Solid State Chemistry Meets

Physcis: Thermoelectric Materials

AN INTERDISCIPLINARY COLLABORATION
TIM HOGAN
MSU, E. ENGINEERING
MEASUREMENTS

S. D. MAHANTI
MSU, PHYSICS
Theory

C. KANNEWURF
Northwestern Univ
E. Engineering

KANATZIDIS
KANATZIDIS
MSU,CHEMISTRY
CHEMISTRY
MSU,
SolidState
StateChemistry
Chemistry
Solid
Synthesis,Discovery
Discovery
Synthesis,

H. Schock, T. Shih
MSU, Mechanical
Engineering
Applications

Ctirad
Ctirad UHER
UHER
Univ
of
Michigan
Univ of Michigan
Physics
Physics

Michigan State University

THERMOELECTRIC POWER
(Seebeck Coefficient)
V

Smeasured=

V
T

Smeasured= Ssample-SCu
sample

Cu block

heater
Cu block
constantan

zero current technique:

extremely useful probe
for investigation of
intrinsic conduction in
granular or polycrystalline
materials

Thermoelectric Applications
Microprocessor
Cooler
www.tellurex.com

Biological samples
Beverage cooler

LASER diode
Cooler

Heat to Electric Energy

Up to 20% conversion efficiency with

right materials

Thermoelectric Benefits

TE coolers have no moving parts, need substantially

less maintenance.
Life-testing has shown the capability of TE devices to
exceed 200,000 hrs. of steady state operation.
TE coolers contain no chlorofluorocarbons.
Temperature control to within fractions of a degree can
be maintained using TE devices.
TE coolers function in environments that are too
severe, too sensitive, or too small for conventional
refrigeration.
TE coolers are not position-dependent.

How does it work?

http://www.designinsite.dk

Thermoelectric applications
Air conditioning (distributed,
environmentally friendly)
Spot cooling of electronic chips,
superconductors etc.
Thermal suits for fire-fighting, soldier etc
Waste heat recovery (automobiles, utilities
etc)
Geothermal power generation

Figure of Merit
electrical conductivity

thermopower

S
ZT =
T
total
2

Total thermal conductivity

Power factor

Todays situation
The most efficient materials today is Bi2Te3
alloy
ZT~0.8-1.0
Further improvements on Bi2Te3 are not
expected.
New materials are needed

Thermoelectric Properties of Optimized Bi2Te3

(e.g. Bi2-xSbxTe3, Bi2Te3-xSex) at Room Temperature

S ~ 220 V/K
~ 950 S/cm
=1/ ~ 1.1 mcm
~ 1.5 W/mK

ZT ~ 1 !

ZT

ZT~1

200

300

T, K

400

Structure of Bi2Te3 and NaCl

NaCl

Bi2Te3 defect NaCl

x
x

TYPICAL BEHAVIOR OF
MATERIALS
semiconductor-like

metal-like

S>50 V/K
S (V/K)

0<S<20 V/K
S (V/K)
p-type

p-type

SMALL

LARGE
T (K)

T (K)
n-type

n-type

-20 V/K<S<0

S>-50 V/K

Power Factor (S2*) vs Carrier

Concentration
conductivity
Thermopower, S

1017

1018

S2*

1019

1020

Carrier Concentration, cm-1

1021

Thermopower and Electronic

Structure

S=

k T d(ln (E))
2 2
B

3e

dE

E = E

Mott Equation

(E) is the electrical conductivity

determined as a function of band filling
or Fermi energy, EF. If the electronic
scattering is independent of energy, (E)
is just proportional to the density of
states (DOS) at EF.
For maximum S, a large asymmetry in the
DOS and/or scattering within a few kT
above and below the Fermi energy is
required.

Band structure Types

E
E

Ef

simple

simple

complex

ZT and Band Structure

B- parameter

CT 5 / 2 mx my m z x

ZT

0.1 -

latt

m= effective mass
= mobility
latt= lattice thermal conductivity
T = temperature
= band degeneracy
High comes with
(a) high symmetry e.g. rhombohedral, cubic
(b) off-center band extrema

1.0 -

0.01

0.1

1.0

10

B-parameter

CB

Energy

B=

10

Ef
VB

Desirable characteristics
Multiple peaks and valleys in
valence/conduction band
Heavy carrier masses
Flat bands

Selection criteria for candidate

materials
Narrow band-gap semiconductors
For operation at room temperature

Heavy elements
High mobility, low thermal conductivity

Large unit cell, complex structure

low thermal conductivity

Highly anisotropic or highly symmetric

Complex compositions
low thermal conductivity, electronic structure

Important Issue:
Thermal Conductivity
Slacks proposal: Phonon-Glass/ ElectronCrystal (PGEC)
Rattling Ions in the lattice: watch thermal
displacement parameters
o

o
o

o
o

o
o

o
o

o
o
o
o

o
o

Crystalline solid

Rattling ions in cavities

or tunnels
scatter heat-carrying phonons

Reaction Chemistry
Investigating the System:
A2Q + PbQ + Bi2Q3 > (A2Q)n(PbQ)m(Bi2Q3)p
Map generates target compounds

A=K, Rb, Cs
Q=Se, Te

A2 Q

Phases shown
are promising new TE
Materials
CsBi4Te6
Rb0.5Bi1.83Te3
APb2Bi3Te7

K5Bi17Se28

A1+xPb4-2xBi7+xSe15

PbQ
Pb6Bi2Se9

Pb5Bi6Se14 Pb5Bi12Se23

-K2Bi8Se13

Bi2Q3

K2Bi8Se13
K ions possess ~2x the
thermal displacement
parameter
of the Bi/Se framework

-K2Bi8Se13
this block is a chunk
from the NaCl lattice

Bi

8,9-coordinate sites
K, Bi

K
Se

z
x

NaCl Structure: The Basic

Raw Material
Modules are cut out of NaCl stock
NaCl Lattice

-K2Bi8Se13
Sn Doped

Thermopower (V/K)

-50

Thermopower (V/K)

-100

-200

-100
-150
-200
-250
-300
-350

-300

-400

-400

50

100

150

200

250

300

50

350

100

150

200

250

300

Temperature (K)

Temperature (K)

400

Conductivity (S/cm)

Conductivity (S/cm)

100

80

60

40

350

300

250
200

20

150

50

100

150 200

Temperature (K)

250 300

50

100

150

200

Temperature (K)

250

300

-K2Bi8Se13 : Room temp ZT=0.9. At 600

K estimated at 1.5 (to be verified)
0

Thermopower (V/K)

-K2Bi8Se13

45

/S (arbitrary unit)

40
35
30
25
20
Eg = 0.59 eV

15
10
0.45

-50
-100
-150
-200
-250

0.5

0.55

0.6

0.65

0.7

0.75

50

Energy (eV)

Uher et al

-K2Bi8Se13

ingot

(W/m. K)

50

100

150

200

Temperature (K)

150

200

250

300

3000
2500
2000
1500
1000
500
0

100

Temperature (K)

Conductivity (S/cm)

DY61243

-K2Bi8Se13

ingot

DY61243

250

300

50

100

150

200

250

300

Temperature (K)

350

Sn Doping in -K2Bi8Se13
0
-50

1.0

-100

Undoped
0.5% Sn
1.0% Sn
1.5% Sn
2.0% Sn
3.0% Sn

-150

0.8
-200

Undoped
0.5% Sn
1.0% Sn
1.5% Sn
2.0% Sn
3.0% Sn

-350

50

100

0.6
150

ZT

-300

wer (V/K)

-250

200

250

300

Temperature (K)

0.4

40

Undoped
0.5% Sn
1.0% Sn
1.5% Sn
2.0% Sn
3.0% Sn

35
30

20

(W/cmK

15

5
0
0

50

50

100

150

200

Temperature (K)

10

ower Factor S

25

0.2

100

150

Temperature (K)

200

250

300

250

300

Michigan State University /Tellurex Corp.

Collaboration

-K2Bi8Se13

New TE material grown at Tellurex

New TE material grown at MSU

Photo of the first TE module containing 63 couples

n--K2Bi8Se13/p-Bi2Te3

Unoptimized
T=36 oC
Th=50 oC
All materials grown
at Tellurex Inc

-K2Bi8Se13 versus -K2Bi8Se13

Mixed K,Bi

-K2Bi8Se13, Eg=0.76 eV

-K2Bi8Se13, Eg=0.59 eV

-, -K2Bi8Se13 : Electronic structure

n-type character

Absorption

Quenched and annealed -K2Bi8Se13

E =0.59 eV
g

after annealing

quenched

0.1

0.2

0.3 0.4 0.5

Energy, eV

0.6

0.7

0.8

CsBi4Te6

C 2/m

51

Undoped as-prepared material

thermopower

conductivity

DY72121

350

120

dy72121(CsBi4Te6 crystal)

100
15

S (V/K)

250
200
150
100

80
60

10

40
5

50

20
0

50

100

150

200

Temperature (K)

250

300

50

100

150

200

Temperature (K)

Thermal conductivity

250

300

(W/m-K)

Cond. (S/cm)

300

20

Crystals of CsBi4Te6

100 m

1 mm
1 mm

Doped CsBi4Te6
SbI doped CsBi Te

~14 mW/cm-K

8000

200

ZTmax~0.8

At 260 K:
S ~174 V/K
Cond. ~1400 S/cm

7000
6000

150

5000
4000

100

3000
2000

50

1000
0

50

100

150

200

250

Temperature (K)

300

350

Seebeck (V/K)

Conductivity (S/cm)

Thermal Conductivity of p-type

CsBi4Te6
6.0
Data by Uher et al

(W/m . K)

5.0
4.0
3.0
2.0

parallel to needle

1.0

perpendicular to needle

0.0

50

100 150

200

250

Temperature (K)

300

350

Doping with SbI3

CsBi4-xSbxTe6

Sb
Bi

x = 0.3

CsBi4Te6
Figure of Merit (ZT)
1.0

1.0
CsBi4Te 6 doped
p-Bi Te Marlow
2

0.8

0.8

0.6

0.4

0.4

0.2

0.2

0.0

0.0
350

ZT

0.6

50

100

150

200

250

Temperature (K)

300

Best TE Materials
1

0.8

ZT

0.6
n-BiSb

ZT

n-SiGe sintered

0.4

CsBi Te
4

LaFe CoSb
3

0.2

Bi Te
2

12

PbTe
0
0

200 RT 400

600

800

Temperature (K)
(K)
Temperature

1000

1200

1400

Conclusions
The strategy to search for new materials in the
(A2Q)n(PbQ)m(Bi2Q3)p (Q=Se, Te) system is
successful
Many new promising compounds identified
All compounds strongly anisotropic
Doping studies are important in ZT optimization
ZT for -K2Bi8Se13 ~0.7 at rt, higher at >400K

References

The Role of Solid State Chemistry In The Discovery of New

Thermoelectric Materials Mercouri G. Kanatzidis, Semiconductors and
Semimetals, 2000, 69, 51-100.
Slack,G. A. New Materials and Performance Limits for Thermoelectric
Cooling in CRC Handbook of Thermoelectrics" Edited by Rowe, D. M.
CRC Press, Boca Raton, 1995, pp. 407-440
Tritt T. M. "Thermoelectrics run hot and cold", Science. 1996, 272, 5266,
1276-1277.
Mahan, G. D. Good thermoelectrics Solid State Phys: 1998, 51, 81-157.
(c) DiSalvo, F. J. "Thermoelectric cooling and power generation",
Science. 1999, 285 5428, 703-706
Thermoelectric Materials 1998- The Next Generation Materials for SmallScale Refridgeration and Power Generation Applications, edited by Tritt,
T. M.; Kanatzidis, M. G.; Mahan, G. D.; Lyon, Jr., H. B. Mat. Res. Soc.
Symp. Proc. 1999, Vol. 545, 233-246.

Collaborators
Prof. Tim Hogan, Dept of
Electrical Engineering, MSU
Prof. S. D. (Bhanu) Mahanti,
Dept. of Physics, MSU
Prof. Carl R. Kannewurf, Dept
of Electrical Engineering,
Northwestern Univ.
Ctirad Uher, Dept. of Physics, U
of M
Art Schultz, Argonne NL

TE Research group

Dr Duck young Chung

Dr Antje Mrotzek
Dr Kuei fang Hsu
Lykourgos Iordanidis
Kyoung-shin Choi
Jun-Ho Kim
Sandrine Sportouch
Rhonda Patschke

Tim McCarthy
Dr. Jun-Huan Do

Acknowledgements

Dr. Antje Mrotzek

Lykourgos Iordanidis
J. A. Aitken
Jun-Ho Kim
Joseph Wachter
Marina Zhuravleva
Xuini Wu
Jim Salvador
Brad Sieve
R G Iyer
Dr. Theodora Kyratsi
Dr. J.-H. Do
Dr. Duck Young Chung
Dr. Servane Coste
Dr. Pantelis Trikalitis
Dr. Susan Latturner
Dr. Kuei-fang Hsu