PELTIER EFFECT IN SEMICONDUCTORS
with certain chronic diseases. Compact refrigerators with
INTRODUCTION
In recent years, devices based on the Peltier effect, which is
the basis for solid-state thermoelectric cooling, have
evolved rapidly to meet the fast-growing industry of elec-
tronics. The main point arises from the fact that the heat
extraction or absorption occurs at the contact between two
different conducting media when a direct current (DC)
electric current flows through this contact. A comprehen-
sive study of the mechanisms of heating and cooling origi-
nated by an electrical current in semiconductor devices is
reported. The thermoelectric cooling in n-n, p-p, and p-n
junction contacts, as well as inhomogeneous bulk semi-
conductors, are analyzed. Both degenerate and nondegen-
erate electron and hole gases are considered. The role of
recombination and nonequilibrium charge carriers in the
contact cooling (heating) effect is discussed. Along with the
above, special attention is paid to several aspects of non-
equilibrium thermodynamics of thermoelectric phe-
nomena involved in Peltier effect in semiconductors that
demand a careful examination. The formulation of an
adequate self-consistent theoretical model describing the
Peltier effect is also presented.
The Peltier effect was discovered in 1834 in a contact of
two metals, and it was described as the heat extraction or
absorption that occurs at the contact metals when a DC
electric current flows through it (1). As long as the
attempts to repeat the experiments to confirm this new
effect failed to give positive results, it was not recognized
by physicists until 1838 when E. H. Lentz managed to
verify visually the Peltier effect (2).
The first theoretical descriptions of thermoelectric
effects were based on the thermodynamic ideas
applied to the simplest models of thermoelectric circuits.
R. Klausius and W. Thomson initiated the development of
a theory almost simultaneously. The first result of these
investigations was the paper by W. Thomson (3). This
paper marked the beginning of the development of
the phenomenological theory of thermoelectricity. In
1931, L. Onsager used the thermodynamics of irreversible
processes to describe thermoelectric effects, but his results
were not different from those obtained by W. Thomson (4).
In the middle of the twentieth century, A. F. Ioffe and his
colleagues led the revival of interest in thermoelectricity (5).
One of the first materials they studied was PbTe, and they
quickly understood that the most prospective materials for
Peltier effect were semiconductors.
The Peltier effect can be used to create a refrigerator
(see Figure 1) that is compact and has no circulating fluid
or moving parts; such refrigerators are useful in applica-
tions where their advantages outweigh the disadvantage of
their very low efficiency (6–14).
Cooling devices play a crucial role in everyday life. We
use them to preserve food and drugs, among many other
purposes. Often, persons cannot travel freely because they
use a medicine that must be kept in a refrigerator. It is easy
to understand that a 10-cubic-foot refrigerator or an icebox
J. Webster (ed.), Wiley Encyclopedia of Electrical and Electronics Engineering. Copyright # 2014 John Wiley & Sons, Inc.
are not acceptable solutions to allow the mobility of persons
eased low power supply requirements (low-power DC
instead of wall alternating current [AC] or lead batteries
used in cars) would be very useful. They would be used in
many different applications, such as in cryogenic skin
surgery, high-availability electronic systems, and defense.
In addition, those refrigerators should have a long life and
be maintenance-free.
Thermoelectric cooling may advantageously replace the
current cooling methods based on chlorofluorocarbons
(CFCs) that are suspected as responsible for the break-
down of the ozone layer. Thermoelectric cooling has some
distinct benefits, as follows:
1. Switch from heating to cooling by inverting the
polarity of the applied bias.
2. Vibration and acoustic noise free.
3. Modulation of the cooling power through the supply
bias.
4. Maintenance free.
5. Free of moving parts.
6. Functioning freely and independently of the
position.
Several interesting results have been reported on the
progress in materials science with applications in thermo-
electrics: Skutterudites, clathrates compounds, half-Heus-
ler alloys, compounds of layered bismuth telluride
structures, and low-dimensional structures (such as quan-
tum dots and superlattices) have been investigated as a
means to increase the thermoelectric figure of merit.
The traditional theory of the Peltier effect is presented
in several books (5–9, 14) and reviews (10, 11, 15, 16), but
many important aspects of the Peltier effect are far from
being covered satisfactorily in common books. In this
article, we will present the current status of the theory
of Peltier effect.
TRADITIONAL THEORY OF PELTIER EFFECT
From the earliest papers on thermoelectrics right up to the
latest publications, this effect has been defined as an
absorption of heat (in addition to the Joule heat) of the
junction of two conductors or its cooling through which a
DC electric current flows (see, for example, References 5, 6,
14, and 16–18). The absorption of this heat or its evolution
depends on the direction of the electric current, and per
unit time, it is equal to
QP ¼ ðP1 — P2 ÞJ (1)
where P1;2 are the Peltier coefficients of the conducting
materials at each side of the junction and J is the total
electric current.
For a nondegenerate system of electrons (subscript n)
and holes (subscript p) (14), the Peltier coefficient is
i
h
Pn;p ¼ ;1=e ðgn;p þ 5=2ÞT — mn;p (2)
2 Peltier Effect in Semiconductors

Figure 1. Schematic of a thermoelectric couple.

where T is the temperature in energy units; mn,p are the while for the degenerate case (jmj T, m > 0)
chemical potentials of electrons and holes that are meas- . Σ
ured from the bottom of the conduction band and the top of p 2T 2 3
the valence band, respectively (mp ¼ —eg — mn, where eg is hei ¼ m þ gþ (8)
the band gap); e is the hole charge; and gn,p are the 3m 2
exponents in the momentum relaxation times (19): In some papers (see, for example, References 15 and 17), it
is emphasized that the Peltier effect manifests itself in the
. Σgn;p thermally uniform systems, i.e., when the temperature
tn;p ðeÞ ¼ t0n;p e (3)
T gradient is absent.
Thus, the authors of Reference 17, when describing the
where e is the carrier energy. The constant quantities t0n;p Peltier effect, wrote the following:
and gn;p for different relaxation mechanisms can be found
in Reference 19. If an electric current is driven in a bimetallic
For degenerate electron and hole gases circuit maintained at uniform temperature,
. Σ then heat is produced at one junction and
p2 3 T2
absorbed at the other (Figure 2). This is because
Pn;p ¼ ; g þ (4) an isothermal electric current in a metal is accom-
3e n;p 2 mn;p
panied by a thermal current q ¼ Pj, where j is the
To understand the physical meaning of equations 2 and 4, electric current density. Because the electric cur-
it is convenient to rewrite these expressions as follows: rent is constant in the closed circuit and the
Peltier coefficients differ from metal to metal,
1h i the thermal currents in the two metals are not
Pn;p ¼ ; hein;p — mn;p (5) equal, and the difference must be produced at one
e
junction and supplied to the other to keep the
temperature uniform.
where hein;p is the mean kinetic energy of the carriers in the
flux,
Once the discussion of the physical principles of the
R1 df n;p ðeÞ Peltier effect is concluded, we will briefly revise its
0
tn;p ðeÞe5=2 de
0 de (6)
hein;p ¼ df n;pðeÞ
R1 0
0 tn;p ðeÞe 3=2 de
de jq = ∏ j
T0 T0
where f 0n;pð Þe are the Fermi-Dirac distribution functions. j
Notice that, similar to the case of the chemical potentials,
the mean energies he i n;p are measured from the bottom of
the conduction band and from the top of the valence band, jq jq
respectively. Often, the chemical potentials mn;p are inter-
preted as the potential energies of electrons and holes (14).
j j
For nondegenerate statistics (jmj T, m < 0)
. Σ
5 T0 T0
hei ¼ g þ T (7)
2 Figure 2. Schematic circuit of Peltier effect for constant T.

applications. Actually there are many of them, for several
reasons. Thermoelectric devices use DC electric current,
and changing its direction switches the device from the
cooling mode to the heating one or vice versa. Precise
temperature control ð< T0:1○ CÞ can be achieved with
Peltier coolers. Having such advantages, thermoelectric
coolers find a lot of applications in areas such as consumer
products (recreational vehicle refrigerators, automobile
seat coolers, portable picnic coolers, motorcycle helmet
refrigerators, and residential water coolers/purifiers), lab-
oratory and scientific equipment (coolers of infrared detec-
tors, laser diode coolers, integrated circuit coolers, heat
density measuring), industrial equipment (personal com-
puter [PC] microprocessors, fine temperature control),
medical instruments (portable and fixed pharmaceutical
refrigerators, blood analysis, insulin coolers), restaurants,
and restaurant industry products (hotel room refrigera-
tors, noiseless air conditioners, ice makers). This list is not
complete and can go on and on.
At the same time, it is necessary to point out some
disadvantages of thermoelectric coolers. First, they have
a low efficiency compared with conventional refrigerators.
Current thermoelectric devices operate at about 10% of
Carnot efficiency, whereas the efficiency of a compressor-
based refrigerator is about 30%. Thus, the use of thermo-
electric coolers is restricted to applications where their
unique advantages outweigh their low efficiency. Although
some large-scale applications have been considered,
Peltier coolers are generally used in applications where
small size is needed and the cooling demands are not too
great, such as cooling electronic components (see, for the
sake of example, References 20 and 21).
Summing up, one could say that the traditional
explanation of the Peltier effect presupposes the following
(22, 23):
1. An isothermal state of the structure (bimetallic cir-
cuit) exists, through which an electric current flows;
consequently, there is total absence of thermal fluxes
that would be proportional to a temperature gradi-
ent. The only thermal fluxes are those accompanying
the electric current.
2. If a thermal interaction between this structure and
the external heat reservoirs is necessary to maintain
the previously described isothermal state (a Peltier
heat source and a Peltier heat sink), then it becomes
necessary to take into account the external sources of
heat.
An important question arises regarding these consider-
ations: What do authors imply by the concepts of thermo-
electric “cooling” or “heating” in the traditional theories?
The presence of heat fluxes from the external reservoirs
into the structure and vice versa from the structure to the
external reservoirs does not describe heating or cooling
processes under an isothermal condition for the structure.
Another question is as follows: Can the Peltier effect
occur in the thermoelectric circuit without a thermal
interaction with the surroundings at the junctions; i.e.,
can the Peltier effect occur as a physical phenomenon in a
structure adiabatically insulated?
Peltier Effect in Semiconductors 3
The answer given by the cited works to the second
question is negative. But, it can be readily shown that
the Peltier effect in an adiabatic structure may take place
beyond the traditional interpretation of the Peltier effect.
PHYSICS OF PELTIER EFFECT IN n-n AND p-p STRUCTURES
The origin of the Peltier effect is not associated with the
external Peltier heat sources or the Peltier heat sinks. This
effect can also exist in an adiabatically insulated thermo-
electric structure. It is necessary to understand the con-
cepts of “cooling” or “heating” of the junctions as the
decrease or increase in the junction’s temperature com-
pared with the equilibrium one in absence of electric
current. Of course, this statement contradicts the hypoth-
esis isothermal conditions, from where a natural question
immediately arises: Why is a nonuniform temperature
profile established across the structure in the absence of
external heat sources when an electric current flows per-
pendicularly to the two media interface?
Let us consider the simplest structure composed of two
uniform semiconductors through which the electric cur-
rent flows in the direction 0x (Figure 3). Assume that the
electric contacts x ¼ —d1 and x ¼ d2 are kept at the equi-
librium temperature T 0, that the lateral surfaces are
insulated adiabatically, and that the structure’s cross-
sectional area is equal to the unit measurement every-
where. For simplicity, we shall assume initially that a heat
resistance of the junction located at x¼0 can be neglected
(this assumption will be removed later on); this assump-
tion implies temperature continuity at the interface in
x ¼ 0.
T1ðx ¼ 0Þ ¼ T2ðx ¼ 0Þ (9)
where T1;2 ðxÞ are the temperature distributions in each
region of the structure.
Usually, the thermal flux Pj is named the Peltier heat
flux (16). For the theory stated, it is more convenient to
name this heat flux a “drift heat flux” because it is associ-
ated with the charge drift transport in the external electric
field, and accordingly, for holes the “drift heat flux” and
current have the same direction while they are opposite for
electrons. An important feature of the drift heat flux is that
Figure 3. Schema of the simplest Peltier device consisting of two
different media.
4 Peltier Effect in Semiconductors

it is associated with particle drift in a single direction; this j

is in strong contrast with the movement in two opposite
directions in the thermal diffusion flux that will be ana-
lyzed below. (1) = – κ dT1 (2) = – κ dT2
qdif 1 qdif
According to the Le Cha ^ telier-Braun principle in the dx 2
dx
irreversible thermodynamics (24), “some internal fluxes
appear in the system in the stationary state when an
external influence affects this system, and these internal
fluxes weaken the results of this influence.” Applying this
principle to our problem, one can say that the discontinuity ddr(1) = ∏ j1 ddr(2) = ∏ j2
in the drift fluxes at the junction x ¼ 0 that appears because
of the different Peltier coefficients (P16¼P2) must lead to
other thermal fluxes tending to reduce this discontinuity
(22).
These thermal fluxes can only be thermal diffusion x=0
fluxes (qdif ¼ —kdT=dx, k being the thermal conductivity)
because the other drift heat fluxes are absent. The Figure 4. Heat fluxes in an n-n structure assuming Pj2 < jP1 ,j j
“diffusion heat flux” nature greatly differs from the one k1;2 is thermal conductivity in each region.
of the drift heat flux. To understand the origin of the
diffusion heat flux, let us consider a material with a
nonhomogeneous temperature profile across it; under second side too, as compared with the temperature on the
these conditions, the equilibrium in the microscopic fluxes surface x ¼ d2. As a result, an induced thermal diffusion
and balance will be removed. Inside the material, two flux qdif
2 ¼ —k 2dT2=dx arises in the second sample, where

fluxes of quasiparticles will take place: one of particles
moving from the hotter area into the cooler one and a
second flux of particles in opposite direction. The total
particle flux balance is null in the absence of electrical
current or when particles are not charged (phonons). But
because the energy of carriers in the hotter area is larger
than the ones in the cooler one, the total heat flux is
nonzero and is directed from the hot side toward the
cold side. This flux is the diffusion heat flux.
Thus, a temperature heterogeneity arises inevitably in
the structure in the presence of an electric current.
Because of this temperature distribution, the temperature
of the junction can be lower (thermoelectric cooling) or
higher (thermoelectric heating) than the equilibrium one.
Because we are not interested in carrying calculations
in real structures, let us keep considering the simple
structure of Figure 3, assuming that it is composed of
two n-type semiconductors and using the same subscript
convention. Both drift heat fluxes drq1;2¼ P1;2j flow in this
structure in the direction opposite to the electric current
direction, as it is pointed in Figures 4 through 6, because
P1;2 < 0 in the n-type materials (14).
Let us suppose thatj P2j < jP1 jfor definiteness. In this
case, the drift thermal flux increases when coming from
side 2 into side 1 (Figure 4). According to the Le Cha ^ telier-
Braun principle, a thermal diffusion flux q1dif ¼ —k1dT1=dx
(k1 being the thermal conductivity of the left side) should
arise in the first side, tending to compensate this increase
of drift heat flux. It is clear that the direction of this flux
should be opposite to the direction of the drift flux
q1dr ¼ P1j. We name these arising thermal diffusion fluxes
the “induced thermal diffusion fluxes.”
In turn, this means that the temperature of the junction
from the side of the first sample decreases in comparison
with the temperature on the surface ¼x—d1. The condi-
tion of the temperature continuity (eq. 9) requires a reduc-
tion in temperature in the junction from the side of the
k2 is the thermal conductivity of the right side. Let us
notice that this thermal flux direction coincides now with
the direction of a drift heat flux drq2¼ P2j in this sample
(Figure 4), tending to decrease the discontinuity in drift
heat fluxes.
The corresponding temperature distributions in the
structure are qualitatively represented in Figure 5. It is
obvious that for jP2j < jP1j and the chosen electric current
direction, the junction temperature T (x ¼ 0) decreases as
compared with the equilibrium temperature T 0. The low-
ering of the temperature caused by the emergence of the
induced thermal diffusion fluxes is the essence of the
Peltier thermoelectric cooling.
If the conditionj P2j > Pj 1 takes
j place and the electric
current has the same direction, then the drift heat flux
decreases when passing through the junction. In this case,
the induced thermal diffusion flux arises in the first sample
again, but its direction changes to the opposite compared
with the previous case (Figure 6). Now this flux tends to
T(x)
T0
–d1 0 d2 x
T1(x) T2(x)
Figure 5. Temperature distribution in an n-n structure assuming
jP2j < jP1j.
 Peltier Effect in Semiconductors 5

dT1 dT2
(1)
qdif =–κ1 (2)
qdif =–κ2
dx dx

ddr(1) = ∏ j1 ddr(2) = ∏ j2

Figure 8. Heating or cooling of a metal-n-type semiconductor

contact.

x=0
Figure 6. Heat fluxes in an n-n structure assuming jP2 j > jP1j.
increase the drift thermal flux q1 ¼ P j, which has
1
dr
decreased compared with q2drP¼
2j.
Further reasoning is similar to that used in the analysis
of the previous situation, and it leads to the temperature
distributions in the structure presented in Figure 7. In this
case the junction temperature increases in comparison
with the equilibrium temperature T 0, and this situation
corresponds to the Peltier thermoelectric heating.
Thus, we have to understand the Peltier effect as the
lowering or raising of the junction temperature (depending
on the current direction) as a result of the appearance of
the induced thermal diffusion fluxes in the structure, but
not as an evolution or absorption of the additional heat on
the junction.
To demonstrate an additional physical meaning (25) of
the Peltier effect, a metal-n-type semiconductor contact is
normally used (see Figure 8). It is easy to verify that the
surplus of the electron energy in the semiconductor in
comparison with the metal is De ¼ hei — mn ¼ ðg þ 5=2ÞT —
mn and P1 P—2 De=e.
¼ Some additional assumptions will be introduced. Let us
The obtained result is clear for this type of contact. At
the same time, these contacts are not really used in appli-
cations. The consideration of other contacts does not have
the same obvious understanding, and a priori the following
questions arise:
T(x)
● What does the potential energy for the degenerate gas
of the charge carriers mean?
● What is the physical meaning of the energy change in
a metal-p-semiconductor contact and in a p-n
junction?
● Why does the approach stated above ignore the work
of the built-in electric field within the contact?
● It is easy to show that the value h ie—m in any type of
contacts is different on the left and on the right from
the contact plane. It means that single electron tran-
sitions cannot determine the work of the refrigerator.
Therefore, the description of the contact refrigeration
based on the consideration of the separate electron
transitions is not valid. One needs to take into
account the statistics of these transitions. How can
one reflect this fact in the preceding scheme?
In the usual scheme of n-n or p-p junctions, the contact
heating or cooling is explained by the electron (hole) tran-
sitions between he i–levels (see Figure 9). The latter are
counted from the common Fermi level.
consider first the n-n contact between nondegenerate semi-
conductors (Figure 10). If the momentum scattering in
both semiconductors is the same, then (see eq. 2):
m1 — m2 x0 — x1 — x0 — x2 Dec
P1 — P2 ¼ ¼ 1 2 ¼ wc þ (10)
e e e

T1(x) T2(x)

–d1 T0 0 d2 x

Figure 7. Temperature distribution in an n-n structure assuming Figure 9. Energy band diagram of n-n or p-p contacts in equili-
jP2j > jP1j. brium (j ¼ 0).
6 Peltier Effect in Semiconductors
Figure 10. Energy band diagram of the contact of two nonde-
generate semiconductors. e0 is the vacuum level, and xi and xi0 are
the work functions and electron affinities, respectively.
where xi and x0i (I ¼ 1, 2) are work functions and electron
affinities of materials 1 and 2, wc ¼ ðx2 — x1Þ=e is the
contact voltage, and Dec ¼ x0 — 1
x0 is
2
the work of the
valence force. As is known, this is a result of the length
of the forbidden region that is position dependent. It means
that the contact cooling or heating is connected with the
work of the built-in electric field Wc and the work of the
valence forces Wn. The total work is W ¼ QP ¼ Wc þ Wn,
where Wc ¼Jwc and Wn ¼JDec=e. Here, the valence force
is caused by the abrupt change of the conduction band.
Similar reasoning is valid for the p-p junction.
If we have a contact between degenerate and nonde-
generate semiconductors, i.e., the nþ-n or pþ-p junction,
then the Peltier effect does not depend on the contact
properties, and it is determined only by the parameters
of the nondegenerate semiconductor (see Figure 8).
mn
P1 — P2 ¼ —
e describe this junction by the coefficient of the surface
In the case of a contact between two degenerate n- or p-type
semiconductors (or two metals), the Peltier effect depends
on the contact properties again (see Figure 11 and eq. 4),
Figure 11. Energy band diagram of the contact between two
metals.
and the work of the built-in electric field jointly with the
work of the valence forces occurs.
Now,
. Σ
p2 3 T2
P1 — P2 ¼ gþ ðm1 — m2Þ (12)
3e 2 m1m2
Comparing equations 10 and 12, we see that the Peltier
heat in the contact between degenerate materials is essen-
tially less than that in the contact between the nondegen-
erate semiconductors.
Let us also note that the work of the built-in electric
field and the valence forces will give rise to the qualita-
tively different temperature of the contacts in the cases of
nondegenerate and degenerated branches of the circuit. In
the former
3
Wc / ðTðEÞ — T0 Þ (13)
2
where T(E) is the nonequilibrium temperature, E is the
built-in electric field, and T0 is the room temperature. In
the latter,
Wc / p T ðEÞ — T0
2 2 2
(14)
4 m
The quantitative calculation of the thermoelectric cooling
or thermoelectric heating requires a solution to the heat
transfer equation with the corresponding boundary condi-
tions. The next section is devoted to this calculation.
ENERGY AND HEAT BALANCE EQUATIONS FOR
UNIPOLAR SEMICONDUCTORS
Let us now remove the assumption about the absence of the
(11) thermal resistance at the junction x ¼ 0. Instead, we shall
thermal conductivity (26–29), which can take arbitrary
values. Later, we shall show that the junction is described
not only by the surface thermal conductivity but also by
some other surface parameters.
The searched temperature distribution in the structure
can be obtained from the energy balance equation. In a
steady state, it is given by (16)
rw ¼ 0 (15)
where w¼qþcj is the energy flux of charge carriers
(electrons or holes), q¼ — k rT þPj is a total heat flux of
these carriers, c ¼w— m=e is the electrochemical poten-
tial, w is the electric potential, m is the chemical potential,
and e— is the electron charge.
Now equation 15 can be rewritten in the form
rq þ jrc ¼ 0 (16)
We have made the assumption that nonequilibrium carri-
ers are absent in the structure (30), i.e., j 0. Let us note
r ¼
that it is necessary to take into account the nonequilibrium
carriers in p — n structures (17, 18).

Using the equation for the electric current (31)
j ¼ —sðrc þ arTÞ (17)
to eliminate the electrochemical potential c (s is electric
conductivity and a is the Seebeck coefficient), we arrive at
the heat balance equation
rq ¼ j 2=s þ ajrT (18)
It is easy to see, from the shape of this equation, that there
are only two sources of heat: one of them is the Joule heat,
and the remaining source of heat can be named the Thom-
son heat because of its proportionality to the product of j
and T r (32).
Because the temperature gradient has appeared from
the Peltier effect, we can say that the Thomson effect
occurs as a consequence of the Peltier effect in the ther-
moelectric cooling (heating) phenomenon.
Let us note that according to our definition following
from the heat balance equation (eq. 18), the Thomson
coefficient is equal to the Seebeck coefficient a. From
this definition, it follows that the Thomson heat occurs
even in the case when the Seebeck coefficient does not
depend on temperature. Moreover, it is possible to claim
that thermoelectrics contains only one fundamental
parameter, which is the Seebeck coefficient.
Thus, only one thermoelectric relationship was named
the second thermoelectric relationship, P ¼ aT (15, 16). As
it was shown in Reference 16, it follows from the Onsager’s
principle of kinetic coefficients symmetry. The first ther-
moelectric relationship actually determines the Thomson
coefficient t. As it follows from equation 18, it can be
reduced to the trivial equality¼t a.
The Thomson coefficient was determined by the
equation t ¼ @P=@T — a in the previous publications
(5–9, 14, 18, 31, 41). The authors of these works formed
the term by combining j@P=@T rT from divq with the term
T presented on the right-hand side of equation 18. This
aj r
is incorrect because ajrT is the source of heat while
j@P=@T rT is just a part of the thermal flux change.
This is trivially wrong from the formal point of view. We
cannot state that the left-hand side of equation 18
is still the complete divergence of the thermal flux vector
q ¼ —k rT þ Pj when the term j@P=@Tr T is moved to the
right-hand side of equation 18 or that it is the divergence of
another vector in this case.
Now, the sense of the Thomson heat is very transparent.
It is the charge carriers heating or cooling in the thermo-
electric field Ete ¼ arT. In a certain sense, it can be named
the Joule effect associated with the thermoelectric field.
The Joule heating takes place in the electric field. It is
important to note that the Joule effect leads to heating in
any case, whereas the Thomson effect may lead to either
the electric
heating currentdepending
or cooling and the temperature gradient.
on the relative Subse-
directions of
quent development of these ideas can be found in Refer-
ence 32.
Equation 18 demonstrates that the Peltier source of
heat is absent everywhere in the structure volume, as it
was pointed out previously in this article. For this reason,
the statement about the Peltier’s heat absorption or
Peltier Effect in Semiconductors 7
generation loses its physical sense in the bulk of the
structure (the analysis of this situation at the junction is
presented next).
Let us now obtain the boundary conditions for equation
18 (22, 23). Because equation 18 is an equation of the
second order in relation to unknown temperatures T1ðxÞ
and T2 ðxÞ for two-layer samples, it is necessary to obtain
four boundary conditions. Two of them correspond to the
assumptions that were made before
T1ðx ¼ —d1Þ ¼ T0 (19)
T2ðx ¼ d2Þ ¼ T 0 (20)
The next boundary condition describes the total heat flux
continuity at the boundary of the two media
ðq1ðx ¼ 0Þ ¼ q2ðx ¼ 0ÞÞ in the most simple case of the
absence of heat sources and sinks on the interface x ¼ 0.
k1 rTðx ¼ 0Þ — P1 j ¼ k2 rT 2 ðx ¼ 0Þ — P2 j (21)
Last, the fourth boundary condition determines the heat
flux through the interface x¼0 with the surface thermal
conductivity h (33).
h½T 1 ðx ¼ 0Þ — T 2 ðx ¼ 0Þ] ¼ —k1 rTðx ¼ 0Þ þ P1 j (22)
The right-hand side of equation 22 determines the total
thermal flux flowing into the interface of the two media.
The expression on the left-hand side of the equation deter-
mines the same thermal flux in the surface layer ¼ x 0 (for
simplification, we neglect the surface Peltier coefficient
(33) in the given work, supposing it negligibly small in
comparison with the bulk Peltier coefficient).
TEMPERATURE DISTRIBUTION IN n-n AND p-p
STRUCTURES
To obtain the required temperature distributions we will
use the heat flux continuity equation (eq. 18) in the linear
approximation of j, which for a homogeneous medium in
one dimensional case reduces to
d2T=dx2 ¼ 0 (23)
Together with the boundary conditions (19–22), equation
23 results in the following temperature distributions:
( Σ Σ
T ¼ T 1 T P T hd2;1 ðP — P Þ
1;2 0 1;2 1 2
k2;1
. Σ
j d1;2 Σ ) .
—d1 ≤ x ≤ 0
Tx
0 ≤ x ≤ d2
× h .d11 d22 Σi ;
T0k1;2 1 þ h k þ k : ð24Þ
The second term in the square brackets of equation 24
determines the contribution of the Peltier effect to the
temperature distribution in the structure with a finite h.
This term defines the Peltier thermoelectric heating or
cooling considered in the introduction. As it has been
shown in Reference 25, the value ð P1 —P2 Þj determines
the change in the kinetic energy flux on the junction. This
8 Peltier Effect in Semiconductors
change is completely dependent on the electric potential
barrier parameters on the junction, such as the work
functions of the contacting semiconductors and their elec-
tron affinities.
Let us note, as it has not been previously mentioned,
that the Peltier effect depends strongly on the junction
surface thermal conductivity. The contribution of this
effect to the total effect of thermoelectric cooling increases
with an increase in surface thermal conductivity and it
slackens with a decrease in surface thermal conductivity.
The term in the square brackets of the numerator of
equation 24 determines a new cooling or heating effect that
cannot be reduced to the Peltier effect. First, it is deter-
mined not by the difference between the Peltier coefficients
but by each Peltier coefficient separately. This implies that
this effect can be observed in a structure composed of a
single material and radically distinguishes it from the
Peltier effect. Besides, this effect is not associated with
the electric potential barrier on the interface ¼ x 0, being
determined exclusively by the junction surface thermal
properties.
The heat balance equation (eq. 18) is in the general case
a nonlinear equation of the density of the electric current j.
This follows from the nonlinear terms describing the Joule
and the Thomson heat. In the case of the Thomson heat, it
is necessary to take into account that the temperature
gradient in the problem considered is not created by any
external sources. It arises only as a result of an electric
current flow. Thus, both the Joule and the Thomson heat
sources are nonlinear terms in j. As it was shown in
Reference 32, the magnitudes of both heat sources are of
the same order. The Thomson heat even exceeds the Joule
heat in good thermoelectric materials, i.e., those materials
that exhibit a figure-of-merit ZT, where Z is ¼ Z a2s=k (5),
exceeding the unity (more details about ZT will be given in
the section titled, “Applications”). Besides, both the
coefficient of thermal conductivity and the Seebeck
coefficient depend on temperature, which is also a function
of the electric current.
At the same time, it is easy to observe that the non-
equilibrium temperature distributions occur even in the
linear approximation with respect to the electric current.
So, thermoelectric cooling or heating are linear effects in
an electric current and manifested themselves “in the pure
state” only at small values of current when the Joule and
the Thomson heat do not play a noticeable role. For this
reason, it is convenient to consider the problem of thermo-
electric cooling just in the linear approximation to the
electric current j.
Let us notice that all the equations obtained above
remain true for the structures composed of semiconductors
with the p-type conductivity. It is only necessary to con-
sider that P1;2 > 0 in this case.
The Peltier effect occurs at the junction of semiconduc-
tors with electron and hole conductivities too. However,
the thermoelectric processes in this case depend essen-
tially on the recombination rates in areas close to the
junction (see References 25, 30, 34–36). In the case of an
infinitely strong recombination, all the equations above are
correct. The essential difference between this case and the
previous ones is that now the material with the n-type
conductivity is characterized by the Peltier coefficient
Pn < 0, whereas the material with the p-type conductivity
is characterized by the Peltier coefficient Pp > 0. In the
last case, both areas close to the junction will be heated or
cooled (depending on the direction of the electric current)
simultaneously and the effect of thermoelectric cooling
(heating) is more intense.
In fact, let us assume for simplicity that the structure
represented in Figure 3 is composed of p- and n- materials
identical in length and with equal values of the coefficients
of thermal conductivity d ¼1 d2¼ d; k1¼ k2 ¼ k; that the
recombination rate on p-n junction is infinitely high; and
that the Peltier coefficients of both materials are equal in
absolute magnitude (P1 P¼2).—
In this case, the Peltier effects are
. Σ
jPjd
Tðx ¼ 0Þ ¼ T 0 1 — j (25)
T0k
where j P j ¼Pj1 jP¼
2 j. The
j last equation shows that the
Peltier effects are commensurable in the structure
considered.
COOLING IN INHOMOGENEOUS SEMICONDUCTORS
(BULK PELTIER EFFECT)
Under certain conditions charge carriers in inhomogeneous
semiconductors can be cooled by a static electric field instead
of being heated, and consequently the carrier average
energy of drops below the lattice temperature T0 (37).
This effect can be explained as follows. Let assume that
the impurity concentration N in a semiconductor depends on
a coordinate (x, for example). If the Debye radius is the
smallest parameter having the dimension of length in the
problem, the carrier concentration at each point will coin-
cide with the impurity concentration (26, 27), thus establish-
ing an electron concentration gradient (dN/dx).
It is well known that an associated electrostatic internal
field is then directed along the gradient. An external
electric field applied to the sample will induce a current
in the same direction as this field (31). If the current
direction is opposite to the direction of the concentration
gradient and the external field is weaker than the field
associated to the gradient dN/dx, then the carriers will
move in a (total) field that is oriented against their motion.
Then, the electric field will obviously remove energy from
the carriers, which are thus “cooled.” The energy removed
from the carriers must be liberated outside the sample, to
the current source, for example.
The described effect is somewhat analogous to the
Peltier effect, although the former is of spatial character.
Let us as assume an isotropic quadratic electron dis-
persion law and that collisions between carriers and scat-
tering centers are quasielastic (with the momentum-
transfer average free carrier path lp le (38)).
The concentration of impurities, and therefore that of
the carriers, depends on x and it is given, for simplicity, by
N ¼ N 0 expð—x=lÞ. The magnitude of N0 is such that the
frequency nee of interelectronic collisions greatly exceeds

the frequency ne of collisions between electrons and scat-
tering centers accompanied by energy transfer.
Under the previous assumptions, our problem may be
considered one dimensional (i.e., all quantities will depend
only on the x coordinate).
The electron temperature as a function of the coordi-
nates can be determined by the equation of heat balance,
which can be obtained from the following kinetic equation
(see References 26 and 27, for example):
dq=dx ¼ jE — NðxÞne ðTe — T 0 Þ (26)
where E ¼ —dw=dx,
q ¼ N=N 0 ke T e 1þg ½eE — T e =NdN=dx — ð2 þ gÞdT e =dx]
(27)
is the heat flux in electron subsystem and E is the electric
field strength in the sample (E has only an x component).
j ¼ N=N 0 sT e g ½E— T e =e× 1=NdN=dx — ð1 þ gÞ× 1=edT e =dx]
(28)
is the current and Te is the electron temperature. The
parameters
4Gð7=2þ Þg 0N 4Gð5=2 þ Þ
gN0 e
2 a current from the n-region to p-region) from the interface
ke ¼ pffi ffiffi ; s¼ pffi ffiffi
3 pmn 0 T g0 3 pmn0 T 0g
are, respectively, the electronic heat and the electric con-
ductivity at T¼e T 0. n¼ nð0 TÞð —g is the frequency of
0 e=T0 Þ
collisions with momentum transfer (26, 27) between
electrons and scattering centers. n¼e nð0e TÞð 0 T e=T 0 Þr
—1
(26, 27) is the frequency of collisions with energy transfer
(26, 27) between electrons and scattering centers. r and g
are numerical coefficients with magnitudes close to one (for
which explicit expressions are given in Reference 19),
whose values depend on the scattering mechanism with
respect to the carrier energy and momentum, respectively.
Because under stationary conditions the current density
j does not depend on the coordinate, it is convenient to
express the field E in terms of j. Using equation 28, we
obtain E and substituting it and q into
equation 27, we can finally obtain the expression for the
electron temperature.
This equation must be supplemented with the boundary
conditions for temperature in the planes ¼ x 0 and ¼ x L,
where L is length of sample (see eq. 21).
In the current range 0 < j < jc, where jc ¼ 2le=lð5=2 þ
expðL=lÞ—1 ek
le T0 is the average temperature hT e i < T 0
gÞ expð2L=lÞ—1
RL
where hT e i ¼ 1=L TeðxÞdx, if le < l (37). As the ratio
0
le =l increases, the minimum of hT e i as a function of j is
shifted to higher values of j; hTeimin can be of the order of
unity when le/l 1~(37).
Note that the one-temperature approximation consists
of assuming that the temperatures of all quasiparticles
(electrons, holes, and phonons) in each spatial point
coincide. Until now, this approximation has been widely
used for research of the thermoelectric cooling phenome-
non. However, the criteria for applicability of such an
Peltier Effect in Semiconductors 9
approximation are usually not discussed. Nevertheless,
there are many phenomena in which the temperatures
of current carriers and phonons are different from each
other (as it was shown in this section).
As it is well known (22), the Peltier effect, which under-
lies thermoelectric cooling, is a contact phenomenon. It
occurs in a subsystem of electrical-charged quasiparticles
(electrons and holes). That is, the electron and/or the hole
cooling takes place near an interface. Then, the lattice is
also cooled by means of energy interactions between elec-
trons (holes) with phonons near the interface. As a result of
this two-step process, different temperatures are set in the
subsystems of current carriers and phonons.
Thus, it is obvious that the multitemperature approxi-
mation, when each subsystem of quasiparticles is charac-
terized by its own temperature, is more appropriate for the
investigation of the thermoelectric cooling phenomenon
(39, 40).
PELTIER EFFECT IN p-n JUNCTIONS
Conventionally, a p-n structure is used to make a thermo-
electric refrigerator (5, 6, 9, 41) because of the thermo-
electric drift fluxes directed (at a corresponding direction of
toward the edge in both layers of the p-n structure that
strengthens the cooling phenomenon (22). Traditionally,
the studies of the Peltier effect do not consider the non-
equilibrium charge carriers, so that only majority charge
carriers and their electric current are taken into account in
the expressions for heat fluxes in n- and p-regions, even
though the current of minority charge carriers near the p-n
junction has the same order of magnitude than the current
of majority charge carriers (25, 42) (see Figure 12).
In this way, the thermal generation and extraction of
minority charge carriers must take place near the interface
to allow the flow of electric current (42). As a consequence,
nonequilibrium charge carriers will settle (25, 35, 36).
Let us examine the p-n junction (Figure 13). It is easy to
see From Figure 13 that
P—P mn þ mp (29)
1 2 ¼—
e
Figure 12. Distribution of currents in p-n junctions.
10 Peltier Effect in Semiconductors

Figure 13. Energy band diagram of a p-n junction.

Recombination.

Figure 14. Energy band diagram a p-n junction without

The generation or recombination at the contact causes
recombination.
the Peltier heating or cooling in this case.
At the same time, there are a lot of situations where this
rate is weak enough. What has happened with the Peltier
effect in this case? The situation is similar to the electric
current or thermoelectric current in bipolar semiconduc-
tors. The Fermi quasilevels will set up causing the
redistribution of carriers concentrations and, accordingly,
modifying the electric field profile. As a result, the nature
of the Peltier effect can drastically change.
It follows from Figure 14 that under the chosen current
direction cooling of the junction switches to heating in
absence of recombination.
The equivalent electric circuits are presented in
Figures 15 and 16 for the two limiting cases, very strong
and weak recombination, respectively.
The thermoelectric behavior of p-n junction for Peltier
effect was investigated for the first time in Reference 43.
Experimentally, this phenomenon was discovered in 1974
by Ponomarenko and Stafeev (44). The investigation of
the thermoelectric effect was undertaken in the following
years in a number of studies (45–53). Unfortunately in
all these articles, several assertions were incorrect and
led to erroneous results. Some of the mistakes were
already pointed out and discussed in Ref. 54; this short
paper is free from fundamental errors, but it presents
neither new equations nor a quantitative analysis of the
thermoelectric phenomena. Common mistakes in previ-
ous studies, additional to those discussed in Ref. 54, can
be found in the modeling of the recombination used, in
the energy balance equation, in the boundary conditions,
and so on (35, 36). The analysis of the thermoelectric
cooling that is given in References 43–54 is only approxi-
mate because it ignores several factors as we will discuss
next.

Figure 15. Strong recombination: Carrier movement (left) and schematic of the equivalent circuit (right).

Figure 16. Weak recombination: Carrier movement (left) and schematic of the equivalent circuit (right).
 Peltier Effect in Semiconductors 11

HEAT BALANCE EQUATION IN BIPOLAR The expression for the energy flux w in a bipolar semi-
SEMICONDUCTORS conductor can be written in a reduced form as follows:

The energy balance equation has never been sufficiently w ¼ q þ cnjn þ cpjp (33)
investigated in bipolar semiconductors; nevertheless, even
if in the linear approximation with respect to the gradient where
q ¼ qdr þ qdiff (34)
of the temperature (i.e., assuming a small mismatch of the
temperatures in both regions) a significant population of If the transport energy processes take place in a bipolar
nonequilibrium charge carriers will always set up and, semiconductor, then the rate of change of the energy
consequently, generation-recombination processes must density u in the semiconductor is as follows:
be taken also into account (55).
Let us note that in this case (as it will be shown next), @u
¼ —divw (35)
the recombination has a dual role. On the one hand, it is @t
the source or the absorbent (sink) of heat, and on the other The right-hand side of equation 35 corresponds to an
hand, it bears a significant influence on the drift heat energy change caused by energy transport. If the processes
fluxes. Consequently, the expressions for the sources of that take place in the semiconductor are stationary, then
the total heat flux and the diffusion heat flux are distinctly the energy of each region does not change with time and
different. equation 35 reduces to the following:
The energy flux density in a unipolar semiconductor is
(see eqs. 15 and 16): divw ¼ 0 (36)
w ¼ q þ cj (30) Now a question arises: “What value plays the role of the
Let us recall that, under the approximation of quasineu- source of the heat flux?” To answer to this question, the
trality, nonequilibrium charge carriers in a homogeneous expression for divq needs to be found. By substitution of
unipolar semiconductor will not exist in the linear approxi- the energy flux, w, from equation 33 into equation 36, we
mation with respect to the perturbation (55). Consequently, obtain the following expression (let us recover the vector
the variation of the electrochemical potential dc reduces to nature of several magnitudes to avoid misunderstand-
the variation of the electrical potential dw (56) because ings):
. Σ . Σ
cn;p ¼ w ; ð1=eÞmn;p, where w is the electrical potential, e divq ¼ —rðc Þ · j — c ðr · j Þ — r c · j — c r· j
ð Þ
is the elementary positive charge, and mn mp is the chemical n n n n p p p p
potential of electrons (holes). This explains why, as it follows (37)
directly from equation 30, the variation of the energy flux dw Taking into account the carrier continuity equations (55),
is equal to the variation of the heat flux dq, dw¼dq under
steady-state conditions (divj ¼ 0). in which the rates of the total recombination are the same
and under total absence of external generation (see next
The heat flux density q is equal to the sum of the density
of the drift heat flux qdr ¼ Pj and the density of the section)
diffusion one qdiff ¼ —k rT. Let us remark that formally rjn ¼ eR; rjp ¼ —eR (38)
heat flux is a vector (q), in here we will drop the vector
where R is the recombination rate. Using equation 38,
notation as, for the sake of simplicity, we are considering a
equation 37 transforms into the following:
one-dimensional case.
In a bipolar semiconductor (57, 58), the drift heat flux is . Σ . Σ
divided in the drift heat fluxes of electrons and holes, divq ¼ m n mp R — rð c nÞ ·j n —r c p ·j (39)
p
Pnj n and qdr;p P¼
qdr;n ¼ pjp , whereas the diffusion heat
þ
flux is equal to the sum of the diffusion heat fluxes of Using the expressions for the electrical current (34)
electrons (holes) qdiff ;n ¼ —kn rT (qdiff ;p ¼ —kp rT) and the . . Σ Σ
diffusion heat flux of phonons, qdiff ;ph ¼ —kph rT. jn;p ¼ —sn;p r cn;p þ an;p rT (40)
. Σ
qdiff ¼ qdiff;n þ qdiff;ph ¼ — kn þ kph rT where sn ðsp Þ is the electrical conductivity of electrons
. ¼
qdiff ¼ qdiff;p þ qdiff;ph ¼ — kp þ kph
Σ (31) (holes), and Pn;p Tan;p. The gradients of the electrochem-
ical potentials can be written as follows:
From equation 31, it follows that the energy rT flux in a
. Σ 1
bipolar semiconductor is r cn;p ¼ — j — an;p rT (41)
sn;p n;p
w ¼ qdr;n þ qdiff;n þ cnjn þ qdr;p þ qdiff;p þ cpjp þ qdiff;ph Substituting the expression in equation 41 into equation
(32) 39, the divergence of the heat flux adopts the following
form:
In this expression of the energy flux in a bipolar semi-
conductor is the energy flux of electrons, holes, and pho- . Σ 1 1
nons. Let us note that c n and c p are independent Fermi divq ¼ m n þ m p R þ jn2 þ jp2 þ a nj n · rT þ a pj p · rT
sn sp
quasilevels of electrons and holes (in equilibrium
cn — cp ¼ eg=e, where eg is the energy gap) (14). (42)
12 Peltier Effect in Semiconductors
From equation 42, we can see that recombination creates
the source of the heat flux ð mþn mpÞR. Because mþ n mp is
negative in nondegenerate semiconductors, if the
recombination rate is positive, then this source of heat
flux is negative ðmn þ mp ÞR < 0, while in the case of ther-
mal generation (R < 0), it is positive ðmn þ mpÞ R > 0. These
paradoxical phenomena will be explained subsequently.
Because under a linear approximation mn þ mp ¼ —eg, the
source of heat flux caused by recombination transforms
into —egR and we obtain the following:
divq ¼ —egR (43)
To find the sources of the diffusion heat flux, the diver-
gence of the diffusion heat flux divqdiff must be obtained.
Substituting the heat flux q from equation 34 into equation
42 and taking into account equation 38, we obtain in the
linear approximation the following:
divqdiff ¼ ðgn þ gp þ 5ÞT0R (44)
Taking into account, that (58)
.Σ Σ Σ
Pn;p ¼ Tð1/eÞ gn;p þ 5/2 T — mn;p
gn;p
(45)
t n;p ðeÞ ¼ t0n;p ðe/TÞ
It is worth noting that the source of the diffusion heat flux
caused by the recombination is positive, ðgn þ gp þ
5Þ T0R > 0 because gnþ gp < 5 (19). This means that
recombination causes the increment of the temperature
(heating) in agreement with common sense.
It should be borne in mind that the absolute value of the
Peltier coefficient, equation 45, of minority carriers can
largely exceed the one of majority carriers. Because the
Fermi quasi-levels depend on the concentration of majority
and minority charge carries, the Peltier coefficients will
depend on the coordinate in the space-charge layer near
the p-n junction (—rnD < x < rpD , where rnD;p is the Debye
radius in the n- and p-regions as indicated by the super-
script) even in linear approximation with respect to the
current because of the spatial dependence of the equili-
brium concentrations near the p-n junction (59).
The expression for the diffusion heat fluxes qdiff
n;p is as
follows:
. Σ
n;p n;p
qdiff ¼ — knn;pþ kp þn;pkph rT (46)
where knn;p; knp;p, and kn;pphare, respectively, the electron,
hole, and phonon heat conductivities in the n- and the
p-regions as indicated by the superscript.
Because kn;p kph in nondegenerate semiconductors,
equation 46 reduces to
qdiff
n;p ¼ —kn;p rT
ph
(47)
Taking into account the considerations presented previ-
ously, the heat balance in equation 43 can be rewritten as
follows:
—kph DT þ Pn r · jn þ Pp r · jp þ jn · rPn þ jp · rPp ¼ —eg R
(48)
Because the current densities can be calculated as
(see eq. 40) follows:
jn ¼ —sn ðrw — rmn =e þ an rTÞ
. Σ (49)
jp ¼ —sp rw þ rm = e þ ap r T
p
the calculation of mn; mp , and w is required.
The macroscopic description of the transport of non-
equilibrium charge carriers is performed using the conti-
nuity equations for the electron and hole current densities
(see eq. 38) and the Poisson equation (30)
r · jn ¼ eR (50)
r · jp ¼ —eR (51)
r
Dw ¼ —4p (52)
e
where r is the space charge, e is the permittivity, and R is
the recombination rate in n- and p-regions.
RECOMBINATION IN SEMICONDUCTORS
To make use of the system of equations 50–52, we should
specify the dependences of partial currents, the space-
charge density, and the recombination rates on the non-
equilibrium-carrier concentration.
Unfortunately, many publications devoted to these
problems contain obvious errors; these fallacies are caused
by the recombination itself that is often described by the
incorrect expressions as follows:
divjn ¼ Rn; divjp ¼ —Rp (53)
with Rn ¼ dn=tn; Rp ¼ dp=tp.
Here n ¼ n0 þ dn and p ¼ p0 þ dp are the electron and
hole concentrations, where dn and dp are the concentra-
tions of nonequilibrium charge carriers, and tn and tp are
the lifetimes of nonequilibrium charge carriers, which are
key parameters of the semiconductor under consideration
(60, 61). However, because the condition for the total
current continuity div j ¼ 0 should be satisfied under static
conditions, an additional condition dn=tn ¼ dp=tp arises;
the latter condition does not follow from any physical
concepts and is difficult to interpret. In certain cases
(see, for example, monograph in Reference 62), this condi-
tion is used to reduce the number of variables, which is
completely wrong. Sometimes, this condition is also con-
sidered as an expression relating to the lifetimes of charge
carriers (60). The latter approach is not physically mean-
ingful and, in addition, is hardly constructive because the
carrier lifetimes no longer constitute the semiconductor
parameters; rather, the lifetimes are functions of the non-
equilibrium carrier concentrations that, in turn, should be
determined, which leads to considerable mathematical
difficulties.
Another approach based on the assumption that Rn ¼
Rp ¼ dp/tp, where dp and tp are the concentration and
 Peltier Effect in Semiconductors 13

lifetime, respectively, of the nonequilibrium minority car-
riers, is widely accepted (63). In this case, the condition for
the total-current continuity is identically satisfied; how-
ever, another basic contradiction takes place. This contra-
diction becomes especially evident if we consider a majority
carrier injection. Physically, it is obvious that the injected
nonequilibrium majority carriers recombine. At the same
time, formally, the recombination rate is equal to zero
because there are no nonequilibrium charge carriers
(dp ¼0).
The problem is appreciably complicated if the tempera-
ture distribution in the sample is nonuniform (i.e., the
temperature is coordinate dependent). As a result, it
becomes unclear from which value the nonequilibrium-
carrier concentration is measured (i.e., what is meant by
the quantities n0 and p0). A method to overcome this
difficulty has been suggested recently (34); however, this
method is rather artificial and is applicable only in the case
of a known (fixed) temperature field.
It is relatively straightforward to obtain the following
expressions for recombination processes (64) by rigorous
consideration of transitions between valence and conduc-
tion bands:
where Nt is the impurity concentration; xn and xp are,
respectively, the electron and hole capture coefficients n1
¼ nn ðTÞexp½—et =T]; p1 ¼ np ðTÞexp½ðet — eg Þ=T], where et
is the impurity energy level; nn T ð 1=4 Þ ¼ 2mðnT= ph2
3=2; np T 1=4 2mpT=ph
Þ ð Þ ¼ ð 2 3=2; and mn and mp are the
Þ
electron and hole effective masses. The concentrations n1
and p1 are the parameters characterizing the impurity
level and, physically, represent the electron or hole con-
centrations when the Fermi level in the semiconductor
coincide with the impurity level. nn and np are the densities
of state at the bottom of the conduction band and top of the
valence band.
Unless otherwise indicated, and with no loss of gener-
ality, we shall refer to a semiconductor that contains
impurities with a single energy level able to capture elec-
trons. It follows from equation 56 that one more unknown
value nt (nt is the concentration of electrons captured by
the impurities) arises when the recombination takes place
through the impurity centers.
Subtracting the second equation 53 from the first, we
obtain (30, 55) the following:
divðjn þ jpÞ ¼ eðRn — RpÞ (57)

Rn ¼ Rp ¼ R ¼ xðnp — n2iÞ (54) The charge conservation in steady state can be written as
where x is the recombination factor and ni is the carrier follows (31):
concentration of the intrinsic semiconductor. By lineariza-
divj ¼ divðjn þ jpÞ ¼ 0 (58)
tion of these expressions for the case of weak deviation
from the condition of thermodynamic equilibrium (the
changes in carrier concentrations as a result of current From equations 57 and 58, we obtain the following rela-
are small in comparison with their equilibrium values), we tionship (30):
have (30) (TðxÞ ¼ T0 þ dTðxÞ and dTðxÞ T 0 ):
Rn ¼ Rp (59)
Σ Σ
R ¼ 1=t p0 dn þ n0 —dp ldT (55)
n0 þ p 0 As it follows directly from equations 59 and 56, the
n0 þ p 0
deviation of the concentration of the electrons trapped 0
—1 2ni
where (65, 66) t ¼ ½xðn0 þ p0 Þ] , l¼ dni =dT ¼ in the impurity level dnt from the equilibrium value nt
n0 p0 1
ð3 þ e =T Þ. n0þp0 depends on the deviations of the electron and hole
g 0
n0þp0 T 0
concentrations from their equilibrium values through
Let us note that this baseless idea is widespread; Rn and Rp.
namely, the presence of only interband recombination is The recombination rates Rn and Rp are actually defined
a sufficient condition for dn¼dp to be fulfilled (42, 61, 62). as the difference between the rates of capture of electrons
However, there is no proof of this conclusion; moreover, the and holes and their thermal generation. These two mech-
case of injection obviously contradicts it. anisms cannot create nonequilibrium carriers without an
Thus, the presence of a temperature gradient results in external source of excitation. From equations 59 and 56, we
the appearance of an additional term in expressions for obtain the following expression for dnt:
recombination rates. This term takes into account the
change in the rate of thermal generation (which, as it is n2t0 . p0
well known, is proportional to the squared concentration of dnt × x dn — xpdp
Ntðx n p10
the intrinsic semiconductor at a given temperature). ¼ Σ nno þ xpp10Þ . ΣΣ Σ
eg — e t
The situation becomes even more complicated if — x n ðe =T þ 3=2Þ — x p þ 3=2 dT=T
recombination resulting through the impurity centers n 10 t 0 p 0 0
T0
(traps) is taken into account. Within the framework of (60)
the Shockley–Read–Hall model and with the assumption
that the carriers of impurity centers are characterized by
the temperature T(r), the recombination can be given by To obtain equation 60, we showed that n1 and p1 can be
presented in the following form: n1 ¼ n10 þ dn1 and
the following equations (see References 61, 63, 64, and 67):
p1 ¼ p10 þ dp.1 . Here, dΣn1 ¼ n10 =T 0 ð3=2 þ et =T 0 ÞdT and
—e
dp1 ¼ p10=T0 3=2 — et T0 g dT.
Rn ¼ xn ½nðN t — nt Þ — n1 nt ]
(56) By substitution of equation 60 into equation 56, we
Rp ¼ xp ½pnt — p1 ðN t — nt Þ] obtain equation 55, where t—1 ¼ x nx pN t x ðn þn n0Þþx 0 ðp þp Þ0 10.
þp

0 10n
p
14 Peltier Effect in Semiconductors

QUASINEUTRAL APPROXIMATION loss of physical information. Furthermore, in the limiting

case of rd ! 0 we are in QN, and the Poisson equation does
We can rewrite the Poisson equation (eq. 52) for nonequi- not need to be solved; instead, the value of w0 can be
librium variations in the following form: obtained by taking advantage of the fact that the electro-
chemical potential is constant across the structure in
d2dw=dx2 ¼ —4pdr=e (61) equilibrium (see Reference 72).
where the electrical potential w ¼ w0 þ dw, bulk electrical It should be stressed that beyond the fact that the
charge r ¼r0 dr, quasineutrality concept is useful when dealing with trans-
þ and w0 and r0 are the equilibrium
electrical potential and bulk charge. port phenomena, QN is important in semiconductor
For intrinsic semiconductors dr ¼ eðdp — dnÞ, and for devices because it is the basis of the operation of most
semiconductors of n- or p-type, dr ¼e ðdp — dn — dntÞ. In semiconductor devices. In bipolar semiconductors, the
the last case, it is necessary to use equation 60. movement of charge packets requires a quasineutral
Quasineutrality (QN) is a basic concept in semiconductor nature of the packet (73, 74).
device analysis and is used widely in the literature on
transport phenomena. Its physical meaning has been exten-
sively reviewed (see, for instance, Reference 68). It can be EQUATIONS FOR COOLING AND HEATING IN p-n
readily seen from Poisson’s equation that dr=r0 ~ ðrd=LÞ
2 JUNCTIONS
(rd is the Debye length and L is the characteristic length of
the change of the chemical potential). Ifð rd=L Þ 2 1, then In the linear approximation with respect to the electric
dr !0. Under these conditions, the differential Poisson current, the heat balance equation is given by (see eq. 43)
equation becomes the following algebraic equation: the following:
r · q ¼ —egR (64)
dr = 0 (62)
which does not need boundary conditions. Additionally, Equation 64 represents the total heat flux conservation
this algebraic equation establishes a relationship between law that can be formulated as follows: Any change in the
the excess of both kinds of carrier and renders the Poisson drift component of the heat flux is accompanied by a
equation redundant in the system of equations 50–52. change in the thermal diffusion component of the same
Despite the widespread use of the QN hypothesis, it is in heat flux, and the heat bulk sources and sinks are given by
general mistakenly reduced to a simplified situation in the recombination processes.
which both excesses of majority and minority carriers The expression for qdr in bipolar semiconductors is
are the same: dn = dp (69, 70). This assumption, which is
valid in some situations, can also lead to important errors in qdr ¼ Pnjn þ Ppjp (65)
other cases (55). From the equation dr’ 0, it follows natu-
As introduced previously, the Peltier coefficients in non-
rally that quasineutrality does not necessarily imply
degenerated semiconductors are
dn = dp, but
1 .h Σ
dp ¼ Adn — Bðn0 þ p0ÞdT=T0 (63) 5
(66)
Pn;p ¼ ; g n;p þ = 2 — m n;p
]T
where e
x ðN n þ n2 p =p Þþ x N p The expression for the diffusion heat fluxes qn;p is as
A¼
n
t0 t0 0 10 p t 10 follows (see eq. 47): diff
xnNtn0 þ xpðNtp10 þ n2t0Þ ;
. Σ
eg — e t qn;p ¼ —kn;p rT (67)
þ
T n
xnn10ðet=T0 þ 3=2Þ— xpp0 3=2 2
B¼ 0 t0 diff
where knph;p is the phonon ph
heat conductivity in the n- and the
xnNtn0 þ xpðNtp10 þ n2t0Þ n0 þ p 0
p-regions as indicated by the superscript.
Therefore, quasineutrality can be identified with the
Taking into account the considerations presented pre-
expression dn ¼dp only in intrinsic semiconductors or in
viously, the heat balance equation can be rewritten as
doped ones if the variation in the trapped charge is weak.
follows:
From Reference 55, it follows that if rd ! 0, then w0ðxÞ
tends to a constant value and is null elsewhere. Therefore, —kph DT þ Pn r · jn þ Pp r · jp þ jn rPn þ jp rPp ¼ —eg R
w0ðxÞcan be asymptotically approximated in the p-n junc-
tion by a step function with a discontinuity at the semi- (68)
conductor interfaces. In electrical terms, this means that Because the current densities can be calculated as (see
in quasineutrality, if the Debye length is very small (i.e., eq. 49),
when considering highly doped semiconductors), then the jn ¼ —sn ðrw — rmn =e þ an rTÞ
space charge spread over a length comparable with the . Σ (69)
Debye length in the semiconductor can be replaced by a jp ¼ —s p rw þ rm p=e þ a prT
surface space charge (boundary layer function (71)) that
supports the discontinuity of the electric potential. the calculation of mn, mp, and w is required. It means
Because the Poisson equation cannot provide w0, removing that we need equations 50–52. Under quasineutral approx-
it from the system of equations 50–52 will not lead to any imation, instead of equation 52 we have equation 62.
 Peltier Effect in Semiconductors 15

Because by definition (see Reference 72), n ¼ nn exp dTnð0Þ ¼ dTpð0Þ (79)

½mn=T]; p ¼ np exp½mp=T], where mn;p ¼ m0n;p þ dmn;p , and
dn ¼ n0=T0½dmn þ ð3=2 — m0n=T0ÞdT], dp ¼ p0=T0½dmp þ
3=2
ð —0p=T0 dTÞ. ]
m nitudes refers to the n (p) region and subscript (n or p)
The system of equations 50, 51, 68, and 63 defines
the mathematical framework of thermoelectric cooling,
and it must be complemented with the appropriate bound-
ary conditions that describe the electric currents, the
heat flux, and the electric potential through the interfaces
(75–77). Let us assume that in the y- and z-direction the p-n
junction is adiabatically isolated. Then, the boundary con-
ditions in the remaining direction (i.e., the p-n junction
interface is orthogonal to the x-axis, and assuming that the
interface is located at x ¼ 0, the n region located between
x¼ ln—and x 0, ¼ the p region between x ¼0 and x ¼lp) are
given below.
Assuming that an ideal metal–semiconductor contact is
placed at x¼ — ln, we can write the following boundary
conditions for the excess of temperature and carrier densi-
ties (hereafter a superscript n or p in a magnitude refers to
the n or p region, respectively):
In the preceding equations, the superscript n(p) in mag-
refers to the carriers (electrons or holes); additionally,
subscript 0 in a magnitude denotes equilibrium. Because
the total current density is constant across the junction, it
is enough to formulate boundary conditions for one of the
two current densities. These boundary conditions are
obtained assuming, respectively, continuity of the electro-
chemical potential at the interface, that both heat and
electrical conductivities are very large at the junction,
and the absence of surface recombination. In fact, because
the p-n interface is inside the depletion region, this latter
assumption is not realistic, and boundary conditions with
finite conductivities need to be used (75). In this work, we
use equations 76–79 for the sake of simplicity.
SIMPLIFICATION OF THE MODEL OF PELTIER EFFECT
IN TWO LIMITING CASES

dT n ð—ln Þ ¼ 0 (70) In this section, we will analyze the thermoelectric cooling

in a p-n junction in the two limiting cases: strong and weak
dnð—ln Þ ¼ 0 (71) recombination.

dwð—lnÞ ¼ 0 (72) Weak Recombination

These boundary conditions are justified because of the high
value of the thermal conductivity of metals and the intense
recombination at the metal–semiconductor interface. Sim-
ilar boundary conditions may be written as follows at the
metal–semiconductor interface at x ¼ lp:
. Σ
dT p lp ¼ 0
Let us now consider that volume recombination is weak. In
this case, the conditions lnD;p ln;p rn;p (ln;p Dare the
D
dif-
fusion lengths in n-p regions) are fulfilled, which means
that the weak recombination is correct for thin film p-n
structures. Formally R¼ 0 when ! t 1. Under this condi-
tion, the right-hand side of equation 43 becomes trivially
null and along with equations 65 and 67 transforms into
(73)

. Σ DT ¼ 0 (80)
dp lp ¼ 0 (74)
Equations 50 and 51 transform into
dwðlpÞ ¼ —V (75)
r · jn;p ¼ 0 (81)
where V is the applied voltage. These boundary conditions
assume that the semiconductor is at equilibrium in x ¼ —ln From equation 81, it follows that jn;p are not spatially
and in x ¼ lp; in other situations, the electric potential (i.e., dependent and jnn þ jpn ¼ jnp þ jpp ¼ j0, where j0 is the whole
eqs. 72 and 75) cannot be rigorously defined (78). At the p-n current through the p-n structure. From the boundary
junction interface, we can introduce the following addi- conditions for currents (75, 76), it follows that
tional boundary conditions (75, 76): jnn þ jnp ¼ j0n, jpn þ jpp ¼ j0p (j0n þ 0jp ¼ j0).
It is not difficult to understand that the concentrations
dmn ð0Þ 1 @mnn of the nonequilibrium carriers (dn and dp) are maxima in
n
dwnð0Þ — n — 0
dT ð0Þ this case.
e e @T
dmp ð0Þ 1 @mp It may seem that the calculation of thermoelectric cool-
p n n
0
dTp ð0Þ ing does not require the use of equation 81 in the absence of
¼ dw ð0Þ — — e @T
e ð76Þ recombination because there are no other unknown func-
dmn ð0Þ 1 @mn tions in equation 80. So, it seems that thermoelectric
p n0 n
n
dw ð0Þ þ — dT ð0Þ cooling does not depend on the nonequilibrium carrier
e e @T
dm pð0Þ 1 @mp
p
concentrations. However, the boundary conditions to equa-
p p n0
¼ dw ð0Þ þ tion 80 must be formulated for heat fluxes (eqs. 65 and 67).
— @T dT ð0Þ
e e The drift heat fluxes depend on the current of majority and
minority carriers (eq. 65). The latter essentially depends
qnð0Þ ¼ qpð0Þ (77)
on the distribution of nonequilibrium carrier concentration
jnð0Þ ¼ jpð0Þ because of the terms ðrmn;p Þ=e. Therefore, there are no
(78) reasons to assume a priori that jnnjn and
p j j .p
n n p p
n
16 Peltier Effect in Semiconductors

The problem is reduced to the calculation of the currents
in the electrical circuit composed of two circuits connected
in parallel (see Figure 16). One of them is composed of two
n-type semiconductors connected in series with the con-
centrations nn and np, whereas the other is composed of
two p-type semiconductors connected in series with the
concentrations pn and pp. At a given direction of the
current (from n- to p-region), heating instead of cooling
takes place at weak recombination.
With respect to what was said previously, let us notice
that the classic theory for current-voltage characteristic
through the p-n junction (6, 14) obeys the following
expression:
. . Σ Σ
eV
j0 ¼ js exp —1 (82)
T recombination, the heat flux depends on the nonequili-
where the saturation current (js) varies in direct proportion
to the capture coefficients. It means the current j0 through
the p-n junction is equal to zero when the recombination is
absent under any voltage.
The above means that the model (eq. 82) is not correct
for weak recombination. At the same time, equation 81
(together with eqs. 80 and 63) will give the correct expres-
sion for the current density j0 (at least under weak bias
voltage).
A main result is that the temperature deviation from
equilibrium at the junction may be obtained as follows:
Adding equation 38 we have
. Σ . Σ
r · jnn þ jnp ¼ 0; r · jpn þ jpp ¼ 0 (86)
It is important to emphasize that the nonequilibrium
charge carrier concentrations (dn and dp) are not equal
to zero in the considered approximation. Therefore, there
is no reason to state that jnnjn andp j j .p
p p
n
Therefore, because lnD;p 0, !R differs from zero only at the
interface. The volume equation (eq. 43) transforms again
into equation 80.
Once again, just like in the weak recombination case,
the right-hand side of equation 43 also becomes zero but for
different physical reasons. But as in the case of weak
brium carrier concentrations. The latter are defined by
equations 85, 86, and 80 with the corresponding boundary
conditions. In the previous case, it was noted that equation
82 is not correct when the recombination is weak enough.
Also, it is not difficult to understand that equation 82 is not
correct in the case of strong recombination. It follows from
the expression for js that js ! 1 when t ! 0 at any applied
voltage V. The last statement is not correct from a physical
point of view.
Pnn s pn
p p
Pn sp

Σ.
n Σ2
.
. Σ2 lp . Σ2 l ΣΣ The method described allows the calculation of the
n p p n n
dT ð0Þ / j0l n Pn þ Pp s current-voltage characteristic of the p-n junction in the
Pn p þ Pp
s p
n
n case of strong recombination in the linear regime with
" !# ! respect to the applied voltage V.
. Σ2 lnlp ln
lp The temperature deviation at the junction has been
þ j 0ln H Ppn þþ
spn snp
snp spp analytically obtained as follows:
" !. Σ#
. Σ2 lp ln lp lp h . Σ i
n
þ j 0ln H P p þ þ dTnð0Þ / j ln snsp Pn— Pp þ sns pP n— s s P pn (87)
spn snp spn snn 0 n p n p p p p n n n
" # This expression clearly differs from the commonly used
. Σ2 l l
þ j 0ln H P p þ P n
n p n p expression as follows (6, 9, 14, 18):
np
sp s
n (83) . Σ
dT n ð0Þ / j0 snn spp Pnn — Ppp l n (88)
The expression of H is
T0 . Σ
H¼ kn l þ kp l (84) The differences are not only in magnitude but also in sign.
ph p ph n
lnlp Contrary to equation 88, indicating that the positive values
of j0 only predict a decrease in temperature with j0, equa-
From equation 83, it follows that a positive current will tion 87 predicts that a p-n junction under the same bias
generate heat instead of cooling at the junction, which is in conditions (positive values of j0) may be heated or cooled
strong contrast with the conventional results. depending on the values of the Peltier coefficients and
electrical conductivities in the p-n junction. Moreover,
Strong Recombination equation 87 clearly shows the paramount importance of
the nonequilibrium carriers at both sides of the junction
Let us assume that the recombination is very strong. The
(neglected in equation 88) because they control the sign of
physical meaning is that ln;p lnD:p ! 0 rn;p !
D 0. From a dTnð0Þ.
mathematical point of view, we have t ! 0 in equation 55.
Finally, let us emphasize that only when the following
Because the recombination rate (R) cannot be infinite at
two criteria are met simultaneously:
t ! 0, from equation 55 follows that
p0 n0 Pn sp Pp sn
dn þ dp ¼ ldT (85) n n p p (89)
;
n0 þ p 0 n0 þ p 0 P sp Pn s
p n
n p p n
At the same time, the magnitude R is finite but not defined. Equation 87 reduces to equation 88.
 Peltier Effect in Semiconductors 17

APPLICATIONS magnitudes in the figure of merit (a2s). Although this

Research and development of bulk homogeneous materials
for thermoelectric applications began to increase starting
in the 1950s and resulted in commercial solid-state power
generation and cooling systems (5). With the introduction
of materials and concepts based on nanostructuring, the
field has witnessed truly dramatic growth over the past 15
years. Nanostructuring of semiconductors in the form of
quantum wells and superlattices started in the 1960s and
early 1970s for electrical and optical devices. In contrast,
the primary benefit to date of nanostructuring for thermo-
electric materials has been the impact on thermal propert-
ies rather than electronic (79).
The performance of thermoelectric materials is quanti-
fied by the previously introduced unitless figure of merit
ZT, which is defined as Z¼a2s=k. The theory of thermo-
electric efficiency was outlined by Altenkirch (80, 81). It
was based on a simple procedure of taking into account
Joule losses and losses caused by thermal conductivity.
The resultant expression was given in the form proposed
by Ioffe (5). The process of energy conversion was studied
by Harman and Honig (82), Anatychuk (9), Nolas et al. (6),
and Tauc (14).
In the 1950s, it was discovered that alloys of Bi2Te3 had
a value of ZT =1 near room temperature, and they have
played a dominant role in the field of thermoelectrics
through today. Although each magnitude in the expression
of ZT can individually be changed by several orders of
magnitude, the interdependence and coupling between
these properties have made it extremely difficult to
increase ZT above the unity despite five decades of active
research. The thermoelectrics community is widely target-
ing ZT > 3 to make these solid-state systems competitive
with traditional mechanical energy conversion systems
(79).
In 1993, Hicks and Dresselhaus (13, 83) pioneered the
concept that quantum confinement of electrons and holes
in low-dimensional materials could dramatically increase
ZT above the unity by independently changing the
ignited intense research into nanostructured thermo-
electric materials, there are still many debates about the
exact role that low dimensionality and nanostructures
could play in improving thermoelectrics. Table 1 summa-
rizes major ZT milestones achieved over the past decades
(79).
It is important to note that some of the ZT values in
Table 1 have not yet been independently verified or repro-
duced, and corroboration of these key breakthroughs
would be helpful to the thermoelectrics community.
The field of thermoelectrics presents an important chal-
lenge to synthetic chemists, physicists, and materials sci-
entists. The discovery of new and promising materials
requires a combination of theoretical guidance, keen chem-
ical intuition, synthetic chemistry expertise, materials
processing, and good measurement skills. This powerful
combination can be effectively achieved by reaching across
scientific disciplines (99).
A common theme among many emerging thermoelectric
materials is the concept of nanostructuring to improve
the thermoelectric performance. In these systems, the
enhanced thermoelectric performance is attributable to a
strong decrease in lattice thermal conductivity rather than
an increase in the electrical power factor (a2s). Thus, in
certain cases, nanodots clearly play a significant role in
reducing lattice thermal conductivity, probably by effec-
tively scattering phonons that otherwise would have rela-
tively long mean free paths. In many of these cases, it has
been clearly demonstrated that the reduction in thermal
conductivity far exceeds any concomitant reduction in the
power factor caused by electronic carrier scattering, thus
resulting in enhanced ZT values (99). Thin-film super-
lattices and nanowires make up a significant part of cur-
rent thermoelectric research.
In review (100), strategies to improve the thermo-
electric figure of merit, new discussions on device physics
and applications, and assessments of challenges on
these topics were presented. Understanding of phonon
transport in bulk materials has advanced significantly

Table 1. Thermoelectric Figure-of-Merit ZT as a Function of Temperature and Year Illustrating Important Milestonesm

Material ZT T (K) Year Reference

Bi2Te3/Sb2Te3 (supperlattice) 2.4 300 2001 84
PbSeTe (nano dot superlattice) 1.6 300 2002 85
AgPbmSbTemþ2 2.2 800 2004 86
Bi2Te3 0.77 300 1958 87
Pb1—xEuxTe/PbTe (multi quantum well) 1.2 300 1996 88
CsBi4Te6 0.8 225 2000 89
Si NW (nanowire) 1.0 200 2008 90
Si NW (nanowire) 0.6 300 2008 91
BiSbTe 1.4 373 2008 92
Na1—xSbmSbyTemþ2 1.7 700 2006 93
In4Se3—d 1.48 705 2009 94
PbTe (Ta-doped) 1.5 773 2008 95
Ba8Ga16Ge30 1.35 900 2006 96
SiGe 1.3 1173 2008 97
SiGe NW 0.46 450 2012 98
m
Although there have been several demonstrations of ZT > 1 in the past decade, no material has yet achieved the target goal of ZT ≤ 3. The
material systems that have achieved ZT > 1 have all been based on some form of nanostructuring.
18 Peltier Effect in Semiconductors
Table 2. Main Advantages and Disadvantages of Thermoelectric
Coolers
Favorable Unfavorable
CFC-free operation × A comprehensive study of the mechanisms of heating and
Free of moving parts and fluids × cooling originated by an electrical current in semi-
Vibrations and acoustic noise × conductor devices has been presented in this article.
DC power instead of wall AC ×
or lead batteries
Maintenance ×
Efficiency × lyzed. Both degenerate and nondegenerate electron and
Cooling power × hole gases were considered. The eminent roles of
as the first-principles calculations are applied to thermo-
electric materials, and new experimental tools are being
developed. As a result, some new strategies have been
developed to improve electron transport in thermoelectric
materials.
A thermoelectric device consists of heavily doped semi-
conductor legs that are connected electrically in series and
thermally in parallel. A fundamental understanding of
heat and charge carrier transport inside the thermoelectric
legs will lead to new strategies to design and fabricate
high-efficiency thermoelectric materials. The device effi-
ciency depends not only on materials but also on an opti-
mum choice of the legs’ size, configuration, and contacts.
Finding new applications for thermoelectric devices in
places that they are superior to other technologies is
another challenge for the thermoelectric community.
Table 2 summarizes the main advantages and disad-
vantages of thermoelectric coolers.
As a motivating conclusion of this section, it is impor-
tant to examine more closely the meaning of ZT and its
limits as a figure-of-merit in thermoelectric devices. ZT is a
good parameter to characterize thermoelectric materials.
When a thermoelectric device consists of just one homoge-
neous material (as it is often the case in thermoelectric
generators), ZT will be truly useful to characterize the
efficiency of the device. Nevertheless, in thermoelectric
cooling (Peltier effect), it is necessary to have a contact
between two materials. In this situation, nonequilibrium
electrons and holes will set up. Which parameter that could
characterize the efficiency of cooling system as a whole was
not known until today.
SUMMARY
The Peltier effect is the heat extraction or absorption that
occurs at the contact between two different conducting
media when a DC electric current flows through this
contact. Devices based on the Peltier effect, which is the
basis for solid-state thermoelectric cooling, have evolved
rapidly to meet the pace of the ever-growing industry of
electronics. In recent years, new solid-state cooling solu-
tions based on new materials and devices (such as gra-
phene, Si and SiGe nanowires, etc.) have been proposed. To
drive the quest for new high-efficiency cooling devices, a
suitable knowledge of the theory behind thermoelectric
cooling is of paramount importance.
Thermoelectric phenomena, such as the Peltier effect,
are at the crossroads of several fields of physics and
engineering such as solid-state electronics, nonequili-
brium thermodynamics, transducer devices, and so on.
Thermoelectric cooling in n-n, p-p, and p-n junction con-
tacts and inhomogeneous bulk semiconductors was ana-
recombination and nonequilibrium charge carriers in
heating/cooling of solid-state devices, usually ignored
in the Peltier effect’s literature, has been discussed.
Along with the above, special attention has been paid
to several aspects of nonequilibrium thermodynamics of
the thermoelectric phenomena involved in Peltier effect
in semiconductors that demanded a careful examination.
In particular, some inaccuracies in the traditional theory
widely extended in the literature were discussed, and a
recently formulated self-consistent theoretical model,
better describing the Peltier effect, was presented.
Finally, a glimpse of applications was given with special
emphasis on the evolution of experimental values of the
figure of merit ZT in the past decades. A reflection was
made about the lack of figure of merit for thermoelectric
devices involving two or more materials (such as those
based on the Peltier effect).
ACKNOWLEDGMENTS
Yu. G. Gurevich thanks CONACYT-Mexico for financial
support. J. E. Velazquez-Perez wants to thank Spanish
Ministerio de Economı́a y Competitividad (MINECO) and
FEDER for financial support under grant TEC2012-32777.
We would like also thank Associate Editor Ms. Cassandra
Strikland for her valuable help and assistance in the
processing of this manuscript.
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YU. G. GUREVICH
CINVESTAV-IPN
J. E. VELAZQUEZ-PEREZ
Universidad de Salamanca