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Annu. Rev. Mater. Res. 2011. 41:433–48 Keywords

First published online as a Review in Advance on
April 12, 2011
The Annual Review of Materials Research is online at
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thermoelectrics, thermopower, thermal conductivity, energy harvesting,
power generation
Abstract
Over the past 10–15 years, there have been significant advances in the scien-
tific understanding as well as in the performance of thermoelectric (TE) ma-
terials. TE materials can be incorporated into power generation devices that
are designed to convert waste heat into useful electrical energy. These TE
materials can also be used in solid-state refrigeration devices for cooling ap-
plications. The conversion of waste heat into electrical energy will certainly
play a role in our current challenge for alternative energy technologies to re-
duce our dependence on fossil fuels and to reduce greenhouse gas emissions.
This article provides an overview of the various TE phenomena and discusses
some of the primary TE materials that are currently being investigated. Sev-
eral of the key parameters and terminology are defined and discussed along
with an overview of some of the current and emerging technologies. The
phonon glass–electron crystal approach to new TE materials for developing
new materials is presented along with the role of solid-state crystal chemistry
and the criteria for higher-performance TE materials. This article discusses
TE phenomena, the selection criteria for higher-performance materials, and
a few key materials.

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 MR41CH17-Tritt ARI 3 June 2011 8:42

1. INTRODUCTION TO THERMOELECTRIC PHENOMENA

AND APPLICATIONS

1.1. Background and Applications

Over the past 15 years or so, there has been a heightened interest in the field of thermoelectric
(TE) materials research. Such interest has been driven by the need for more efficient materials
and devices for electronic refrigeration and power generation. Various research groups are cur-
rently investigating a number of different systems of potential TE materials. These range from
thin-film superlattice materials to large single-crystal or polycrystalline bulk materials and from
semiconductors and semimetals to ceramic oxides. Several review articles written on the subject
over the past few years capture much of the work done over the past decade or so [3–6; see also
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generally articles on the theme of “Harvesting Energy Through Thermoelectrics: Power Gener-
ation and Cooling” in the MRS Bulletin, Volume 31 (2006)]. Some of the research efforts focus on
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minimizing the lattice thermal conductivity, whereas other efforts focus on materials that exhibit
high power factors, which are discussed below.
Proposed industrial and military applications of TE materials are generating increased activity
in this field by demanding higher-performance, higher-temperature TE materials compared with
those that are presently in use. The demand for alternative energy technologies to reduce our
dependency on fossil fuels has led to various directions of research, including high-temperature
energy harvesting via the direct recovery of waste heat and its conversion into useful electrical
energy using TE devices. More recently, TEs have been investigated for their use in TE-solar
hybrid systems to take advantage of the IR part of the solar spectrum and for TE-solar power
generation (7). Thus, the development of higher-performance TE materials is becoming more
important. Novel applications of TEs include aspects such as biothermal batteries to power heart
pacemakers, enhanced performance of optoelectronics coupled with solid-state TE cooling, and
power provision for deep-space probes via radioisotope TE generators. More recently, TE gener-
ators have been installed in automobiles to capture waste heat from exhaust and to transform it into
useful electrical energy for automotive electrical systems and for increased fuel efficiency for use in
next-generation vehicles. In addition, TE refrigeration applications include seat coolers for com-
fort and electronic component cooling. Of course, the deep-space applications of NASA’s Voyager
and Cassini missions using radioactive thermoelectric generators (RTGs) are well established (8).
TE refrigeration is an environmentally green method of small-scale, localized cooling in com-
puters, infrared detectors, electronics and optoelectronics, and many other applications. However,
most of the electronics and optoelectronics technologies typically require only small-scale or local-
ized spot cooling of small components that do not impose a large heat load. If significant economical
cooling can be achieved, the resulting cold computing could produce speed gains of 30% to 200%
in some CMOS computer processors. Many researchers perceive cooling of the processors to be
the fundamental limit to electronic system performance (9). Recent utilization of Peltier coolers
in relation to refrigeration of biological specimens/samples is also an emerging TE application.
Thus, the potential payoff for the development of low-temperature TE refrigeration devices, as
well as for the development of high-temperature materials for waste heat recovery, is great. The
requirement for compounds with high-performance properties optimized over wide temperature
ranges has led to this much-expanded interest in new TE materials. The role of bulk materials
applications and needs is demanding new breakthroughs in both materials engineering and device
engineering, especially for automotive applications for cooling and power generation (8).
The development and potential of bulk materials for TE applications include high-temperature
materials such as skutterudites, clathrates, half-Heusler alloys, and complex chalcogenides (10).

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 MR41CH17-Tritt ARI 3 June 2011 8:42

Recently, ceramic oxide materials have also shown potential as high-temperature TE materials
(11). The potential of nanomaterials and their role in TE research are emerging areas of interest
(12). Another emerging area is one that utilizes materials termed TE nanocomposites, which incor-
porate nanomaterials that are then part of a matrix of a given TE material. These nanoparticles may
be mixed into materials and solidified by some method such as hot pressing or spark plasma sinter-
ing. Such nanoparticles can also be nucleated within the material directly through either specific
solid-state synthesis or more external methods such as high-energy ball milling or melt spinning
(13–16). Thin-film properties, applications, and recent results are also very important (17).
A key factor in advancing many of these technologies is the development of higher-performance
TE materials via either the emergence of completely new materials or a more ingenious materials
engineering of some of the existing materials. Recent books and series provide a more complete
overview of the state-of-the-art materials, a theoretical and experimental discussion of the basic
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principles, and an overview of some of the recent developments and materials (2, 18).
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1.2. Seebeck and Peltier Effects

A discussion of TE effects and devices should start with one of the most fundamental phenomena,
the Seebeck coefficient, or the thermopower (19, 20). In the early 1800s, Seebeck observed that if
two dissimilar materials were joined together and the junctions were held at different temperatures
(T and T + T ), then a voltage difference (V) that was proportional to the temperature differ-
ence (T ) developed. The ratio of the voltage developed to the temperature difference (V/T )
is related to an intrinsic property of the materials termed the Seebeck coefficient (α), or the ther-
mopower. This effect can be understood by establishing a temperature gradient across a material;
the more energetic electrons migrate to a lower potential until an electric field is established to
impede the further flow of electrons. This effect is illustrated in Figure 1, which shows the estab-
lishment of an electric field that is the opposite of that of the temperature gradient, ∇T , given
that the sign of α n is negative for electrons:

E = αn ∇T
 . 1.

The Seebeck coefficient is very low for metals (only a few microvolts per degree Kelvin) and is
much higher for semiconductors (typically a few hundred microvolts per degree Kelvin) (21). A
few years after Seebeck’s observation, Peltier discovered a related effect (the Peltier effect): If an
electrical current is passed through the junction of two dissimilar materials, heat is either absorbed
or rejected at the junction, depending on the current’s direction. This effect is due largely to the
difference in the Fermi energies of the two materials. These two effects are related to each other,
as shown in the definition of the Peltier coefficient, Π = αT. The rate that the Peltier heat is
liberated or rejected at the junction ( Q̇ P ) is given by Q̇ P = α I T , where I is the current through
the junction and T is the temperature in degrees Kelvin. Thermomagnetic effects such as the Hall,
Ettingshausen, and Nernst effects are beyond the scope of this article (see Nolas et al. 18 for a
more complete discussion of these effects).

1.3. Definition and Description of the Figure of Merit

and Thermoelectric Performance
The potential of a material for TE applications is determined in large part by a measure of the
material’s dimensionless figure of merit,

α2 σ T α2 T
ZT = = , 2.
κ ρκ

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 MR41CH17-Tritt ARI 3 June 2011 8:42

TC T TH
Δ

TC T TH
Δ
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b – +
+
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– + + + + + + + +
– + + + + + + + + +
+ + + + + + + + +
–
E

Figure 1
A depiction of the thermoelectric effect when a material is subjected to an external temperature gradient and
the system is in equilibrium. (a) The more energetic electrons have a longer mean free path. (b) These more
energetic electrons (denoted by blue dots) then diffuse to the cold side until an electric field (E) is developed to
oppose any further diffusion. We define x as increasing from the cold-side temperature TC to the hot-side
temperature TH , therefore defining the temperature gradient ∇T  as shown. Because the electrons are
negatively charged (and therefore α n is negative), an electric field is established that is the opposite of that of
the temperature gradient to oppose further diffusion when the system is in equilibrium.

where α is the Seebeck coefficient, σ the electrical conductivity, ρ the electrical resistivity, and
κ the total thermal conductivity (κ = κ L + κ E , where κ L and κ E are the lattice and electronic
contributions, respectively). The power factor, α 2 σ T (or α 2 T/ρ), is typically optimized through
doping in narrow-gap semiconducting materials as a function of carrier concentration (typically
approximately 1019 carriers cm−3 ) to give the highest ZT (18). High-mobility carriers are most
desirable to have the highest electrical conductivity for a given carrier concentration. The ZT
for a single material is somewhat meaningless because an array of TE couples is utilized in a
device or module. There are two materials in a TE couple (shown in Figure 2): an n type and a
p type (see, for example, http://www.marlow.com for a look at several TE module designs). If
one ignores parasitic contributions that reduce device performance such as contact resistance and
radiation effects, then the resulting ZT for the couple (based solely on the TE materials) is given
by

(α p − αn )2 T
ZT = . 3.
[(ρn κn )1/2 + (ρ p κ p )1/2 ]2

The thermopower of n-type carriers (α n ) is negative, and that of the holes (α p ) is positive. The
coefficient of performance (φ) (refrigeration mode) and the TE efficiency (ηTE ) (power generation
mode) of the TE couple are directly related to the ZT, as shown in Equation 3 for the efficiency.
The efficiency (ηTE ) of the TE couple is given by the power input to the load (W ) over the net

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 MR41CH17-Tritt ARI 3 June 2011 8:42

Active cooling Heat source

p n p n

Heat rejection Heat sink

I
I
– +
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Refrigeration mode Power generation mode

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Figure 2
A generic diagram of a thermoelectric couple made of n-type and p-type thermoelectric materials. Power
generation or refrigeration modes are possible, depending on the configuration. Red denotes hotter
temperatures, and blue denotes colder temperatures.

heat flow rate (QH ), where QH is positive for heat flow from the source to the sink:
 
W T H − TC (1 + ZT M )1/2 − 1
ηTE = = , 4.
QH TH (1 + ZT M )1/2 + T C /T H
where TH is the hot-side temperature, TC is the cold-side temperature, and TM is the average
temperature. Thus, ηTE is proportional to the Carnot efficiency (ηC ):
T H − TC
ηC = , 5.
TH
which we know from thermodynamics is the maximum efficiency of a heat engine operating
between two temperatures, TH and TC . Figure 3 shows the ratio of ηTE and ηC plotted as a
function of ZT for a heat engine operating between the temperatures of TH = 800 K and
TC = 300 K, which would yield a Carnot efficiency of 62%. This plot assumes that the de-
vices are operating with no parasitic losses such as contact resistance or radiation effects and that
ZT is constant between these two temperatures. Of course, these are not realistic assumptions,
and the plot is used only as a gauge to ascertain where the greatest return in efficiency gain would
be achieved per unit increase in ZT. The biggest return is for a ZT between 2 and 3, and in my
opinion, the ultimate goal of TE materials research is ZT ≈ 2–3 in stable, bulk TE n-type and
p-type materials with low parasitic losses that can operate between these two temperatures with
high ZT values.

1.4. Thermoelectric Modules: Devices

The Peltier effect is the basis for many modern-day TE refrigeration devices, and the Seebeck
effect is the basis for TE power generation devices. The versatility of TE materials is illustrated in
Figure 2, which shows a diagram of a TE couple that is composed of n-type (negative thermopower
and electron carriers) and p-type (positive thermopower and hole carriers) semiconductor materials
connected through metallic electrical contact pads. Both refrigeration and power generation may
be accomplished using the same module as shown in Figure 2. A TE module or device comprises
an array of these couples, which are arranged electrically in series and thermally in parallel. TE
energy conversion utilizes the Seebeck effect, wherein a temperature gradient is imposed across

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 MR41CH17-Tritt ARI 3 June 2011 8:42

0.6

0.5

0.4
TH = 800 K
TC = 300 K

ηTE /ηC
0.3

0.2
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0.1

0
0 1 2 3 4 5
ZT
Figure 3
The ratio of thermoelectric efficiency to the Carnot efficiency (ηTE /ηC ) as a function of the figure of merit,
ZT. The maximum efficiency or Carnot efficiency is given by ηC = (TH − TC )/TH = (800 K − 300 K)/
800 K = 63%, where TH is the hot-side temperature and TC is the cold-side temperature. This plot assumes
no parasitic losses such as contact resistance or radiation effects and that ZT is essentially constant between
these two temperatures. Red denotes hotter temperatures, and blue denotes colder temperatures.

the device, resulting in a voltage that can be used to drive a current through a load resistance or
device. This process reflects the direct conversion of heat into electricity. Conversely, Peltier heat
is generated when an electric current is passed through a TE material to provide a temperature
gradient (with heat being absorbed on the cold side), is transferred through (or pumped by) the
charge carriers in the TE materials, and is then rejected at the heat sink, thus providing refrigeration
capability. The advantages of TE solid-state energy conversion are compactness, quietness (no
moving parts), and localized heating or cooling. In addition, energy in the form of waste heat
(0% efficiency) that would be normally lost may be converted into useful electrical energy (with
7–8%-and-greater efficiency) using a TE power generation device.
The best TE materials that are currently used in devices have a value of ZT ≈ 1. Previous
to the mid-1990s, this value had been a practical upper limit for more than 30 years, yet there
were no theoretical or thermodynamic reasons for ZT ≈ 1 as an upper barrier. As is apparent
from Equation 2, the ZT may be increased either by decreasing κ L or by increasing either α or σ ,
where α 2 σ T is defined as the power factor, which is related primarily to the electronic properties.
However, σ is tied to κ E through the Wiedemann-Franz relationship, and the ratio of κ E /σ is
essentially constant at a given temperature for the majority of TE materials.

κ E = L0 σ T . 6.

The value of the Lorenz number (L0 ) is L0 = 2.48 × 10−8 V2 K−2 for metals and is usually taken
as L = 2.0 × 10−8 V2 K−2 for degenerate, i.e., highly doped, semiconductors. Some of the goals
of current research efforts are to find new materials that either increase the current efficiency of
TE devices (e.g., increase ZT ) or have the capability of operating in new and broader temperature
regimes, especially at lower temperatures (T < 250 K) and at higher temperatures (T > 400 K).
Over the past 30 years, alloys based on the Bi2 Te3 system [(Bi1−x Sbx )2 (Te1−x Sex )3 ] as well as on

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 MR41CH17-Tritt ARI 3 June 2011 8:42

3 Bulk
Thin film
Bi2Te3/Sb2Te3-SL
2.5
LAST-AgPb18SbTe20
2
PbTe-QDSL
(ZT )max

Filled skutterudites
1.5
(RECoSb3)
Nano-p-Bi2Te3
n-SiGe Zn4Sb3 and Pb0.98Tl0.02Te
1
Bi2Te3 alloys
CsBi2Te3
0.5
PbTe
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1950 1960 1970 1980 1990 2000 2010

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Year
Figure 4
The figure of merit, ZT, as a function of the time frame of several key TE materials relative to their
discovery year, thus showing many of the recent advancements in both thin-film and bulk thermoelectric
materials. Abbreviations: LAST, PbAgSbTe compounds; QDSL, quantum dot superlattice; SL, superlattice.

the Si1−y Gey system have been extensively studied and optimized for their use as TE materials
to perform a variety of solid-state TE refrigeration and power generation applications (22, 23).
These traditional TE materials have undergone extensive investigation, and only a few years
ago there appeared to be little room for future improvement in these common bulk structures.
However, recent results on nanostructures of traditional TE materials have shown a promising new
direction for these materials. In addition, entirely new classes of compounds have been recently
investigated. Figure 4 shows the ZT values of the Bi2 Te3 and Si1−y Gey materials and their more
recent nanocomposite forms in the year they were discovered, as well as the ZT values of many of
the more recent bulk and thin-film materials that have been developed over the past several years.

1.5. Transport Properties

The thermopower or Seebeck coefficient (α) can be thought of as the heat per carrier over tem-
perature or more simply the entropy per carrier, α ≈ C/q, where C is the specific heat and q is the
charge of the carrier (20). In the case of a classical gas, each particle has an energy of E = 32 k B T ,
where kB , the Boltzmann constant, is 1.38 × 10−23 J K−1 . The thermopower of a classical electron
gas is then approximately k B /e ≈ 87 μV K−1 , where e is the absolute value of the charge of the
electron. For metals, the heat per carrier is essentially a product of the electronic specific heat and
the temperature divided by the number of carriers (N), and then
 
Cel kB kB T
α≈ ≈ , 7.
q e EF
where EF is the Fermi energy (related to the chemical potential of the material). Only that fraction
of the electrons (k B T/E F ) participate in the conduction process and thus also contribute to the
thermopower of a metal. At T ≈ 0, all states above the Fermi energy are vacant, and all the states
below the Fermi energy are occupied. The quantity k B /e ≈ 87 μV K−1 is a constant and represents
the thermopower of a classical electron gas. Metals have thermopower values that are much lower
than 87 μV K−1 (on the order of 1–10 μV K−1 ) and that decrease with decreasing temperature,
i.e., EF  kB T. The Mott equation describes the behavior of metals as a function of temperature

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 MR41CH17-Tritt ARI 3 June 2011 8:42

and is the diffusion thermopower.

 
π 2 k2B T 1 dσ
αD = . 8.
3e σ (E) d E E=E F

In a semiconductor a charged particle must first be excited across an energy gap EG . In this case
the thermopower is approximated by
 
Cel kB EG
α≈ ≈ . 9.
q e kB T
Thus, the thermopower is much higher than the characteristic value k B /e ≈ 87 μV K−1 and
increases with decreasing temperature. Semiconductors can exhibit either electron conduction
(negative thermopower) or hole conduction (positive thermopower). The thermopower for dif-
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ferent carrier types is given by a weighted average of their electrical conductivity values (σ e and σ p ),
(αe σe + α p σ p )
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α≈ . 10.
(σe + σ p )
It is necessary to dope the semiconductors with either donor or acceptor states to allow extrinsic
conduction of the appropriate carrier type, electrons or holes, respectively. The overall objective is
to have either a predominantly n-type material or a predominantly p-type material. The total ther-
mopower will be lower than that of either of the individual contributions unless the direct band gap
is large enough (typically on the order of 10 kB T0 , where T0 is the operating temperature of the ma-
terial) to effectively minimize minority carrier contributions. Typical values of the thermopower
that are needed for good TE performance are on the order of 150–250 μV K−1 or greater.
For high-temperature applications, the contribution of minority carriers should be minimized
to maintain a high thermopower value. In addition, the thermal stability of the materials is an
essential aspect. Atomic diffusion within the materials and interdiffusion of contacts can seriously
deteriorate the properties of a given material at high temperatures. Aspects of this are discussed
elsewhere (2, 18). These materials and devices are expected to operate at elevated temperatures for
long periods of time without deterioration of the materials’ properties or the devices’ performance.
Diffusion and thermal annealing are important effects to thoroughly investigate and understand
in any set of materials.
Electrical conductivity of metals and semiconductors has been discussed extensively in many
texts on solid-state physics. Many carriers and states, typically n ≈ 1022 carriers cm−3 , are available
for conduction in metals. The electrical conductivity is then very high for metals, on the order
of 106 (-cm)−1 . Again for semiconductors, the carriers must be thermally excited across a gap
for conduction to occur, as shown from the activated behavior that is derived for the temperature
dependency of electrical conductivity:
 
EG
σ ≈ σ0 exp − . 11.
2k B T
Here, σ = neμ. The carrier concentration typically dominates the conductivity, but the mobility μ
and the temperature dependency of the mobility are also very important in relation to the behavior
of electrical conductivity. Many textbooks on solid-state and semiconductor physics describe this
behavior well. Thus, the two primary ways to achieve high conductivity in a semiconductor are
either by having a very small gap to excite across EG  10 KB T or by having very high mobility
carriers. Typical values of the electrical conductivity of a good TE material are on the order of
approximately 103 (-cm)−1 .
The thermal conductivity, κ, is related to the transfer of heat through a material by electrons
and by phonons (quantized vibrations of the lattice) such that κ = κ L + κ E . The electrical and

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 MR41CH17-Tritt ARI 3 June 2011 8:42

thermal conductivities σ and κ are interrelated: σ is tied to κ E through the Wiedemann-Franz

relationship given in Equation 6, and κ E = L0 σ T. The lattice thermal conductivity is discussed
below under Section 2.2. Typical values of thermal conductivity for a good TE material are κ <
2 W m−1 K−1 , and typically κ L ≈ κ E .

2. INVESTIGATING NEW THERMOELECTRIC MATERIALS

2.1. The Phonon Glass–Electron Crystal Approach

Several years ago Slack (24) described the chemical characteristics of materials that might prove
to be candidates for a good TE material; namely, the candidate materials should be narrow-band-
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gap semiconductors with high-mobility carriers. Mahan and colleagues (25, 26) also described
characteristics of good TE materials. The candidate material is typically a narrow-band-gap semi-
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conductor (e.g., EG ≈ 10 kB T0 or ≈ 0.25 eV at 300 K). Also, the mobility of the carriers must
remain high (μ ≈ 2,000 cm2 (V·s)−1 ], whereas the lattice thermal conductivity must be mini-
mized. In semiconductors, the Seebeck coefficient and the electrical conductivity (both in the
numerator of ZT ) are strong functions of the doping level and chemical composition. Therefore,
these quantities must be optimized by band gap engineering for good TE performance. The ther-
mal conductivity of complex materials can often be modified by chemical substitutions, and the
lattice thermal conductivity needs to be as low as possible. Understanding these various effects
and selecting optimization strategies can be exceedingly difficult problems because in complex
materials there are often many possible degrees of freedom. Slack suggested that the best TE
material would behave as a phonon glass–electron crystal (PGEC) material; that is, it would have
the electrical properties of a crystalline material and the thermal properties of an amorphous or
glass-like material. Therefore, a material’s engineering or designer materials approach must be
pursued either to improve more established materials or to discover completely new classes of
materials to investigate.

2.2. Minimum Thermal Conductivity

In many areas of research related to new TE materials, attempts are being made to reduce the lattice
part of the thermal conductivity to essentially its minimum value, at which minimum lattice thermal
conductivity is achieved (that is, when all the phonons have a mean free path that is essentially equal
to the interatomic spacing of the constituent atoms). Such attempts involve scattering phonons in
different frequency ranges through a variety of methods such as mass fluctuation scattering in a
mixed crystal of ternary and quaternary compounds, rattling scattering, grain boundary scattering
due to grain size, and interface scattering in thin films or multilayer systems. In addition, the
advent of TE nanocomposites has proven to be a very viable approach in lowering the lattice
thermal conductivity (3–7).
The lattice thermal conductivity is given by
1
κL = v S C V L ph , 12.
3
where v S is the velocity of sound, CV is the heat capacity at constant volume, and Lph is the mean
free path of the phonons. At high temperatures (T > ≈300 K), the sound velocity and the heat
capacity are essentially temperature independent in typical materials. Therefore, the magnitude
and the temperature dependency of κ L are determined basically by the mean free path of the
phonons at higher temperatures, T > θ D (where θ D is the Debye temperature). Slack (27) defined

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 MR41CH17-Tritt ARI 3 June 2011 8:42

the minimum thermal conductivity (κ min ) as the thermal conductivity when the mean free path
is limited essentially by the interatomic distance between the atoms within the crystal. A typical
analysis of κ min results in values of κ min ≈ 0.25–0.5 W m−1 K−1 (25, 27).

2.3. Minimum Thermopower

There are certain practical limits for each of the parameters used to calculate ZT. These practical
limits must be possible to achieve a material viable for TE applications. For example, in Bi2 Te3 ,
to achieve a ZT ≈ 1 at T = 320 K, σ ≈ 1 m-cm, α ≈ 225 μV K−1 , and κ ≈ 1.5 W m−1 K−1 . I
discuss above the ZT barrier, which in effect is given by minimizing the thermal conductivity. It is
practical to investigate materials in which the electronic and lattice terms are comparable, on the
order of 0.75 to 1 W m−1 K−1 . Let us look at the hypothetical situation of a material in which the
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lattice thermal conductivity is zero (κ L = 0). We also assume the scattering in this system is elastic
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and that the Wiedemann-Franz relationship, slightly rearranged (κ E /σ = L0 T ), is well behaved

in this material. Then we can rewrite Equation 1 as ZT = α 2 T/ρκ E = α 2 /L0 . Therefore, to be a
viable TE material, a material must possess a minimum thermopower that is directly related to the
values of ZT and L0 . Given this description, to achieve a certain value of ZT, the material would
require that α = (L0 )0.5 = 157 μV K−1 for ZT = 1 and α = (2L0 )0.5 = 225 μV K−1 for ZT =
2. Of course, any real material will possess a finite κ L , so these thermopower values will have to
be higher to achieve the projected ZT values!

3. DESIGNER MATERIALS APPROACHES TO ADVANCED

THERMOELECTRIC MATERIALS
TE materials research has always been a materials design problem involving intricate tuning
of structure/property relationships in complex solids through principles of solid-state chemistry
materials science and solid-state physics. The discussion thus far indicates that new materials must
be able to eventually achieve certain minimum values of important parameters to be considered as
a potential TE material. Whether a material has a κ L ≈ κ min does not matter. If a material cannot
be tuned or doped to attain a minimum thermopower (150 μV K−1 ), then it cannot achieve
ZT ≈ 1.

3.1. The Classical Approach: Bulk Binary Semiconductors

Within the framework of the simple electronic band structure of solids, in general metals are
poor TE materials. Hence, most of the early TE work emphasized semiconductors (28). As stated
above, to have a maximum ratio of electrical to thermal conductivity, the material should have
relatively few carriers (≈1019 cm−3 ) with very high mobilities. Crystal structure and bonding
strongly influence mobility. Materials with either diamond or zinc blend structures with a high
degree of covalent bonding frequently have high mobilities (e.g., Si, Ge, or InSb) and high thermal
conductivity values. In contrast, low lattice thermal conductivities are found in conjunction with
low Debye temperatures and high anharmonic lattice vibrations. These conditions are best satisfied
by highly covalent intermetallic compounds and alloys of the heavy elements such as (Pb, Hg, Bi,
Tl, or Sb) and (S, Se, or Te). Once a material system has been selected with a favorable electrical-to-
thermal-conductivity ratio, one optimizes the composition to further enhance the ZT by doping the
material to maximize the density of states at the Fermi level and hence the high Seebeck coefficients.
The most-studied TE materials are probably Bi2 Te3 alloys that crystallize in a layered structure
with rhombohedral-hexagonal symmetry with a space group R3̄m (D5 3d ). The hexagonal unit cell

442 Tritt
 MR41CH17-Tritt ARI 3 June 2011 8:42

dimensions at room temperature are a = 3.8 Å and c = 30.5 Å. The layers are stacked along the
c axis in the following sequence:
· · · Te − Bi − Te − Bi − Te · · · Te − Bi − Te − Bi − Te · · · .

The Bi and Te layers are held together by strong covalent bonds, whereas the adjacent Te layers
exhibit van der Waals bonding. This weak binding between the Te layers accounts for the ease
of cleavage along the plane perpendicular to the c axis and the anisotropic thermal and electrical
transport properties of Bi2 Te3 . For example, the thermal conductivity along the plane perpen-
dicular to the c axis (1.5 W m−1 K−1 ) is nearly twice that of the value along the c-axis direction
(0.7 W m−1 K−1 ). When grown from a melt or by zone refining, Bi2 Te3 crystals are always non-
stoichiometric and show p-type behavior. In contrast, n-type materials can be grown from melt
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containing excess Te, I, or Br. The thermal conductivity values of both p-type and n-type Bi2 Te3
are ∼1.9 W m−1 K−1 , giving a ZT of ∼0.6 near room temperature. Ioffe (21) suggested that
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alloying could further reduce the lattice thermal conductivity of Bi2 Te3 through the scattering
of short-wavelength acoustic phonons. The optimum compositions for TE cooling devices are
normally Bi2 Te2.7 Se0.3 (for n type) and Bi0.5 Sb1.5 Te3 (for p type) with ZT ≈ 1 near room tem-
perature. As stated above, the incorporation of in situ nanostructures that are nucleated by either
high-energy ball milling or melt spinning in these materials has proven beneficial in reducing the
lattice thermal conductivity and in achieving ZT ≈ 1.4 between 300 K and 400 K (14–16).
In contrast to Bi2 Te3 , PbTe crystallizes in a cubic NaCl-type crystal structure, and the TE
properties are isotropic. Both p-type and n-type thermoelements can be produced by doping of
acceptors (e.g., Na2 Te or K2 Te) or donors (PbI2 , PbBr2 , or Ge2 Te3 ). In analogy to Bi2 Te3 , solid-
solution compositions (e.g., PbTe-SnTe) have been made to lower the lattice thermal conductivity
(29). The ZT value is low near room temperature but increases to ZT ≈ 0.7 at 700 K, making this
a prime candidate for power generation in the higher-temperature range. High ZT values (ZT ≈
1.5) were recently achieved in Tl-doped PbTe materials by using the concept of energy filtering
to enhance ZT. Such values can be achieved by inducing a large variation in the density of states
near the Fermi level, thus significantly enhancing the thermopower (30). This energy-filtering
effect can be understood through a modified Mott diffusion equation for the thermopower by
manipulating the chemical potential term with an addition of only 2% Tl.
 
π 2 k2B T 1 d n(E) 1 d μ(E)
α= + . 13.
3e n dE μ d E E=E F
It is possible to achieve ZT in excess of unity at 700 K in a structurally related solid-solution
composition, AgSbTe2 (80%)–GeTe (20%) (termed TAGS, which denotes alloys containing Te,
Ag, Ge, and Sb). However, due to high-temperature stability issues, these compositions are not
currently favored in TE devices.
Neither Si nor Ge is a good TE material because both have a very high lattice thermal conduc-
tivity (150 W m−1 K−1 and 63 W m−1 K−1 for Si and Ge, respectively). However, the lattice thermal
conductivity can be substantially reduced by alloy formation between the two elements. The best
alloy composition is Si0.7 Ge0.3 , which possesses a thermal conductivity that is ∼10 W m−1 K−1 , and
the reduction is apparently due to increased phonon-phonon and phonon-electron scattering (18).
Remarkably, such a large reduction does not unduly reduce the carrier mobility, and ZT ≈ 0.6–0.7
can be realized at elevated temperatures. Due to their exceptional stability at high temperature
(∼1,200 K), these alloys are of interest to NASA for use in RTGs in deep-space probes. Nanos-
tructuring in these materials has also led to a further reduction in the lattice thermal conductivity
and to higher ZT values; such nanostructures are stable at high temperatures (31).

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 MR41CH17-Tritt ARI 3 June 2011 8:42

3.2. Complex Inorganic Structures

Most of the above-mentioned investigations focused on binary intermetallic semiconductor sys-
tems. Recent approaches to high-performance bulk TE materials focus on ternary and quaternary
chalcogenides containing heavy atoms with low-dimensional or isotropic complex structures to
take advantage of the high carrier effective masses and low lattice thermal conductivities associ-
ated with such systems (32). Along these lines, CsBi4 Te6 possessing a layered structure has been
identified as a material showing a ZT of 0.8 at 225 K; this ZT value is 40% greater than that of
the Bi2−x Sbx Te3−y Sey alloys (33). Other potential low-temperature TE materials currently under
investigation are low-dimensional semiconducting or semimetallic doped layered pentatellurides
(e.g., ZrTe5 and HfTe5 ) (34). These compounds have a structure similar to that of Bi2 Te3 , with
a van der Waals gap between the individual layers. Although doped pentatellurides exhibit very
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high power factors (exceeding the optimally doped Bi2 Te3 solid solutions) in the low-temperature
range (<250 K), the thermal conductivity is relatively high (κ ≈ 4–8 W m−1 K−1 ). These materials
Annu. Rev. Mater. Res. 2011.41:433-448. Downloaded from www.annualreviews.org

need to be compositionally tuned further to be useful TEs.

Cubic quaternary compounds with a complex formula Agn Pbm Mn Tem+2n (M = Sb, Bi) and
that crystallize in a PbTe structure were recently reported (35). The composition AgPb10 SbTe12
shows exceptionally high ZT values (>2) at elevated temperatures (shown in Figure 4). Such
values are due to the very low total thermal conductivity of the bulk materials, which possibly
arises from compositional modulations (seen as a nanodot) similar to the kinds of nanostructures
that are found in superlattices. These materials have ZT values of >1.7.
Another group of materials under investigation is half-Heusler alloys with a gen-
eral formula MNiSn, where M = Zr, Hf, Ti. A complex composition of the type
Zr0.5 Hf0.5 Ni0.5 Pd0.5 Sn0.99 Sb0.01 shows a ZT of 0.7 at T ≈ 800 K, highlighting the intricate balance
in structure/composition/property relationships in these compounds (36). The β-Zn4 Sb3 system
has been reinvestigated for TE power generation applications at the Jet Propulsion Laboratory
(37).

3.3. Crystal Structures with Rattlers

The method of lowering the lattice thermal conductivity through a mixed-crystal or solid-solution
formation does not always produce enough phonon scattering to lower the lattice thermal con-
ductivity to κ min . Slack’s PGEC concept, described above, avoids this limitation. The concept of
κ min is successfully verified in crystal structures with large empty cages or voids, where atoms can
be partially or completely filled in such a way that they rattle, resulting in the scattering of the
acoustic phonons. This approach works especially well in highly covalent semiconductor materials
based on clathrates (Si, Ge, or Sn) and void structures formed by heavy elements of low electroneg-
ativity differences, e.g., CoSb3 -based skutterudites. Some doped skutterudites show exceptionally
high ZT values at elevated temperatures (ZT ≈ 1.2 at 600–800 K). More recently, multiple filler
atoms (e.g., Ce, Yb, and Ba) and In doping along with nanostructuring have resulted in significant
improvements in these materials (38–41).

3.4. Oxide Thermoelectrics

Numerous oxides with metal atoms in their common oxidation states are stable at elevated temper-
atures and show electrical properties ranging from insulating to superconducting. Nevertheless,
oxides have received very little attention for TE applications because of their strong ionic char-
acter: They have narrow conduction bandwidths arising from weak orbital overlap, which leads

444 Tritt
 MR41CH17-Tritt ARI 3 June 2011 8:42

to localized electrons with low carrier mobilities. This situation changed with the unexpected
discovery of good TE properties in a strongly correlated layered oxide, NaCo2 O4 (42). This oxide
attains ZT ≈ 0.7–0.8 at 1,000 K. Inspired by the striking TE performance of NaCo2 O4 , most
of the current research is currently focused on Co-based layered oxides such as Ca3 Co4 O9 and
Bi2 Sr3 Co2 Oy that crystallize in misfit layered structures (24). Among the n-type oxides, Al-doped
ZnO (Al0.02 Zn0.98 O) exhibits reasonably good TE performance (ZT ≈ 0.3 at 1,000 K) (43).

3.5. Thin-Film and Superlattice Materials

The approaches in bulk materials research rely heavily on the thermodynamic stability of phases
at a given condition, whereas thin-film deposition can yield metastable designer phases with novel
properties. Quantum well (0-D, 1-D, and 2-D) systems take advantage of a low-dimensional
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character through physical confinements in quantum dots, nanowires, and thin-film structures
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to enhance the electronic properties of a given material (44). In addition, nanostructured semi-
conductor materials may scatter mid- to long-wavelength phonons and thereby reduce the lattice
thermal conductivity to κ min . Researchers at the Research Triangle Institute have demonstrated
a significant enhancement in ZT through the construction of Bi2 Te3 /Sb2 Te3 superlattices (17,
45). These materials exhibit ZT ≈ 2.4. The enhancement is attributed to creating a nanoengi-
neered material that is efficient in thermal insulation while remaining a good electrical conductor.
The thermal insulation arises from a complex localization-like behavior for phonons, whereas
electron transmission is facilitated by the optimal choice of band offsets in these semiconductor
heterostructures. Also, there have been reports on PbTe/PbTeSe quantum dot structures that
yield ZT ∼ 1.3–1.6 (46). These materials have been grown as thick films. Such films have been
floated off the substrate to yield freestanding films, which were measured to yield these results.

4. CONCLUSIONS
Currently, there are no theoretical or thermodynamic limits to the possible values of ZT. The
current need for alternative energy technologies and materials to replace the depleting supplies
of fossil fuels is becoming more urgent. Energy-related research will grow rapidly over the next
few years, and higher-performance TE materials and devices are direly needed. Slack (24) esti-
mated that an optimized PGEC material could exhibit values of ZT ≈ 4. Such projections give
encouragement that such materials may be possible. However, as is evident from Figure 3, if
we could find TE materials with ZT ≈ 2–3 and that were stable over a broad temperature range
with low parasitic losses, then the problem would be almost entirely solved. Thus, a systematic
search and subsequent thorough investigation of promising materials may eventually yield these
much-needed materials for next-generation TE devices. Although many strategies are being em-
ployed in hopes of identifying the next generation of TE materials, the PGEC approach appears
to be the best, especially for bulk materials. One has to decide whether holey semiconductors
(materials with cages such as skutterudites or clathrates) or unholey semiconductors such as SiGe
or PbTe are the best to pursue and which tuning parameters are available to improve these mate-
rials (47). To date, none of the new materials have displaced the current state-of-the-art materials
(Bi2 Te3 , PbTe, and SiGe) in a commercial TE device. These materials have held that distinction
for more than 30 years. Nanostructuring and in situ growth of stable nanostructures, thus yield-
ing TE nanocomposites, have further improved the TE properties of these materials. Although
the thin-film results are very exciting, they may be most appropriate for small-scale electronic
and optoelectronics applications in which small heat loads or low levels of power generation are
more appropriate. To address large-scale refrigeration (home refrigerators) or power generation

www.annualreviews.org • Thermoelectric Phenomena, Materials, and Applications 445

 MR41CH17-Tritt ARI 3 June 2011 8:42

(automotive or industrial applications) requirements, higher-performance bulk materials will have

to be developed. Theoretical guidance in terms of band structure calculations and modeling will
be essential to identify the most promising TE materials. In addition, rapid yet accurate char-
acterization of materials and verification of results are also necessary to effectively advance this
field of research. A multidisciplinary approach will be required to develop higher-efficiency TE
materials and devices. The techniques used to develop designer materials for thermoelectrics will
most likely prove important in other areas of materials research.

SUMMARY POINTS
1. Thermoelectric materials can be incorporated into devices that can be used for solid-state
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refrigeration or power generation.

2. The interrelationship of the properties of these materials makes it very difficult to find
Annu. Rev. Mater. Res. 2011.41:433-448. Downloaded from www.annualreviews.org

materials that can achieve high ZT values, i.e., ZT > 1.

3. The broad range of properties that must be investigated in the search for high-efficiency
thermoelectric materials make them some of the most interesting materials to study. One
must appreciate the intricate role of both electrons and phonons in a given material and
further understand how to manipulate their properties in a favorable manner to achieve
a high ZT, i.e., designer or phonon glass–electron crystal (PGEC) materials.
4. In the past the low efficiency (<10%) of current materials has limited them to mainly
niche applications.
5. However, over the past 10 years there has been significant improvement in several ther-
moelectric materials, and these are opening up new markets.
6. Several automotive applications are beginning to use thermoelectric materials either
for climate-controlled cooling in automotive cabins or for waste heat recovery from
automobile exhaust systems.
7. Slack’s (24) PGEC methodology and the advent of TE nanocomposites hold promising
potential for achieving materials that possess ZT values of the order of 2–3 and that are
thermally stable over the range of temperatures in which they are to be used.
8. Future world energy demands will certainly make us look at all types of alternative energy
sources as opposed to fossil fuels. Hopefully, thermoelectric materials and devices can
play a small but contributing role in meeting those demands.

DISCLOSURE STATEMENT
The author is not aware of any affiliations, memberships, funding, or financial holdings that might
be perceived as affecting the objectivity of this review.

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Materials Research

Contents Volume 41, 2011

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Materials Science of Biological Systems

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Advances in Drug Delivery

Brian P. Timko, Kathryn Whitehead, Weiwei Gao, Daniel S. Kohane,
Omid Farokhzad, Daniel Anderson, and Robert Langer p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 1
Crystallization Pathways in Biomineralization
Steve Weiner and Lia Addadi p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p21
Deformation and Fracture Mechanisms of Bone and Nacre
Rizhi Wang and Himadri S. Gupta p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p41
Linear and Nonlinear Rheology of Living Cells
Philip Kollmannsberger and Ben Fabry p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p75
Mussel-Inspired Adhesives and Coatings
Bruce P. Lee, P.B. Messersmith, J.N. Israelachvili, and J.H. Waite p p p p p p p p p p p p p p p p p p p p p p99
Nanomechanics of the Cartilage Extracellular Matrix
Lin Han, Alan J. Grodzinsky, and Christine Ortiz p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 133
Plant Stems: Functional Design and Mechanics
Thomas Speck and Ingo Burgert p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 169

Current Interest
Elastic and Mechanical Properties of the MAX Phases
Michel W. Barsoum and Miladin Radovic p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 195
Electrocaloric Materials
J.F. Scott p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 229
Electrochromic Materials
Roger J. Mortimer p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 241
Nanowire Solar Cells
Erik C. Garnett, Mark L. Brongersma, Yi Cui, and Michael D. McGehee p p p p p p p p p p p p 269
Nonconventional (Non-Silicon-Based) Photovoltaic Materials
T. Unold and H.W. Schock p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 297

v
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On the Future Availability of the Energy Metals

T.E. Graedel p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 323
Oxide Electronics Utilizing Ultrafast Metal-Insulator Transitions
Zheng Yang, Changhyun Ko, and Shriram Ramanathan p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 337
Point Defects in Oxides: Tailoring Materials Through
Defect Engineering
Harry L. Tuller and Sean R. Bishop p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 369
Recent Developments in Semiconductor Thermoelectric Physics
and Materials
by Stanford University - Main Campus - Lane Medical Library on 09/29/12. For personal use only.

Ali Shakouri p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 399

Annu. Rev. Mater. Res. 2011.41:433-448. Downloaded from www.annualreviews.org

Thermoelectric Phenomena, Materials, and Applications

Terry M. Tritt p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 433

Index

Cumulative Index of Contributing Authors, Volumes 37–41 p p p p p p p p p p p p p p p p p p p p p p p p p p p 449

Errata

An online log of corrections to Annual Review of Materials Research articles may be

found at http://matsci.annualreviews.org/errata.shtml

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