Thermoelectric effects are described as a phenomenon when a current is passed through a

couple of dissimilar conductors/semiconductors under the difference of temperature.

Thermoelectric effects behavior depends in part on the Seebeck, Peltier, and Thomson

coefficients , , , respectively.

Thermoelectric arises because thermoelectric effects arise because charge carriers in

metals and semiconductors are free to move much like gas molecules, while carrying
charge as well as heat. When a temperature gradient is applied to a material, the mobile
charge carriers at the hot end tend to diffuse to the cold end. (G. JEFFREY SNYDER*
AND ERIC S. TOBERER - Complex thermoelectric materials)

1. Seebeck and Peltier effects

Seebecks and Peltier effect happens at the junction between two kinds of material after
heating this junction due to the difference in their band gap, which is determined by the
internal properties involved. Actually, Seebeck and Peltier coefficients have a tightly
relationship, or in other words they are related each other.

The Seebeck coefcicient describes the direct conversion from thermal energy into
electrical current. For Seebeck effect, we construct a simple model of a metal with one
side heated and the left side remains at its first temperature. When a temperature gradient
is applied to a material, the charge carriers at hot side tend to diffuse to cold side. In order
to mitigate the further migration of the carriers due to the concentration of carriers at cold
side, which is the reason creating the broken in the charge neutrality, an internal electrical
field is formed.

Peltier found that the passage of an electric current produces small heating or cooling
effect depending on its direction. Peltier effect accompanies with Joule heating effect.

Thomson establishes the correlation between Peltier and Seebeck effect by a coefficient
through showing the reversible heating and cooling when applying both an electric
current and a temperature gradient. We consider a couple of dissimilar conductors named
A and B, which are connected by a junction following the under picture. We notice that,
Seebeck and Peltier effects only occur to different kinds of material due to the difference
energies in different materials, which is their internal properties. When a current passes
from one material to another, the energy transported by the electrons is altered, the
difference temperature appearing as heating or cooling at the junction, that is as the
Peltier effect. Likewise, when the junction is heated, electrons are enabled to pass from
the material in which the electrons have the lower energy into that in which their energy
is higher, giving rise to an electromotive force. More Specifically heat is liberated if an
electric current flows in the same direction as the heat flows, otherwise it is absorbed.
( ta nhit nu dng in v nhit cng hng, ngc li ta c s hp th)

(Julia book figure 1.1)

Simple Thermal couple

Seebeck coefficients is defined by a coefficient:

dV
S ab
dT
(V/K)

If electrons move from hot side to cold side Seebeck coefficient is positive, conductors
absorb heat. (n-type)

By contrast, holes move from hot side to cold side coefficient is negative. (p-type)

In fact that, no materials remain its superconductor states at ordinary temperature, so it

might be thought that the absolute Seebeck coefficients of other materials can be obtained
at low temperatures. However, the diffusing charges are scattered by impurities,
structural imperfections, and lattice vibrations. As far as these scattering processes are
energy dependent, the hot and cold carriers will diffuse at different rates.
 q
AB
I
Peltier coefficients is defined by a coefficient: will be regarded as positive of the
current entering into A is heating and the current leaving from A is cooling. In which, q is
cooling or heating at each junction to current I.

It might be easy to think that calculating Seebeck coefficient less complicated than
calculating Peltier coefficient. By determining Seebeck coefficient we can express the
Peltier coefficient in terms of the Seebeck coefficient by a relevant equation:

AB S AB .T
(W/A = V)

The Thomson coefficient is defined as the rate of heating or cooling per unit length that
results from the passage of unit current along a conductor in which there is unit
temperature gradient. The appropriate Kelvin relation is

d AB
A B T
dT
Or

d
T
dT

VK 1
Thomson coefficient is expressed in unit.

2. Seebeck coefficient representing to thermoelectric power can be thought as the

heat per carrier over temperature or the entropy per carrier.

Seebeck coefficient is also given by:

Where n is the carrier concentration, m* is the effective mass of the carriers.

For metals, the heat per carrier is essentially a product of the electronic specific heat
and the temperature divided by the number of carriers. So we have another form of
Seebeck coefficient equation:

Cel k B kBT
( )
Q e EF

EF is Fermi energy ( related to the chemical potential of material)

e 2 n
ne
m
3. Electrical conductivity: the electrical conductivity coefficient will
be always positive and it is related to the charge and mass of the carriers

Where is the carrier mobility, e is the charge of electron.

(2) and (3) show another conflicts large effective masses produce high thermopower but
low electrical conductivity.

Effective mass: increases with flat, narrow bands with high density at the Fermi surface.

In general, heavy carriers move slowly leading to low mobility, which is the reason why
materials having limited electrical conduction. However the relationship between
effective mass with mobility is very complicated, which depends on electronic structure,
scattering mechanisms and anisotropy

4. Lattice thermal conductivity : depending on two main contributions:

(T) e (T) l (T)

Which is defined by the motion of charge carriers and the vibration of atom around
their equilibrium positons in lattice.
5. Thermoelectric device

6. Power factor
7. The figure of merit

2 2T
ZT

The ground state of N free electron is constructed by occupying all one-electron levels k
(k) h2 k 2 / 2m F F
with energies less than , where is determined by requiring the total
F
number of one electron levels with energy less than to be equal to the total number of
electrons. (Solid state Physics Ascroft. Mermmit)
For a thermocouple ZT is typically given by:

( p n ) 2 T
ZT
( n n )1/2 ( p P )1/ 2

In general, holes and electrons transport depend on energy information. Pure

semiconductor contains equal number of electrons and holes. Density of state (DOS) is
the number of electrons and holes for unit volume per unit energy for a given energy
level.

W

QH1
Efficiency is defined by the ratio:

The relation between the Figure of Merit and the efficiency of a thermoelectric device is
given by the following formula:

TH TC 1 ZT 1
(%) 100.( ).
TH 1 ZT (TH / TC )

To increase efficiency -> increase ZT. ZT is large whence Seebeck is large, electrical
conductivity is large and thermal conductivity as small.

Strategies to improve the ZT:

e
+) difficulty have to solve: Seebeck, , are related each other. It is impossible to
increase one of them without affecting the left.