Introduction to Thermoelectrics

In 1822, Seebeck observed that when two electrically conducting materials are connected in
a closed loop as shown in Figure 1, and a temperature difference at the two junctions T1 and T2,
then there was a deflection of the magnetic needle in his measurement apparatus [1, 2]. The
deflection was dependent on the temperature difference between junctions and the materials
used for the conductors. Shortly after this, Oersted discovered the interaction between an
electric current and a magnetic needle. Many scientists subsequently researched the
relationship between electric currents and magnetic fields including Ampre, Biot, Savart,
Laplace and others.
Material A

T2

T1

Material B
Figure 1. Closed circuit Seebeck effect.
Through these studies it was discovered that the observation by Seebeck was not caused by
a magnetic polarization, but was caused by electrical current flowing in the closed loop circuit.
The electromotive force, or voltage, driving this electric current, can be measured by breaking
the closed loop of Figure 1, and measuring the open circuit voltage, V , which is given by
T2

V = S AB dT

(1)

T1

where SAB is the Seebeck coefficient for the two conductors which is defined as being positive
when a positive voltage is measured for T1 < T2. The voltage is measured across terminals
maintained at a constant temperature T0 as shown in Figure 2.
Material A

T2

T1
Material B
+

Material B

Figure 2. The open circuit Seebeck effect.

While the Seebeck effect is associated with a couple formed by two materials, it was later
discovered through the Thompson effect that an absolute Seebeck coefficient could be
associated with each material individually as SAB = (SA SB ) . We refer to the absolute Seebeck
coefficient for a given material as the thermopower of the material. A positive thermopower for a
material corresponds to a p-type material, and a negative thermopower is an n-type material.
Twelve years after Seebeck's discovery, a watchmaker and scientist named Jean Peltier
reported a temperature anomaly at the junction of two dissimilar materials as a current was
passed through the junction. It was unclear what caused this anomaly and while Peltier
attempted to explain it on the basis of the electrical conductivities and/or hardness of the two
materials, Lenz removed all doubt in 1838 with one simple experiment. By placing a droplet of
water in a dimple at the junction between rods of bismuth and antimony, Lenz was able to
freeze the water and subsequently melt the ice by changing the direction of current through the
junction. In this way, Lenz had made the first thermoelectric cooler. The rate of heat ( Q& )
absorbed or liberated from the junction was later found to be proportional to the current or:
Q& = I

(2)

where the proportionality constant () named the Peltier coefficient. This Peltier coefficient is
directly proportional to temperature and the Seebeck coefficient of the junction as:
= TS AB = T (S A SB ) . To maximize the heat absorbed or liberated, the junction should be
formed of materials with thermopowers of opposite sign (one material n-type, one p-type).
The ability to absorb or emit heat at the junction of the two materials leads to a useful
temperature controlling device, however to gain greater access to the junction, the typical
configuration for such thermoelectric modules is to bridge the junction with a metal interconnect
as shown in Figure 3 below:
Emitted heat

Absorbed heat
p

Emitted heat

+
V

Tc

Th

Absorbed heat
I

Th

Tc
I

Figure 3. Thermoelectric module that converts electric current into controlled heat flow.
The absorption and emission of heat at the junctions can be seen in terms of the energy
absorbed or given up by the electrons flowing from the thermoelectric material into the metal
electrodes (and visa versa) at each junction as depicted in Figure 4.

 E tn

EF

Et p

EF

Absorbed
Heat

Emitted
Heat

E tn

Et p
EF

EF

Figure 4. Thermal energy absorption and emission as electrons and holes cross the junctions
between thermoelectric material and metal.
This process is reversible: electrical current can be supplied through the junction to create a
temperature gradient (and heat flow), or a temperature gradient can be supplied to create
electric current flow as shown in Figure 5.

Th
n

_
Tc

I
Ro
Figure 5. Thermoelectric module that converts heat flow into electric current.
The efficiency of this power generation device is measured as the ratio of electrical power
delivered to the load resistor, P0, over the heat flow, Q& h , into the hot side of the thermoelectric
module:

Po
Q&

(3)

The electrical power is given as:

Po = I 2 R o

(4)

The heat flow into the hot side will consist of three components. The heat flow through the
thermoelectric material due to thermal conductance of the material, KT; the absorbed heat at
the hot side junction due to the Peltier coefficient, = STh ; and the heat that arrives at the hot
side due to Joule heating, I 2R, of the thermoelectric material with the assumption that half of this
heat goes to the hot side and half to the cold side of the module. The resistance of the
thermoelectric materials is R.
1
Q& h = KT + ST h I I 2 R
2

(5)

The electrical current through the module is adjusted by changing the load resistance, the
optimal conversion efficiency, opt, can be found as:

opt =

T
Th

( 1 + ZT 1)

T
1 + ZT + c
Th

(6)

where the average temperature T =

Z=

S 2

T h + Tc
and Z is the figure of merit given by:
2
(7)

The higher the value of Z, the higher the efficiency.

The units of Z are (1/K), so it is common to use the unitless figure of merit, ZT, for comparing
individual materials, and modules. A comparison of various thermoelectric materials is shown in
Figure 6 where the figure of merit peaks for each material at a given temperature such that each
material has an optimal operating temperature range.

2
p-type Materials
Na

1.5

0.95

Pb SbTe
20

22

Ag Pb Sn Sb Te
0.5

0.2

CeFe Sb

Zn Sb
4

Tl BiTe
9

ZT

Bi Te
2

(AgSbTe )

12

2 0.15

(GeTe)

0.85

Ce
CsBi Te

10

0.28

Fe Co Sb
1.5

2.5

12

Yb MnSb
PbTe

14

11

0.5

200

400

600
800
Temperature (K)

1000

1200

2
Pb Ag
18

0.86

SbTe

PbTe-PbS(8%)

1.5

Ba

Mg Si Sn
2

ZT

n-type Materials

20

0.4

Ni

0.30

Co

0.05

La Te

Sb

3.95

12

Mg Si Sn
2

0.6

0.6

0.4

SiGe
Bi Te
2

CoSb

PbTe

0.5

0
200

400

600

800
1000
Temperature (K)

1200

1400

The data for these plots were estimated from graphs given in the following references:
Material

Tl9BiTe6

Zn4Sb3

PbTe

Ce0.9Fe3CoSb12
TAGS-85

Reference 1
B. Wlfing, C. Kloc, J. Teubner, E. Bucher.
Phys Rev Lett. 86(19) (2001) 4350-3. High
performance thermoelectric Tl9BiTe6 with an
extremely low thermal conductivity.
T. Caillat, J.-P. Fleurial, A. Borshchevsky,
Preparation and Thermoelectric Properties of
Semiconducting Zn4Sb3, Journal of Physics
and Chemistry of Solids, 58, (7), pp. 11191125, (1997).
A. F. Ioffe, Semiconductor Thermoelements
and Thermoelectric Cooling (London:
Infosearch) (1957).
T. Caillat, S. Borshchevsky, J. Snyder, J-P.
Fleurial. High efficiency segmented
thermoelectric unicouples. In: El-Genk M,
editor. Proceedings of Space Technology and
Applications International Forum. AIP
Conference Proceedings No. 504. Melville, NY:
American Institute of Physics; 2000. p. 1508
12.
Skrabek E, Trimmer D (1976) Thermoelectric

Reference 2

G. Jeffrey Snyder, T. Caillat, Using the

Compatibility Factor to Design High Efficiency
Segmented Thermoelectric Generators, MRS
Proceedings, Vol. 793, p. 37, (2004).
G. Jeffrey Snyder, T. Caillat, Using the
Compatibility Factor to Design High Efficiency
Segmented Thermoelectric Generators, MRS
Proceedings, Vol. 793, p. 37, (2004).

H. J. Goldsmid and G. S. Nolas, "A Review of

the New Thermoelectric Materials," 20th
International Conference on Thermoelectrics,
pp. 1-6, 2001.
G. Jeffrey Snyder, T. Caillat, Using the

SiGe (n-type)

Ba0.3Ni0.05Co3.95
Sb12

CsBi4Te6

Bi2Te3

Na0.95Pb20SbTe
22

Ag0.5Pb6Sn2Sb0
.2Te10 (LASTT)
Pb18SbAg0.86Te
20

LAST

PbTe-PbS(8%)

Yb14MnSb11
NaxCoO2

device including and alloy of GeTe and

AgSbTe2 as the p-type element. U. S. Patent
No. 3,945,855, issued March 23, 1976
J. P. Dismukes, L. Ekstrom, E. F. Steigmeier, I.
Kudman, and D. S. Beers, "Thermal and
Electrical Properties of Heavily Doped Ge-Si
Alloys up to 1300 K," Journal of Applied
Physics, vol. 35, pp. 2899-2907, 1964.
X. Tang, Q. Zhang, L. Chen, T. Goto, and T.
Hirai, "Synthesis and thermoelectric properties
of p-type- and n-type-filled skutterudite
RyMxCo4-xSb12 (R=Ce,Ba,Y; M=Fe,Ni),"
Journal of Applied Physics, vol. 97, pp.
093712, 2005.
D.-Y. Chung, T. P. Hogan, M. Rocci-Lane, P.
Brazis, J.R. Ireland, C. R. Kannewurf, M.
Bastea, C. Uher, and M. G. Kanatzidis, "A New
Thermoelectric Material:CsBi4Te6," Journal of
the American Society of Chemistry, vol. 126,
pp. 6414-6428, 2004.
M. V. Vedernikov, V. A. Kutasov, L. N.
Luk'yanova, and P.P. Konstantinov,
"Optimization of (Bi,Sb)2(Te,Se)3 - based
thermoelectrics for low-temperature
applications," presented at 16th International
Conference on Thermoelectrics, 1997.
P. F. P. Poudeu, J. D'Angelo, A. D. Downey, J.
L. Short, T. P. Hogan, M. G. Kanatzidis
Angewandte Chemie International Edition 45,
23, 2006, 3835-3839 High Thermoelectric
Figure of Merit and Nanostructuring in Bulk ptype Na1-xPbmSbyTem+2
J. Androulakis, K-F. Hsu, R. Pcionek, H. Kong,
C. Uher, J.J. D'Angelo, A. Downey, T. Hogan,
M.G. Kanatzidis. Nanostructuring and high
thermoelectric efficiency in p-type Ag(Pb1ySny)mSbTe2+m. Advanced Materials
(Weinheim, Germany) (2006), 18(9), 11701173.
K-F. Hsu, S. Loo, F. Guo, W. Chen, J. S. Dyck,
C. Uher, T. Hogan, E. K. Polychroniadis, M. G.
Kanatzidis Science 303. 5659, 2004, 818 - 821
Cubic AgPbmSbTe2+m: Bulk Thermoelectric
Materials with High Figure of Merit
J. Androulakis,C.-H. Lin, H.-J. Kong, C. Uher,
C.-I. Wu, T. Hogan, B.A. Cook, T. Caillat, K.M.
Paraskevopoulos, M.G. Kanatzidis, J. Am.
Chem. Soc. 2007; 129(31); 9780-9788.
Spinodal Decomposition and Nucleation and
Growth as a Means to Bulk Nanostructured
Thermoelectrics: Enhanced Performance in
Pb1-xSnxTe-PbS
S. R. Brown, S. M. Kauzlarich, F. Gascoin, G.
J. Snyder. Chem. Mater., 18 (7), 1873 -1877,
2006. Yb14MnSb11: New High Efficiency
Thermoelectric Material for Power Generation
K. Fujita, T. Mochida, K. Nakamura Jpn. J.
Appl. Phys. Vol. 40 (2001) 4644-4647 HighTemperature Thermoelectric Properties of

Compatibility Factor to Design High Efficiency

Segmented Thermoelectric Generators, MRS
Proceedings, Vol. 793, p. 37, (2004).
G. Jeffrey Snyder, T. Caillat, Using the
Compatibility Factor to Design High Efficiency
Segmented Thermoelectric Generators, MRS
Proceedings, Vol. 793, p. 37, (2004).

D.-Y. Chung, T. Hogan, P. Brazis, M. RocciLane, C. Kannewurf, M. Bastea, C. Uher, and

M. G. Kanatzidis, "CsBi4Te6: A HighPerformance Thermoelectric Material for LowTemperature Applications," Science, vol. 287,
pp. 1024-1027, 2000.
O. Yamashita and S. Sugihara, "Highperformance bismuth-telluride compounds with
highly stable thermoelectric figure of merit,"
Journal of Materials Science, vol. 40, pp. 64396444, 2005.

G. Jeffrey Snyder, T. Caillat, Using the

Compatibility Factor to Design High Efficiency
Segmented Thermoelectric Generators, MRS
Proceedings, Vol. 793, p. 37, (2004).

Mg2Si1xSnx

NaxCoO2- Single Crystals

V. K. Zaitsev, M. I. Fedorov, E. A. Gurieva, I. S.
Eremin, P. P. Konstantinov, A. Yu. Samunin,
M. V. Vedernikov, Highly effective Mg2Si1xSnx
thermoelectrics, Physical Review B, 74,
045207, (2006).

References

A. F. Ioffe, Semiconductor Thermoelements and Thermoelectric Cooling, Infosearch

Limited, London, 1957.

Paul E. Gray, The Dynamic Behavior of Thermoelectric Devices, Published jointly by The
Technology Press of The Massachusetts Institute of Technology and John Wiley & Sons,
Inc., New York, 1960.