Thermoelectric effect

The thermoelectric effect is the direct conversion of temperature differences to electric

voltage and vice versa. On the measurement-scale of everyday life, a thermoelectric
device creates a voltage when there is a different temperature on each side. Conversely
(and, thermodynamically speaking, reversibly) when a voltage is applied to it, it creates a
temperature difference. On the scale of atoms (specifically, charge carriers), an applied
temperature difference causes charged carriers in the material, whether they are
electrons or holes, to diffuse from the hot side to the cold side, similar to a classical gas
that expands when heated; hence, the thermally-induced current.
This effect can be used to generate electricity, to measure temperature, to cool objects, or
to heat them or cook them. Because the direction of heating and cooling is determined by
the sign of the applied voltage, thermoelectric devices make very convenient temperature
controllers.
Traditionally, the term thermoelectric effect or thermoelectricity encompasses three
separately identified effects, the Seebeck effect, the Peltier effect, and the Thomson
effect. In many textbooks, thermoelectric effect may also be called the PeltierSeebeck
effect. This separation derives from the independent discoveries of French physicist Jean
Charles Athanase Peltier and Estonian-German physicist Thomas Johann Seebeck. Joule
heating, the heat that is generated whenever a voltage difference is applied across a
resistive material, is somewhat related, though it is not generally termed a thermoelectric
effect (and it is usually regarded as being a loss mechanism due to non-ideality in
thermoelectric devices). The PeltierSeebeck and Thomson effects are reversible,
whereas Joule heating is not[citation needed].
o

1.

Seebeck effect

The Seebeck effect is the conversion of temperature differences directly into electricity.
Seebeck discovered that a compass needle would be deflected when a closed loop was
formed of two metals joined in two places with a temperature difference between the
junctions. This is because the metals respond differently to the temperature difference,
which creates a current loop, which produces a magnetic field. Seebeck, however, at this
time did not recognize there was an electric current involved, so he called the
phenomenon the thermomagnetic effect, thinking that the two metals became
magnetically polarized by the temperature gradient. The Danish physicist Hans Christian
rsted played a vital role in explaining and conceiving the term "thermoelectricity".

Reference
junction

Wire A

Measurement
junction

Wire B

Figure 1. Elements of a thermocouple.

When a metallic bar is subjected to a voltage (V) or a temperature gradient, the
electric current is generated. For small temperature gradients, we may assume a
linear relation between the electric current density j and the gradients:
j = (-V/x) + A(-T/x)
= E A(T/x)
where is the electric conductivity (1/(ohm m)). If there is no electric current
flows, the above equation leads to
E - AT/x = 0
where E is the field generated by the thermal emf. The Seebeck coefficient S is
defined through
E = S(T/x), S = A/ .
The effect is that a voltage, the thermoelectric EMF, is created in the presence of a
temperature difference between two different metals or semiconductors. This causes a
continuous current in the conductors if they form a complete loop. The voltage created is
of the order of several microvolts per kelvin difference. One such combination, copperconstantan, has a Seebeck coefficient of 41 microvolts per kelvin at room temperature.
In the circuit:

(which can be in several different configurations and be governed by the same

equations), the voltage developed can be derived from:

T2

T1

[ S B (T ) S A (T )]dT

SA and SB are the Seebeck coefficients (also called thermoelectric power or thermopower)
of the metals A and B as a function of temperature, and T1 and T2 are the temperatures of
the two junctions. The Seebeck coefficients are non-linear as a function of temperature,
and depend on the conductors' absolute temperature, material, and molecular structure. If
the Seebeck coefficients are effectively constant for the measured temperature range, the
above formula can be approximated as:
V [ S B S A ][T2 T1 ]

The Seebeck effect is commonly used in a device called a thermocouple (because it is

made from a coupling or junction of materials, usually metals) to measure a temperature
difference directly or to measure an absolute temperature by setting one end to a known
temperature. Several thermocouples when connected in series are called a thermopile,
which is sometimes constructed in order to increase the output voltage since the voltage
induced over each individual couple is small.
In thermocouples two wires, A and B, made out of different materials are joined
together to a closed electric circuit. The junctions are called measure (hot)
junction and reference (cold) junction. The associated temperatures are T R, TM.
This is also the principle at work behind thermal diodes and thermoelectric generators
(such as radioisotope thermoelectric generators or RTGs) which are used for creating
power from heat differentials.
The Seebeck effect is due to two effects: charge carrier diffusion and phonon drag
(described below). If both connections are held at the same temperature, but one
connection is periodically opened and closed, an AC voltage is measured, which is also
temperature dependent. This application of the Kelvin probe is sometimes used to argue
that the underlying physics only needs one junction. And this effect is still visible if the
wires only come close, but do not touch, thus no diffusion is needed.

Thermopower
The thermopower, or thermoelectric power, or Seebeck coefficient of a material
measure the magnitude of an induced thermoelectric voltage in response to a temperature
difference across that material. The thermopower has units of (V / K), though in practice
it is more common to use microvolts per kelvin. Values in the hundreds of V/K, negative
or positive, are typical of good thermoelectric materials. The term thermopower is a
misnomer since it measures the voltage or electric field induced in response to a
temperature difference, not the electric power. An applied temperature difference causes
charged carriers in the material, whether they are electrons or holes, to diffuse from
the hot side to the cold side, similar to a classical gas that expands when heated. Mobile
charged carriers migrating to the cold side leave behind their oppositely charged and

immobile nuclei at the hot side thus giving rise to a thermoelectric voltage
(thermoelectric refers to the fact that the voltage is created by a temperature difference).
Since a separation of charges also creates an electric potential, the buildup of charged
carriers onto the cold side eventually ceases at some maximum value since there exists an
equal amount of charged carriers drifting back to the hot side as a result of the electric
field at equilibrium. Only an increase in the temperature difference can resume a buildup
of more charge carriers on the cold side and thus lead to an increase in the thermoelectric
voltage. Incidentally the thermopower also measures the entropy per charge carrier in the
material. To be more specific, the partial molar electronic heat capacity is said to equal
the absolute thermoelectric power multiplied by the negative of Faraday's constant.[1]
The thermopower of a material, represented by S (or sometimes by ), depends on the
material's temperature and crystal structure. Typically metals have small thermopowers
because most have half-filled bands. Electrons (negative charges) and holes (positive
charges) both contribute to the induced thermoelectric voltage thus canceling each other's
contribution to that voltage and making it small. In contrast, semiconductors can be
doped with an excess amount of electrons or holes and thus can have large positive or
negative values of the thermopower depending on the charge of the excess carriers.
The sign of the thermopower can determine which charged carriers dominate the electric
transport in both metals and semiconductors.
If the temperature difference T between the two ends of a material is small, then the
thermopower of a material is defined (approximately) [2] as:
S

V
T

and a thermoelectric voltage V is seen at the terminals.

This can also be written in relation to the electric field E and the temperature gradient , by
the approximate[2] equation:
S

E
T

In practice one rarely measures the absolute thermopower of the material of interest. This
is because electrodes attached to a voltmeter must be placed onto the material in order to
measure the thermoelectric voltage. The temperature gradient then also typically induces
a thermoelectric voltage across one leg of the measurement electrodes. Therefore the
measured thermopower includes a contribution from the thermopower of the material of
interest and the material of the measurement electrodes.
The measured thermopower is then a contribution from both and can be written as:
S AB S B S A

VB VA

T
T

Superconductors have zero thermopower since the charged carriers produce no entropy.
This allows a direct measurement of the absolute thermopower of the material of interest,
since it is the thermopower of the entire thermocouple as well. In addition, a
measurement of the Thomson coefficient, , of a material can also yield the thermopower

through the relation: S dT

T

The thermopower is an important material parameter that determines the efficiency of a

thermoelectric material. A larger induced thermoelectric voltage for a given temperature
gradient will lead to a larger efficiency. Ideally one would want very large thermopower
values since only a small amount of heat is then necessary to create a large voltage. This
voltage can then be used to provide power.

Figure 2.jpg

Figure 3.jpg

Figure 4.jpg

Thermocouple Circuit
A typical thermocouple circuit can be illustrated as follows:

Typical Thermocouple Circuit

Suppose that the Seebeck coefficients of two dissimilar metallic materials, metal A
and metal B, and the lead wires are SA, SB, and SLead respectively. All three Seebeck
coefficients are functions of temperature. The voltage output Vout measured at the
gage (see schematic above) is,

where TRef is the temperature at the reference point, TTip is the temperature at the
probe tip. Note that mathematically the voltage induced by the temperature and/or
material mismatch of the lead wires cancels, whereas in reality the lead wires will
introduce noise into the circuit.
If the Seebeck coefficient functions of the two thermocouple wire materials are precalibrated and the reference temperature TRef is known (usually set by a 0C ice
bath), the temperature at the probe tip becomes the only unknown and can be
directly related to the voltage readout.
If the Seebeck coefficients are nearly constant across the targeted temperature
range, the integral in the above equation can be simplified, allowing one to solve
directly for the temperature at the probe tip,

In practice, vendors will provide calibration functions for their products. These
functions are usually high order polynomials and are calibrated with respect to a
certain reference temperature, e.g., 0 C (32 F). Suppose that the coefficients of
the calibration polynomials are a0, a1, a2, ..., an. The temperature at the probe tip can
then be related to the voltage output as,

Note that the above formula is effective only if the reference temperature TRef in the
experiment is kept the same as the reference temperature specified on the data
sheet. Furthermore, these coefficients are unit sensitive. Make sure to use the
vendor-specified temperature unit (i.e. Celsius/centigrade, Fahrenheit, or Kelvin)

when plugging in numbers.

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Thermoelectric Sensitivity
The Seebeck coefficients (thermoelectric sensitivities) of some common materials at
0 C (32 F) are listed in the following table.
Material

Seebeck
Coeff. *

Material

Seebeck
Coeff. *

Material

Seebeck
Coeff. *

Aluminum

3.5

Gold

6.5

Rhodium

6.0

Antimony

47

Iron

19

Selenium

900

Bismuth

-72

Lead

4.0

Silicon

440

Cadmium

7.5

Mercury

Silver

6.5

Carbon

3.0

Nichrome

Constantan

-35

Nickel

Copper

6.5

Platinum

Germanium

300

Potassium

0.60
25

Sodium

-2.0

-15

Tantalum

4.5

Tellurium

500

-9.0

Tungsten

7.5

*: Units are V/C; all data provided at a temperature of 0 C (32 F)

The above table also reveals some possible wire pairings. For instance, iron or copper
can be put on the positive terminal while constantan can be used for the negative
terminal of a thermocouple circuit (Type J and T).

Charge-carrier diffusion
Charge carriers in the materials (electrons in metals, electrons and holes in
semiconductors, ions in ionic conductors) will diffuse when one end of a conductor is at a
different temperature than the other. Hot carriers diffuse from the hot end to the cold end,
since there is a lower density of hot carriers at the cold end of the conductor. Cold carriers
diffuse from the cold end to the hot end for the same reason.
If the conductor were left to reach thermodynamic equilibrium, this process would result
in heat being distributed evenly throughout the conductor (see heat transfer). The
movement of heat (in the form of hot charge carriers) from one end to the other is called a
heat current. As charge carriers are moving, it is also an electrical current.
In a system where both ends are kept at a constant temperature difference (a constant heat
current from one end to the other), there is a constant diffusion of carriers. If the rate of
diffusion of hot and cold carriers in opposite directions were equal, there would be no net

change in charge. However, the diffusing charges are scattered by impurities,

imperfections, and lattice vibrations (phonons). If the scattering is energy dependent, the
hot and cold carriers will diffuse at different rates. This creates a higher density of
carriers at one end of the material, and the distance between the positive and negative
charges produces a potential difference; an electrostatic voltage.
This electric field, however, opposes the uneven scattering of carriers, and an equilibrium
is reached where the net number of carriers diffusing in one direction is canceled by the
net number of carriers moving in the opposite direction from the electrostatic field. This
means the thermopower of a material depends greatly on impurities, imperfections, and
structural changes (which often vary themselves with temperature and electric field), and
the thermopower of a material is a collection of many different effects.
Early thermocouples were metallic, but many more recently developed thermoelectric
devices are made from alternating p-type and n-type semiconductor elements connected
by metallic interconnects as pictured in the figures below. Semiconductor junctions are
especially common in power generation devices, while metallic junctions are more
common in temperature measurement. Charge flows through the n-type element, crosses
a metallic interconnect, and passes into the p-type element. If a power source is provided,
the thermoelectric device may act as a cooler, as in the figure to the left below. This is the
Peltier effect, described in the next section. Electrons in the n-type element will move
opposite the direction of current and holes in the p-type element will move in the
direction of current, both removing heat from one side of the device. If a heat source is
provided, the thermoelectric device may function as a power generator, as in the figure to
the right below. The heat source will drive electrons in the n-type element toward the
cooler region, thus creating a current through the circuit. Holes in the p-type element will
then flow in the direction of the current. The current can then be used to power a load,
thus converting the thermal energy into electrical energy.

Phonon drag
Phonons are not always in local thermal equilibrium; they move against the thermal
gradient. They lose momentum by interacting with electrons (or other carriers) and
imperfections in the crystal. If the phonon-electron interaction is predominant, the
phonons will tend to push the electrons to one end of the material, losing momentum in
the process. This contributes to the already present thermoelectric field. This contribution
is most important in the temperature region where phonon-electron scattering is
predominant. This happens for
where D is the Debye temperature. At lower temperatures there are fewer phonons
available for drag, and at higher temperatures they tend to lose momentum in phononphonon scattering instead of phonon-electron scattering.

This region of the thermopower-versus-temperature function is highly variable under a

magnetic field.

Spin Seebeck Effect and Magnetic Batteries

Physicists have recently discovered that heating one side of a magnetized nickel-iron rod
causes electrons to rearrange themselves according to their spins. This so-called "spin
Seebeck effect" could lead to batteries that generate magnetic currents, rather than
electric currents. A source of magnetic currents could be especially useful for the
development of spintronics devices, which use magnetic currents in order to reduce
overheating in computer chips, since, unlike electric currents, magnetic currents do not
generate heat [3].

2. Peltier effect
This effect bears the name of Jean-Charles Peltier (a french physicist) who discovered in
1834, the calorific effect of an electrical current at the junction of two different metals.
When a current I is made to flow through the circuit, heat is evolved at the upper junction
(at T2), and absorbed at the lower junction (at T1). The Peltier heat absorbed by the lower
junction per unit time, is equal to

Q AB I

Where IIAB is the Peltier coefficient of the entire thermocouple, and IIA and IIB are the
coefficients of each material. P-type silicon typically has a positive Peltier coefficient
(though not above ~550 K), and n-type silicon is typically negative, as the names suggest.
The Peltier coefficients represent how much heat current is carried per unit charge
through a given material. Since charge current must be continuous across a junction,
the associated heat flow will develop a discontinuity if IIA and IIB are different. This
causes a non-zero divergence at the junction and so heat must accumulate or deplete
there, depending on the sign of the current. Another way to understand how this effect
could cool a junction is to note that when electrons flow from a region of high density
to a region of low density, they expand (as with an ideal gas) and cool.
The conductors are attempting to return to the electron equilibrium that existed before the
current was applied by absorbing energy at one connector and releasing it at the other.
The individual couples can be connected in series to enhance the effect.
An interesting consequence of this effect is that the direction of heat transfer is controlled
by the polarity of the current; reversing the polarity will change the direction of transfer
and thus the sign of the heat absorbed/evolved.

A Peltier cooler/heater or thermoelectric heat pump is a solid-state active heat pump

which transfers heat from one side of the device to the other. Peltier cooling is also called
thermo-electric cooling (TEC).

3. Thomson effect
The Thomson effect was predicted and subsequently experimentally observed by
William Thomson (Lord Kelvin) in 1851. It describes the heating or cooling of a currentcarrying conductor with a temperature gradient.
Any current-carrying conductor (except for a superconductor), with a temperature
difference between two points, will either absorb or emit heat, depending on the
material.
If a current density J is passed through a homogeneous conductor, heat production per
unit volume is:
q J 2 J

dT
dx

where
is the resistivity of the material
dT/dx is the temperature gradient along the wire
is the Thomson coefficient.
The first term J is simply the Joule heating, which is not reversible.
The second term is the Thomson heat, which changes sign when J changes direction.
In metals such as zinc and copper, which have a hotter end at a higher potential and a
cooler end at a lower potential, when current moves from the hotter end to the colder end,
it is moving from a high to a low potential, so there is an evolution of heat. This is called
the positive Thomson effect.
In metals such as cobalt, nickel, and iron, which have a cooler end at a higher potential
and a hotter end at a lower potential, when current moves from the hotter end to the
colder end, it is moving from a low to a high potential, there is an absorption of heat. This
is called the negative Thomson effect.
The Thomson coefficient is unique among the three main thermoelectric coefficients
because it is the only thermoelectric coefficient directly measurable for individual
materials. The Peltier and Seebeck coefficients can only be determined for pairs of
materials. Thus, there is no direct experimental method to determine an absolute Seebeck

coefficient (i.e. thermopower) or absolute Peltier coefficient for an individual material.

However, as mentioned elsewhere in this article there are two equations, the Thomson
relations, also known as the Kelvin relations (see below), relating the three thermoelectric
coefficients. Therefore, only one can be considered unique.
If the Thomson coefficient of a material is measured over a wide temperature range,
including temperatures close to zero, one can then integrate the Thomson coefficient over
the temperature range using the Kelvin relations to determine the absolute (i.e. singlematerial) values for the Peltier and Seebeck coefficients. In principle, this need only be
done for one material, since all other values can be determined by measuring pairwise
Seebeck coefficients in thermocouples containing the reference material and then adding
back the absolute thermoelecric power (thermopower) of the reference material.
It is commonly asserted that lead has a zero Thomson effect. While it is true that the
thermoelectric coefficients of lead are small, they are in general non-zero. The Thomson
coefficient of lead has been measured over a wide temperature range and has been
integrated to calculate the absolute thermoelectric power (thermopower) of lead as a
function of temperature.[4]
Unlike lead, the thermoelectric coefficients of all known superconductors are zero.

4. The Thomson relationships

The Seebeck effect is actually a combination of the Peltier and Thomson effects. In fact,
in 1854 Thomson found two relationships, now called the Thomson or Kelvin
relationships, between the corresponding coefficients. The absolute temperature T, the
Peltier coefficient and Seebeck coefficient S are related by the first Thomson relation
S T

which predicted the Thomson effect before it was actually formalized. These are related
to the Thomson coefficient by the second Thomson relation
T

dS
dT

Thomson's theoretical treatment of thermoelectricity is remarkable in the fact that it is

probably the first attempt to develop a reasonable theory of irreversible thermodynamics
(non-equilibrium thermodynamics). This occurred at about the time that Clausius,
Thomson, and others were introducing and refining the concept of entropy.

5. Thermoelectric cooling
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Thermoelectric cooling uses the Peltier effect to create a heat flux between the junction
of two different types of materials. A Peltier cooler, heater, or thermoelectric heat pump is
a solid-state active heat pump which transfers heat from one side of the device to the
other side against the temperature gradient (from cold to hot), with consumption of
electrical energy. Such an instrument is also called a Peltier device, Peltier diode, Peltier
heat pump, solid state refrigerator, or thermoelectric cooler (TEC).[1] Because heating
can be achieved more easily and economically by many other methods, Peltier devices
are mostly used for cooling. However, when a single device is to be used for both heating
and cooling, a Peltier device may be desirable. Simply connecting it to a DC voltage will
cause one side to cool, while the other side warms. The effectiveness of the pump at
moving the heat away from the cold side is totally dependent upon the amount of current
provided and how well the heat from the hot side can be removed.
Peltier devices can also be used to generate electricity (thermogenerator) if a temperature
difference is maintained between the two sides.

Performance
Thermoelectric junctions are generally only around 510% as efficient as the ideal
refrigerator (Carnot cycle), compared with 4060% achieved by conventional
compression cycle systems (reverse Rankine systems like a compressor). Due to the
relatively low efficiency, thermoelectric cooling is generally only used in environments
where the solid state nature (no moving parts, maintenance-free) outweighs pure
efficiency.
Peltier (thermoelectric) cooler performance is a function of ambient temperature, hot and
cold side heat exchanger (heat sink) performance, thermal load, Peltier module
(thermopile) geometry, and Peltier electrical parameters.
However recent developments prove that series Peltier effect modules could soon surpass
I.C. engines both in efficiency and power density for fuel based power generation [1].

Uses
Peltier devices are commonly used in camping and portable coolers and for cooling
electronic components and small instruments. Some electronic equipment intended for
military use in the field is thermoelectrically cooled. The cooling effect of Peltier heat
pumps can also be used to extract water from the air in dehumidifiers.

The effect is used in satellites and spacecraft to counter the effect of direct sunlight on
one side of a craft by dissipating the heat over the cold shaded side, whereupon the heat is
dissipated by thermal radiation into space.
Photon detectors such as CCDs in astronomical telescopes or very high-end digital
cameras are often cooled down with Peltier elements. This reduces dark counts due to
thermal noise. (A dark count is the event that a pixel gives a signal although it has not
received a photon but rather mistook a thermal fluctuation for one. On digital photos
taken at low light these occur as speckles (or "pixel noise").
Thermoelectric coolers can be used to cool computer components to keep temperatures
within design limits without the noise of a fan, or to maintain stable functioning when
overclocking. A Peltier cooler with a heat sink or waterblock can cool a chip to well
below ambient temperature.

Underlying principles
Main article: Thermoelectric effect
Thermoelectric coolers rely on the thermoelectric effect. When a current is run through
an appropriately-configured thermoelectric device, heat is transported from one side of
the device to the other.