Department of Chemistry (Chemicum) research in society from basics to applications research-based education knowledge in service Welcome to the Department.

Department of Chemistry (Chemicum)

research

in society

from basics to applications

research-based education

knowledge in service Welcome to the Department of Chemistry!

Department Composition (education)

• Laboratory of Analytical Chemistry Inorganic Chemistry Organic Chemistry Physical Chemistry Polymer Chemistry Radiochemistry

• Centre for Chemistry Education

• Chemistry ICT Center (eChemicum)

• Laboratory for Instruction in Swedish

• VERIFIN

Strategic Focuses in Research (2004-2006)

Green chemistry

Material and nanochemistry

Computational and theoretical chemistry

Science teacher education and its

reseach

Green Chemistry is the use of chemistry for pollution prevention.

More specifically, green chemistry is the design of chemical

products and processes that are more environmentally benign.

.

Micro- and optoelectronics

Space applications

Nuclear waste purification

Biomaterials

Pharmaceuticals

MATERIALS CHEMISTRY

Application areas

MOSFET transistor

Grid filter for X-ray detector

Polysilicon

Spacer, by ALD?

Metal oxide gate-dielectric, by ALD?

Metal gate,by ALD?

SourceSi-substrate Drain

CoSi2

Channel

.

Templating by porous materials→ nanowires, nanorods Templating by fibers → nanotubes Electrospinning → nanowires, nanotubesPatterning with SAMsNanoparticlesSmart polymers and materials

MAKING OF NANOMATERIALS

.

Nanowires, nanorods coated by ALDGlancing angle evaporation Patterning with SAMsStar polymersBlock copolymers

MAKING OF NANOSTRUCTURES

+ oblique evaporation

+ electrodeposition

+ dissolution of alumina

+ ALD

free standing porous alumina

.

Dielectrics for gate oxides in MOSFETs

Dielectric films for DRAMs and FERAMs

Metal films

Nitride films for barriers

THIN FILM MATERIALS FOR MICROELECTRONICS

Al2O3 film deposited by ALD from AlCl3 and Al(OiPr)3.

14 nm TiN

TiCl4 + Zn + NH3 TiNin collaboration with Intel

In collaboration

with NIST

INORGANIC IX MATERIALS: ”ION SIEVES” FOR HIGHLY SELECTIVE RADIONUCLIDE

SEPARATIONS

EXAMPLES:

S

HOOC

S

ON

CH3

CNH

CN

(Cpa-RAFT-PNIPAM Mn = 6450 PDI = 1.11)

55

CH3

HOOCS

S

(Cpa-RAFT-PS Mn = 10000 PDI = 1.07)

94

Gold nanoparticles with hydrophilic and hydrophobic polymer grafts

PNIPAM

PS

+ HAuC l4 Au

PNIPAM /PS-M PC

Development of miniaturized analytical devices

• Electrospray devices–PDMS

–SU-8

• Miniaturized atmospheric pressure chemical ionization (APCI) and photoionization sources (APPI)

(B ) (C )

m/z

100 150 200 250 300 350 400 450 500

Abso

lute

inte

nsi

ty [

cps]

0

1e+7

2e+7

3e+7

4e+7

5e+7

[M+H]+

(A)

O

H

H

OH

H

TIC +MRM: 455,2/165,1amu ja 455,2/ 303,4 amu

0,00E+00

1,00E+05

2,00E+05

3,00E+05

4,00E+05

5,00E+05

6,00E+05

0 10 20 30 40 50 60

time, min

inte

nsit

y, c

ps

Development of miniaturized analytical devices

• Methods based on porous silicon–Desorption Ionization On Silicon (DIOS)

–Filtration devices

• SU-8 microchannels for CE

laser MS

porous area sample

Midazolam MW: 325

Milestones in noble-gas chemistry

• First compounds predicted already in 1902!

• Pauling 1933: XeF6 and KrF6 should be preparable.

• Bartlett 1962: first noble-gas compound, Xe[PtF6].

• In matrices: First : KrF2 (Turner and Pimentel, 1963). Others: XeCl2 (Nelson and Pimentel, 1967); ClXeF (Bondybey, 1971).

• Strong interactions in matrices: Cr(CO)5---Rg (Perutz and Turner, 1975); Rg---BeO (Thompson and Andrews, 1994).

• XeAuF (Cooke and Gerry, 2004).

• HRgY Pettersson et al., 1995-)

2300 2200 2100 1300 1250 1200 1150 1100

0.0

0.5

1.0

1.5

2.0

2.5

C

B

A

XeH

2

HXeIab

sorb

ance

wavenumber (cm-1)

HI

photolyzedinitial sampleHI/Xe, 1:1000

annealed to 45 K

18

Noble gas hydrides

Ar Kr Xe

HXeHHXeIHXeBr

HKrCl HXeClHArF HKrF

HKrCN HXeCNHXeNCHXeOHHXeOHXeSHHXeNCO

HKrCCH HXeCCHHXeCCXeHHXeCC

HKrC4H HXeC4H

H Xe I1.68 Å 3.1 Å

+0.129 +0.347 -0.476MP2/43333/433111/41111(Xe, I)/6-311++G(3d,3p) (H)

Van der Waals -distances:

H Xe3.8 Å 4.3 Å

I

Experimental: 1-

Xe-H cm11931-

Xe)-(Hcm2200

(HNg)+ + Y-

H + Ng + Y

Avoided crossing

HNgY molecules correlate with neutral atomic asymptote

H-Ng-Y

1980 1970 1960

-0.1

0.0

0.1

HF / 36Ar

HF / 40Ar

H-A

r st

r.

Abso

rbance

690 680

H-A

r-F b

end.

440 430

F-A

r st

r.

1480 1470 1460 1450

0.0

0.1

DF / 40Ar

D-A

r st

r.

Abso

rbance

520 510

Wavenumber (cm-1)D

-Ar-

F b

end.

440 430

F-A

r st

r.

Effect of isotopic substitution on the fundamentals of HArF

132.9 196.9

Predicted organo-Ng-molecules

• Numerous Xe-containing organic molecules are known, normally containing F.

Examples:• R2Xe, where R = C6F5 or 2,4,6-C6H2F3

• [CF3CCXe][BF4]

• So far, no organic Ar compounds known. • Non-halogen containing organic molecules predicted in 2002:

Lundell et al. J. Phys.Chem. A 106 (2002) 11950.

HXeC6H5

HXeCCH

HXeOC6H5

HXeCCXeH

Predicted organo-Ng-molecules

• The MP2/LJ18/6-311++G(2d,2p) calculated structure and Mulliken charges of HCOOXeH

• Works for larger acids, glycine, alanine and valine.

• J. Lundell et al., Computers&Chemistry, 24 (2000) 325-330.

Xe H

Acetylenic systems

• HNgC6H and HNgC8H-molecules expected to be more stable than HNgC4H and HNgC2H

• First halogen-free organic Xe compounds.

• First organic Kr compounds.

• Challenge: Organic Ar-compound!

C2H 2.956

C4H 3.558

C6H 3.809

C8H 3.996

Electron affinity:

• Electron affinity of C2nH radicals localized at the C end.

Bond lengths

(Kr) 1.58 2.26 1.24 1.37 1.22 1.06

(Xe) 1.74 2.33 1.24 1.37 1.22 1.06

(Xe) 1.75 2.32 1.23 1.06

(Kr) 1.60 2.25 1.23 1.06

MP2/LJ18(Xe)/6-311++G(2d,2p) level

Recent computational predictions

• H-Xe-CC-H

• H-Xe-CC-Xe-H

• H-Xe-CC-Xe- CC-Xe-C C-Xe-...-H• E. C. Brown, A. Cohen and B. Gerber, JCP, 122 (2005) 171101.

• F-Kr-CC-H

• F-Kr-SiF3

• S. Yockel, A. Garg, A. Wilson, CPL., 411(2005)91.

Applications?

• Very high energy compounds, could form solids!

• Specific activation of functional groups: ”Xe-catalysis”.

• Function of Xe in aenesthesia

• Solving the ”missing Xe-problem”