and
Free-electron part
Regular part
In spherical muffin-tin model matrices are site-diagonal
KKR-CPA method (code S. Kaprzyk)
Lloyd formula Kaprzyk et al. Phys. Rev. B (1990)
CPA
Densityof states
Green function
Fermi energy N(EF)=Z
Korringa-Kohn-Rostoker with coherent potential approximation
Bansil, Kaprzyk, Mijnarends, JT, Phys. Rev. B (1999) conventional KKR
Stopa, Kaprzyk,JT , J.Phys.CM (2004)novel formulation of KKR
Novel formulation of the KKR equations
- monotonic dependence of eigenvalues with energy,- very important in the case of many bands – huge, complex systems !! - numerically easy to find bands E(k),
Adequate normalisation of Schrodinger eq. solutions
diagonalisation of full Green function
Ground state properies KKR-CPA code (S. Kaprzyk)
Total density of states DOS
Component, partial DOS
Total magnetic moment
Spin and charge densities
Local magnetic moments
Fermi contact hyperfine field
Bands E(k), total energy, electron-phonon coupling, magnetic structures, transport properties, magnetocaloric, photoemission spectra, Compton profiles, superconductivity, …
Metal–semiconductor-metal crossovers
Seebeck coefficient Resistivity
FeTiSb (VEC=17)Curie-Weiss PM
(0.87µB)NiTiSb (VEC=19)
Pauli PM JT et al., PRB (2001)
1-hole system 1-electron system
p
n
Resistivity
Semiconductor from alloyed metals
Density of states at EF
M SC M
JT, et al., PRB (2001)
Complex energy bands & Fermi surface
Stopa, JT, Kaprzyk, European Conference on Thermoelectrics 2004
semiconductorx =0.50
FS pecularities
Group velocity
Life-time
)(ERev k kk ∇=
1
)Eh
k k( Im=τ
Influence of disorder on residual resistivity & thermopower
Stopa, JT, Kaprzyk, European Conference on Thermoelectrics 2004
a (Å)Compound corresponding mixtures were first molten in an induction furnace in a water cooled copper crucible;
resulting ingots were sealed in silica tube under argon and annealed during one week at 1073K;
purity of the sample was checked by powder X-ray diffraction (Guinier camera Co Kα);
cell parameters have been refined by a least square procedure from powder X-ray diffraction data recorded with high purity silicon (a = 5.43082 Å ) as internal standard.
New alloys with M-SC-M transitionstheoretical predictions (1)
JT et al., JALCOM (2004)
JT et al., JALCOM (2004)
New alloys with M-SC-M transitionstheoretical predictions (II)
Not many semiconductors of R3T3X4 comparing to the Heusler XYZ phases. different unit cells
12 atoms in MgAgAs-type 40 atoms in Y3Cu3Sb4-type→ bigger problem for electronic structure computations
Cava et al., APL (2001)
Electronic structure of Y3Cu3Sb4
zoom near Fermi level
Y3Cu3Sb4Partial density of states
Energy gap (or pseudo-gap ?) appears near the Fermi level,due to strong hybridisation p-states of Sb and d-states of R,d-Cu states form a large peak well below EF ( plays a role of electron „reservoir” filling bonds completing VEC=62).
Electronic structure of La3Cu3Sb4
zoom near Fermi level
La3Cu3Sb4partial density of states
In comparison with Y3Cu3Sb4, bands are narrower in La3Cu3Sb4, but interestingly, states near EF suggests rather pseudogap than the true energy gap.
Dispersion curves E(k)
Eg ~ 0.1-0.2 eVKKRThe value of computed band gap strongly depends on applied positional parameters of Sb
Young et al., APL (1999)FLAPW Eg=0.23 eV (Y3Cu3Sb4)Eg=0.61 eV (Y3Au3Sb4)
Y3Cu3Sb4 similarly in La3Cu3Sb4
Experimental dataElectrical resitivityThermopower
Thermal conductivitySkolozdra et al.. Acta Phys. Pol. (2002)
+28.4+56.8+85.2
+38 +20+72 +39+100 +63
100 K200 K300 K
TheoryExper.Temperature
S(T) = AT + BT3 + …
S/T (µV/K2) = 0.2877 x 10-2 d lnNtot(E)/dE Ntot(E) (states/Ry) at E=EF
σ(E) ~Ntot(E) μ(E)
Mott formula
La3Cu3Sb4 Simplified estimation of thermopower from DOS
Residual electrical conductivity
Seebeck coefficient
S/T (µV/K2)=0.28 (±0.05 !!)Very sensitive on EF position !!
Half-Heusler compounds: RCuSb (hypot.)
LaCuSbLarge peak at EF
tentatively explainsPreference of ZintlstructureBut it is less evident in the case of YCuSb
More detailed analysis of total energy necessary to give answer – a difficult task40 atoms in unit cell !!
Chevrel phases
R-3 (rhomboedral) Mo (6f) : (x,y,z)Se (6f) : (x,y,z)Se (2e) : (x,x,x)M (1a) : (0,0,0) big cations (Sn, Pb)M (6f) : (x,y,z) small cations (Cu, Zn)
P-3 triclinicboth open structures
MX(2)
X(1)Mo
Crystal parameters of lattice structure
Search for Chevrel phases as thermoelectrics Band structure calculations:
Roche et al. (1998) TB-LMTO; Roche et al. (1999) KKR
TiMo6Se8
Cd2Mo6Se8
Resistivity experiments
CrMo6Se8
TiMo6Se8
Zn2Mo6Se8
Search for Chevrel phases as thermoelectrics (2) Band structure calculations:
Mo6Se8
Zn2Mo6Se8 (narrow gap Eg<0.1 eV)
Singh et al. (1999) FP-LAPW
LixMo6Se8
jiij kk
EM∂∂
∂=−2
1)(
Effective masses
me= 0.2 mo
mh = 1.2 mo
JT et al. (1999) KKR
Thermoelectrical properties of Chevrel phases Thermopower Resistivity
Thermal conductivityCaillat et al., Solid State Sciences (1999)
The best ZT for TixMo6Se8
ZT = 0.6 at T=1100 K
Very low thermal conductivity ! 0.1 W/(K m)
Chevrel phases with defects (2)
MSe(2)X
Mo
Real samples: TixMo6Se8-y, SnxMo6Se8-y
defects not only in M network but also in Se sublattice
DOS in ordered Chevrel compounds
total
Se
Mo
Ti
s-states4 holes
2 holes
Semiconductor or semimetal
Ti
total
TiMo6Se8 – a very narrow gap semiconductor
KKR calculations
FLAPW calculations
KKR-CPA DOS in Mo6Se8-y with defectstotal Mo Se
JT, Pecheur, ....,J. Phys. CM (2003)
KKR-CPA DOS in TiMo6Se8 with defectstotal Mo Se Ti