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Rational Design of Advanced Thermoelectric Materials
Jihui Yang,* Hin-Lap Yip, and Alex K.-Y. Jen*
Advanced thermoelectric technologies can drastically improve energy efficien-
cies of industrial infrastructures, solar cells, automobiles, aircrafts, etc. When
a thermoelectric device is used as a solid-state heat pump and/or as a power
generator, its efficiency depends pivotally on three fundamental transport
properties of materials, namely, the thermal conductivity, electrical conduc-
tivity, and thermopower. The development of advanced thermoelectric mate-
rials is very challenging because these transport properties are interrelated.
This paper reviews the physical mechanisms that have led to recent material
advances. Progresses in both inorganic and organic materials are summarized.
While the majority of the contemporary effort has been focused on lowering
the lattice thermal conductivity, the latest development in nanocomposites
suggests that properly engineered interfaces are crucial for realizing the energy
filtering effect and improving the power factor. We expect that the nanocom-
posite approach could be the focus of future materials breakthroughs.
1. Introduction
Thermoelectric (TE) devices are solid-state heat pumps with
electrons and holes as the working fluid. When used for
heating/cooling applications, these devices can be electroni-
cally controlled and are completely reversible. In addition, a
TE device has the virtue of no mechanical movement as com-
pared to a vapor-compression based air conditioning unit, and,
therefore, has a much longer service life. TE power generators
can also convert heat energy into electricity. Due to rising con-
cerns of sustainable environment and energy efficiency, there
have been worldwide efforts to incorporate TE technologies
into large scale applications, such as waste heat recovery for
transportation, power plants, and industrial infrastructures,
etc.[1] Since the 1990s, cooled/heated seat units for automotive
use have been produced and sold for over 7 million units.[2]
Recent efforts based on similar concept of TE-based distributed
heating/cooling have also gained significant traction owing to
the potential for drastic fuel savings and CO2 reduction.[3]
The efficiency (for power generation) or coefficient of per-
formance (COP for heating/cooling) of a TE device is governed
by the materials TE figure of merit ZT,
Prof. J. Yang,[†] Dr. H.-L. Yip,[†] Prof. A. K.-Y. Jen
Department of Materials Science and Engineering
Box 352120, University of Washington
Seattle, WA 98195-2120 USA
E-mail: jihuiy@uw.edu; ajen@u.washington.edu
[†] J. Y. and H. L. Y. made equal contributions to this work
DOI: 10.1002/aenm.201200514
Adv. Energy Mater. 2013, 3, 549–565 © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
REVIEW
S2 σ T S2 σ T
ZT = =
κ κ L + κe (1)
where S is the thermopower, σ the conduc-
tivity, κ the thermal conductivity (which
includes a lattice κL and an electronic κe
component), and T the absolute tempera-
ture (Equation (1)). Current materials used
for TE power generation and for heating/
cooling have a maximum ZT of ∼1. It
has been estimated that achieving ∼40%
improvement of device efficiency is possible
if the ZT values can be doubled, which will
lead to significant energy savings and envi-
ronmental benefits. For example, several
million gallons of fuel savings and more
than 40 million metric tons of reduction of
CO2 could be achieved annually if TE waste
heat recovery generators and TE distributed
automotive heating/cooling are used.[4]
Other than the system-level engineering challenges and
cost/benefit contemplations, materials discovery and develop-
ment represent a real impediment in the implementation of TE
technology. In this report, we summarize up-to-date TE mate-
rial advances, reflecting two major approaches in the field of TE
materials research. The first approach is focused on reducing
κL of inorganic materials while maintaining their electrical per-
formance. The second approach is relevant to improvement of
the electrical properties of intrinsically low κL organic mate-
rials. At the end, we highlight the importance of interface engi-
neering in recent development of nanocomposites.
2. Inorganic Materials
2.1. Nanostructured Bulk Materials
In the past two decades, we have witnessed the significant
progress made in TE performance by incorporating low dimen-
sional and nanostructural materials. The benefit of low dimen-
sionality and nanostructures arises from two aspects. Firstly, the
characteristic sizes of low dimensionality systems and nanos-
tructures limit phonon but not electron mean free path, hence,
reducing the lattice thermal conductivity (κL) while leaving elec-
trical conductivity (σ) intact. Secondly, the reduced dimension-
ality could result in enhanced thermopower (S). According to
the Mott relation for degenerate semiconductors
 
π 2 k 2B T d ln σ (E ) 
S= 
3e dE E =E F (2)
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where kB is the Planck constant, e the electron charge, E the

electron energy, and EF the Fermi energy. In the case of degen- Jihui Yang received his
erate semiconductors, electrical conductivity can be written as Ph. D. in Physics from the
University of Michigan in
σ (E ) = n(E )eμ(E ) (3) 2000. He is currently the
Kyocera Associate Professor
where n is the carrier concentration and μ the carrier mobility. in the Materials Science and
In materials with reduced dimensionality, the sharp increases in Engineering Department
the electronic density of states g(E), i.e., large d[lng(E)]/dE which of the University of
is proportional to d[lnn(E)]/dE would lead to much enhanced S Washington (UW). Prior to
values; providing that the Fermi energy is adjusted to an energy joining the UW in 2011, he
position where sharp g(E) increase occurs. This mechanism for was the Lab Group Manager
improving ZT was proposed by Shik[5] and modeled by Hicks and GM Technical Fellow
and Dresselhaus for quantum wires and quantum dots.[6,7] of the Electrochemical Energy Laboratory at GM Research
Of course the ZT increase here hinges upon the increase of and Development Center.
power factor S2σ (Equation (1)), which means that any mobility
decrease has to be offset by the increase of S.
The second mechanism of possible ZT improvement comes Hin-Lap Yip received his B.S.
from the d[lnμ(E)]/dE term in Equations (2) and (3). For degen- and M.S. degree in Materials
erate semiconductors: Science from Chinese
University of Hong Kong
eτ (E ) eτ0 E λ in 2001 and 2003, respec-
μ(E ) ≈ ∗
≡ tively. He received his Ph.D.
m m∗ (4)
degree in Materials Science
where τ(E) is the electron scattering relaxation time, τ0 a con- and Engineering from the
stant, m∗ the electron effective mass, and λ the power law University of Washington in
component. Equations (2)–(4) suggest that increased dτ(E)/dE 2008 under the supervision
or λ value can lead to enhanced S by preferential scattering of of Prof. Alex Jen. Currently
charge carriers depending on their energy (hence the name he is a research scientist and
“energy filtering”). Again, in order to increase S2σ and therefore thrust leader of the organic photovoltaics team in Prof.
ZT, S needs to increase more rapidly than any σ decrease as λ Jen’s research group. His research focuses on the use of
increase. Ioffe suggested the use of ionized impurity scattering an integrated approach combining materials, interface,
(λ = 3/2) instead of lattice phonon scattering (λ = −1/2) of device, and process engineering to improve organic elec-
charge carriers to improve S2σ.[8] This has been experimentally tronic devices.
demonstrated in bulk skutterudites,[9] as well as in a number
of nanostructured materials.[10–14] Since the grain size is sig-
Alex Jen is currently the
nificantly reduced in bulk nanocomposites, grain boundary
Boeing-Johnson Chair
scattering becomes more predominant. The grain boundary
Professor and Chair of
barrier could also preferentially scatter lower energy charge
the Materials Science and
carriers and, thereby, improve S2σ if the barrier height is close
Engineering Department
to the Fermi energy.[15] This has been shown in a number of
at the University of
systems.[11,16]
Washington. He is also
Despite the many recent successes in quantum wires,
serving as the Director of
quantum dots, thin-films, and superlattices,[17–22] these low
the Institute of Advanced
dimensional systems are generally difficult to synthesize and
Materials for Energy.
scale up, and of high cost. In addition, their TE properties are
hard to measure and/or validate. For practical applications,
there are also challenges involved in device construction and
thermal management. Recently, the vast majority of effort have
been focused on developing high efficiency nanostructured
bulk materials, which are easy to produce and scalable. There
have been a number of reviews and reports on nano-grained exceed the largest value of Z in any individual component.[32]
materials, TE composites, and the effect of nanosize on TE This is because it is assumed that the carrier de Broglie wave-
performance.[23–31] This review is mainly focused on rational length (λp) is much less than the grain size (G) in classical com-
design of inorganic/organic nanocomposites. In a composite posites; hence, there is no quantum mechanical interference
material, the grain boundary (interfacial) barrier scattering of between adjacent grains. Since it is possible to have G that is
carriers can be visualized in Figure 1(a). Bergman et al. investi- comparable to λp for nanocomposites, the key criterion for real-
gated the TE properties of a composite medium based on clas- izing potential power factor gains is λp ≈ G in order to achieve
sical physics and concluded that Z of the composite can never significant grain boundary scattering of carriers. Figure 1(b) is a

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to be about 1–2 nm, for which κL would be

REVIEW
E Enhance S 2
Before After significantly reduced due to the small G
and many interfaces. Recent results on bulk
materials with grain sizes of 10 - 15 nm made
EF by Spark Plasma Sintering suggest that it is
EB
EC possible to achieve bulk materials with 5–10
nm grains.[35] Data in Table I also suggest
EV that grain boundary charge carrier scattering
Grain Grain Grain
could be manifested for materials with long
Boundary
de Broglie wavelength.
Figure 1. (a) Interfacial energy filtering for power factor enhancement of TE composites. (b) A
From the TE material design point of view,
schemetic drawing of composite material structures showing the carrier de Broglie wavelength another important factor is the κL reduc-
λp comparable to the grain size. tion in nanostructures. Regarding this, the
cumulative lattice thermal conductivity con-
cept developed by Chen is very useful.[36]
schematic drawing of nanocomposite structures showing inor- The cumulative lattice thermal conductivity with respect to the
ganic and/or organic interfacial layers as well as the optimal λp phonon mean free path is a measure of the amount of contribu-
≈ G condition. Our preliminary ab initio λp calculations for var- tion from phonons with various mean free paths. For example,
ious potential matrix materials are listed in Table I; they imply the calculations from Chen showed that phonons with mean
that the range of G values would be around 5–10 nm.[33] Based free path of >100 nm have the potential to carry 25% of the heat
on this, we have estimated the thickness of interfacial layer d in the bulk material. If one ignores the interfacial phonon scat-
tering, nanocomposites with a length scale of 100 nm could
reduce thermal conductivity by 25%, which has been validated
Table I. Charge carrier de Broglie wavelengths of various potential by the experimental data generated for Half-Heusler alloys.[37]
composite matrix materials at different doping levels, given by ab initio In addition, the maximization of interfacial phonon scattering
calculations. requires high acoustic mismatch or high degree of surface
roughness.[38,39]
System p-type or Carrier Concentration λp In the following paragraphs, we summarize recent developed
n-type (1020 cm3) (nm)
inorganic materials that have high de Broglie wavelength values
CoSb3 n 13.2 1.39 (λp > 3 nm), such as the Bi2Te3-based nanostructural materials,
n 0.2 5.71 the caged structure skutterudites and clathrates, and the Si/Ge
p 0.2 13.4 alloys. We have chosen to include nanocomposite chalcogenides
ZrNiSn n 17.5 2.79
because the band structure modulation induced by large lattice
strain field in nanostructures could be beneficial to other mate-
p 17.5 1.50
rials, even though their de Broglie wavelengths are low. In light
GaAs n 2 1.90 of lacking bulk InSb- and GaAs-based high ZT materials,[11] we
n 0.02 15.4 have chosen not to include these in our review.
p 0.5 3.56
InSb n 2 2.00 2.1.1. Nanocomposite Chalcogenides
p 0.5 4.00 PbTe-AgSbTe2 nanocomposites were found to be efficient ther-
Bi2Te3 n 0.5 4.85 moelectrics possessing one of the highest ZT values, reaching
p 0.5 4.86 2.1 near 800 K as shown in Figure 2.[40] Most of these materials
PbTe n 2.5 1.33
n 1.0 1.62
p 1.0 1.75
Si n 1.3 1.94
n 0.39 2.58
p 1.1 2.20
p 0.36 2.78
SiGe n 0.5 2.26
p 0.5 3.69
NaCoO3 n 20 0.87
Figure 2. ZT as a function of temperature (left) of AgPb18SbTe20, and a
TEM image of the sample (right) showing a nano-sized region that is
p 20 0.51 Ag-Sb-rich in composition. The surrounding structure, which is epitaxially
B8Ga16Ge30 n 1 2.23 related to this feature, is Ag-Sb-poor with a unit cell parameter of 6.44 Å,
close to that of PbTe. Reproduced with permission.[40] Copyright 2004,
p 1 3.46
The American Association for the Advancement of Science.

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Figure 3. Left: (a) High resolution TEM image of a single crystal (PbTe)18-(AgSbTe2) sample; (b) and (c) are the magnified images of typical nanopre-
cipitates in (a). The corresponding simulated images in (d) and (e) are based on the atomic positions predicted by the ab initio calculations shown in
(f) and (g)[51]. Reproduced with permission.[51] Copyright 2009, The American Physical Society.The diffusive nature of the nanoprecipitates is caused by
Ag atoms that taking interstitial positions. Right: Calculated band structures forPbTe, PbTe-AgSbTe2with 32 pairs of Ag-Sb(LAST32) in the 1000-atom
supercell.[53] Reproduced with permission.[53] Copyright 2011, The American Physical Society.

have been synthesized by using conventional melting and
annealing methods. Mostly, the ZT improvement arises from
the very low lattice thermal conductivity values attributed to
phonon scattering by nanometer scale precipitates, as shown
in the transmission electron microscopy (TEM) image in
Figure 2. The literature on TE properties of AgSbTe2, GeTe-
AgSbTe2, SnTe-AgSbTe2 and PbTe-AgSbTe2 date back to the
early 1960s.[41,42] The lattice thermal conductivity κL of AgSbTe2
at room temperature is extremely low ∼0.63 W/m-K[43] which
is close to the minimum lattice thermal conductivity – a
minimum value of lattice thermal conductivity in solid when
the mean free path of phonons is less than the phonon wave
length.[44] This is attributed to its enormously large Grüneisen
parameter and, hence, the anharmonicity of the crystal.[45]
Because of the nanoprecipitates, the κL of PbTe-AgSbTe2
system is lower than the values given by the solid solution
model for PbTe and AgSbTe2.[46] Therefore, the nanoprecipi-
tates offer an additional handle for optimizing TE performance.
A number of chalcogenides-based nanocomposites (both n- and
p-type) have been reported to possess nanostructures that are
endotaxially embedded in the matrix.[47–50] Ideally, one would
hope that these endotaxially embedded nanoprecipitates do not
cause additional charge carrier scattering, hence, maintaining
the power factors of the matrix materials. In reality, the power
factor for most of these cases is also reduced because the nano-
inclusions increase carrier scattering and reduce the carrier
mobility subsequently. To date, the dramatic enhancements
of ZT in bulk nanostructured materials come from very large
reductions in κL but with only modest reductions in power
factor.[46]
A critical question surrounding these nanocomposites is
whether they are thermodynamically stable. Recent ab initio cal-
culations that employ a massive 1728 atoms supercell reveal that
the formation of AgSbTe2 nanoprecipitates is thermodynami-
cally preferred over a uniform dispersion of Ag and Sb atoms
in PbTe, and the growth of nanoprecipitates is driven by two
fundamental forces, ie., the dipole–dipole attraction between
Ag-Te-Sb pairs and a strain field weakening the dipole–dipole
interaction.[51] On the experimental side, an in-situ synchrotron
diffraction study showed that the nanoprecipitates remain ther-
mally stable to at least 800 K,[52] and samples annealed at 870 K
for 3 months showed persistence of nanoprecipitates, the elec-
trical and thermal transport properties;[46] further validating the
thermodynamic stability of these nanoprecipitates.
Experimental results and ab initio calculations of these nano-
composites[51,53] also uncovered an interesting atomistic struc-
tural feature that is not revealed in previous studies.[54–57] The
Ag atoms in PbTe-AgSbTe2 deviate significantly from the ideal
lattice positions, up to 72% of an ideal bond length (Figure 3 left
panel). Electronic band structures of nanocomposites unveiled
a sizable widening of band-gap driven by nanodopant-induced
lattice strain and a band splitting caused by the spin-orbit inter-
action in nanodopant (Figure 3). In general, band-gap widening
is beneficial to the enhancement of power factor at elevated
temperatures, while band splitting at the conduction band min-
imum is detrimental. These substantial yet competing effects
elucidate the underlying mechanisms of experimental power
factor variations amongst different nanocomposite systems,
and further suggest that dopant atoms possessing weak SOI
should be used to minimize the band splitting or power factor
reduction.
While it is clear that nanometer scale precipitates are very
effective in scattering lattice phonons to achieve lattice thermal
conductivity values lower than those given by the solid solution
model (point defect scattering), the role of nanoprecipitates on
charge carrier scattering is still uncertain. Given that the values
of κL for these nanocomposites have already approached the
minimum lattice thermal conductivity,[44] further ZT improve-
ment needs to come from the enhancement of power factor.
Therefore, it is crucial to understand, design, and optimize the
charge carrier scattering mechanisms in these nanocomposites.
Amongst various recent approaches that attempt to combine
low κL with improved S2σ, distortion of g(E) near the Fermi
energy,[58] interplay between two valence bands in PbTe[59], and

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Figure 4. Nanograined BixSb2-xTe3:(a) Bright field-TEM image of multigrains, (b) HRTEM of
grainboundaries, (c) HRTEM images of smaller grains, and (d) particle size distribution histo-
gram for the nanograined bulk material with the inset zooming in on the distribution of small
size particles less than 200 nm. Reproduced with permission.[61] Copyright 2009, The American
Chemical Society.
g(E) modification and nanostructure shape control seem to be
most promising.[60]
2.1.2. Ball Mill and Rapid Solidification Methods
In term of developing scalable and cost effective materials and
processes, there are two separate yet comparable efforts in syn-
thesizing nanostructured bulk materials. One method uses ball
milling to convert bulk materials into nanopowders while the
other exploits a rapid solidification technique (melt spinning)
to create nanostructured ribbons. Hot press or spark plasma
sintering (SPS) techniques are subsequently used to consoli-
date nanopowders or ribbons into bulk samples. These tech-
niques have created abundant multiscale structural features
that are very effective in scattering lattice phonons. Figure 4
shows the microscopic structure of BixSb2-xTe3, in which 12%
of the grains have a diameter of <20 nm and 5% have a diam-
eter in the 20–40 nm range.[61] Phonons with mean free paths
that are comparable to grain size are strongly scattered by the
grain boundary, leading to substantially reduced κL. The wide
grain size distribution shown in Figure 4d is responsible for
scattering phonons with a variety of wavelengths.[34] In addi-
tion, it was suggested that the Bi-rich grain boundary layers
was also observed in the materials, creating Bi vacancies in the
grain. This not only raises hole concentration, but also reduces
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the bipolar contribution of the electronic
thermal conductivity; leading to substantial
ZT increase between 50 and 250 °C (ZTmax =
1.4 at 100 °C).[34]
The top panel in Figure 5 shows the micro-
structural features of melt-spun (MS)Bix
Sb2-xTe3 across the thickness of a ribbon.[62]
There is an essentially amorphous phase near
the contact surface while it gradually crosses
over to the 5–10 nm fine nanocrystal regime
with coherent grain boundaries. After a quick
SPS process (bottom panel), the sample con-
tains some nanocrystalline domains in the
amorphous phase while the majority of it
comprises coherently packed nanocrystals.
When compared with zone melted ingots
with SPS consolidation (ZM-SPS) and zone
melted ingots without SPS (ZM), the MS-SPS
sample possesses superior TE performance
(shown in Figure 6), reaching ZT of >1.4 at
temperatures between 300 and 360 K.
Ball milling and melt spinning produce
wide range of nanocrystals with coherent inter-
faces in between μm size grains and a mixture
of coherent/incoherent interfaces, respectively.
In both cases, power factor does decrease but
much slower than the κL reduction. Further-
more, the mixture of coherent/incoherent
interfaces seems to be more effective in
reducing κL to improve ZT. These techniques
have been successfully applied to a variety of
bulk materials such as skutterudites,[63–66] half
Heuslers,[37,67,68] SiGe alloys,[69] and Zn4Sb3.[70]
2.2. Cage-Structured Semiconductors
Two of the most studied semiconductor compounds for TE
applications in the past two decades are skutterudites and cla-
thrates.[71–73] The unit cells of these two materials are shown
in Figure 7. Both materials possess large interstitial voids that
can be filled with filler atoms. These fillers have large atomic
displacement parameters and, therefore, rattle inside their
crystallographic sites. This unique characteristic provides high
degree of flexibility in tuning their thermal and electrical trans-
porting properties to generate a very rich spectrum of physical
phenomena. In the following sections, we will summarize the
latest advances in improving TE properties.
2.2.1. Multiple-Element-Filled Skutterudites
The concept of multiple filling in n-type CoSb3-based skut-
terudites originated from a study on the vibrational frequency
(or energy) of a list of rare earth, alkaline earth, and alkaline
fillers.[74] It was found that the vibrational frequencies of these
fillers could be grouped according to their chemical nature.
Although the frequencies for fillers are comparable when they
have similar chemical nature, there is significant difference
amongst various groups. If a resonant scattering model is used
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and eventually triple-element filling (shown

in Figure 8), while the electrical transporting
properties maintain as solely dependent on
the electron concentration, not affected by
the mixture of fillers (with different valence
charges).[75,76] Importantly, at high tempera-
tures, κL of triple-filled materials approached
the minimum lattice thermal conductivity
(the amorphous limit) leading to very high
ZT values at elevated temperatures (ZTmax =
1.7 at 850 K, Figure 9).
The success of n-type skutterudites devel-
opment necessitates the continuing develop-
ment of the p-type skutterudites for optimal
device configurations. Despite the long-term
research efforts, the ZT of p-type skutteru-
dites have plateaued to values lower than
1.2.[77–79] The challenge of developing effi-
cient p-type skutterudites lies in their high
electrical resistivity[80] and bipolar thermal
conductivity at elevated temperatures.[81] A
recent ab initio study of 4d and 5d elements
based p-type skutterudites offers the possi-
Figure 5. Top: (a) Diagram of the MS process indicating the free surface (FS) and the contact
surface (CS) of the resulting melt-spun ribbon is shown. (b) TEM images of ribbon’s cross
bility of achieving lower electrical resistivity
section. (c)–(e) show the TEM images in different areas in (b). (f) TEM image of free surface from materials with light valence band and
of ribbon sample. Bottom: HRTEM images of MS-SPS bulk material. The NC domains in (a) smaller electron-phonon interactions.[82]
the amorphous phase and (b) the coherently packed nanocrystals inherited from ribbon sample
after the SPS process.[62] Reproduced with permission.[62] Copyright 2009, American Institute
of Physics. 2.2.2. Transition Metal Substituted Clathrates
In a typical type I clathrate Ba8Ga16Ge30the
for phonon scattering between the filler-induced non-dispersive framework structure is formed by the tetrahedrally bonded net-
localized modes and those of the heat carrying lattice phonons, work of Ge. The Ba atoms reside in both the Ge20 and Ge24 cages
multiple filling with different group elements will be an effec- at the 2a and 6d crystallographic positions, respectively. Type I
tive method to create broader range of phonon scattering (as clathrates have very low thermal conductivity values originating
compared to single element filling) for achieving additional from the static and dynamic disorder of the guest atom inside the
reduction of κL in filled skutterudites. cages.[71] Despite many recent improvements, the maximum ZT
This optimization strategy succeeded in progressively value of type I clathrates remains below 1, except for several single
decreasing κL of filled skutterudites from single-, to double-, crystal samples.[83] When transition metal (TM) was substituted on
the framework, the power law coefficient (α) of
temperature dependence of electron mobility
(μH ∝ Tα) was found to change from −1.5 to
0.3. This indicates a mixed electron-phonon
and ionized impurity scattering of electrons in
TM-substituted clathrates, leading to enhanced
thermopower and power factor as compared to
Ba8Ga16Ge30 (Figure 10).[84–87] The combined
power factor improvement and the TM point
defect scattering of phonons provide much
improved ZT values (ZTmax = 1.2 at 1000 K,
Figure 11). Band gap (Eg) of these materials can
also be adjusted via TM alloying (as shown in
Figure 11), which offers a great opportunity to
optimize TE properties of these materials in a
wide temperature range.

2.3. Si/Ge Alloys

Figure 6. Thermoelectric transport properties of ZM, ZM-SPS, and MS-SPS samples.[62] Since 1970s, the SiGe alloys are well estab-
Reprinted with permission.[62] Copyright 2009, The American Institute of Physics. lished high temperature TE materials for

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3. Organic-Based Thermoelectric
Materials
As discussed in the previous sections, inor-
ganic semiconductors are currently the most
commonly studied TE materials due to their
intrinsically high mobility, tunable electric
conductivity through doping, and generally
high S. However, the relatively high cost for
production, scarcity of certain components,
and toxicity of these materials may limit their
large-scale deployment for TE devices.
Carbon-based π-conjugated materials such
as conducting polymers and small mole-
Figure 7. Left: the skutterudite unit cell centered at the void, which is enclosed in an irregular
dodecahedral (12-fold) cage of Sb atoms (filled circles). Right: A unit cell of Ba8Ga16Ge30 with cules, carbon nanotubes and graphenes, and
two different types of polyhedral, the dodecahedron (12 pentagonal faces, in brown) and the their hybrids offer new opportunities for TE
tetrakeidecahedron (12 pentagonal and 2 hexagonal faces, in blue). applications because of their low κL, large S,
and tunable high conductivity. Recently, TE
conversion in a single molecule has been
explored due to the possibility of achieving
large S in conjugated molecules since charge
transport through single molecules is con-
trolled by discrete energy levels.[91–93] How-
ever, fundamental understanding of phonon
and electron transport across molecular junc-
tions remains at a very rudimentary level
and there are only limited reports on bulk
TE properties of devices involving molecular
junctions.[94]
In general, carbon-based materials are
abundant, non-toxic, easy to scale-up, and
compatible with solution-based processes for
large-scale production. They are also light-
weight and mechanically flexible, which
provide a new form factor to produce flex-
Figure 8. (a) Room temperature and (b) high-temperature (850 K) lattice thermal conductivity ible and portable TE devices. The versatility
as a function of total filling fraction. The solid linesare guides to the eye. Estimated high power of chemical synthesis allows semiconducting
factor region (between the red lines) are also shown to demonstrate how to simultaneously molecules and polymers to be made with
maximize power factors and minimize lattice thermal conductivity.[75,76] Reproduced with per- diverse molecular structures. They can also
mission.[76] Copyright 2011, American Chemical Society.
be used to modify carbon nanotubes and
graphenes to provide tunable physical prop-
space applications due to their high melting points, large erties for targeted applications. Although TE properties of cur-
energy gaps, and good chemical stability.[88,89] In particular, the rent carbon-based materials are still inferior to their inorganic
Si0.8Ge0.2 alloys were used because of their low lattice thermal counterparts, significant progress has been made in the past
conductivity values.[71] few years in improving their performance. By optimizing their
Figure 12 shows the comparison of experimental data of electrical and thermal properties, ZT of >0.1 have been shown
electrical and thermal transport properties between a ball- for several new π-conjugated material systems. The important
milled 5–10 nm particle size nanocomposite (SGMA04) and factors that govern the TE property of carbon-based materials
a bulk Si0.8Ge0.2 alloy (P-JIMO) which are both p-type mate- are discussed in the sections below and several recent break-
rials.[90] These encouraging data show that, due to strong throughs in achieving high ZT are also highlighted.
interfacial scattering, the nanocomposite has higher S and
higher electrical resistivity (lower σ) and the increase in S is
substantially larger than the decrease in σ; which results in 3.1. Conducting Polymers for TE
a noticeable S2σ increase between 300 K and 1000 K. At the
same time, κL is also significantly reduced in the nanocom- Since the realization of high electrical conductivity in
posite. Such simultaneous S2σ improvement and κL reduc- π-conjugated polymers in the late 70s, this class of organic
tion has only been observed in nanostructured materials, electronic materials has attracted significant attention due to
and this was attributed to the energy filtering effect at the the feasibility of tuning their mechanical, electrical, and optical
interfaces.[90] properties through chemical modifications. In addition, these

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Figure 9. ZT vs. temperature for single-, double-, and triple-element-filled

CoSb3 skutterudites. Data for Bi2Te3, PbTe and SiGe are also plotted for
comparison.

polymers can be easily processed to reduce the cost for practical

applications. So far, conjugated polymers have been extensively
investigated for various types of organic electronic applications
including light-emitting diodes, field-effect transistors, and
solar cells.
Conjugated polymers are also considered as a class of poten-
tially high ZT TE materials oweing to their intrinsically low
thermal conductivity (ca. ∼0.2–0.4 W/mK).[95] The electrical con-
ductivity of conjugated polymers can also be modulated through
chemical doping. For example, p-doped polyacetylene (PAc) can Figure 10. (a) Room temperature carrier scattering parameter α as
achieve σ as high as ∼105 S/cm, which is comparable to that of a function of y, (b) Thermopower as a function of electron density at
[96] room temperature, and (c) Temperature dependence of power factor, for
common metals. Conjugated polymers can also have high S
Ba8NiyGazGe46-y-z. The solid line in (b) represents a S ∝ n−1/3 relation.[85]
with values over 1000 μV/K when they are in neutral or slightly Data for Ba8Ga16Ge30 are taken from Refs. [86,87]. Reproduced with
doped form. However, similar to that of inorganic TE materials, permission.[84]
their S will decrease when σ increase. As a result, a finite bal-
ance between these two factors is required to optimize the power charge carriers. As a result, the electronic states close to the
factor S2σ, which is in the range between ∼1–3 × 10−3 W/mK2 Fermi energy will be delocalized, resulting in metallic conduc-
for the best conducting polymers reported so far. This gives a tion and a significantly reduced S. The metallic nature of highly
ZT of ∼0.1–0.25 at room temperature.
Since conjugated polymers are intrinsically
semiconductors in their neutral form, doping
is required to optimize the power factor (S2σ)
for improving ZT. Typically, doping for con-
jugated polymers is carried out by exposing
the polymer films to the vapor or solution
of dopants electrochemically or chemically.
Although this process will increase σ of
polymers, charge carriers generated through
doping will also decrease their S. Similar to
inorganic semiconductors, when the doping
level in conducting polymers increases, the Figure 11. Left: theoretical and experimental E of Ba Ni Ga Ge
g 8 y z 46–y–z andBa8ZnyGazGe46–y–z
Fermi energy is pushed within the conduc- versus y/ymax. The solid lines are guides for the eye. Right: temperature dependence of ZT for
tion band due to the increased number of TM-doped Ba8Ga16Ge30. Reproduced with permission.[84]

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factor achieved from polyacetylene was ∼1.3 ×

REVIEW
10−3 W/mK2 with a σ of ∼60000 S/cm and a
S of ∼15 μV/K.[108] However, this polymer is
unstable under ambient conditions and is dif-
ficult to process. Therefore, the development
of environmentally stable conducting poly-
mers and dopants that can be easily processed
from solution is critical for applying con-
ducting polymers to practical TE applications.

3.1.1. P-type Poly(3,4-ethylenedioxythiophene)

Figure 12. Comparison of (a) Electrical resistivity, (b) Seebeck coefficient, (c) Power factor, and charge compensated usually by H , gives this
(d) Lattice thermal conductivity between a p-type Si0.8Ge0.2 nanocomposite (SGMA 04) and polyelectrolyte complex its water solubility.
Bulk Si0.8Ge0.2 (P-JIMO).[90] Copyright 2006, Cambridge University Press.
conducting polymers is confirmed by the evidence of metallic
thermopower over a wide range of temperatures. Therefore, [ 96 ]
the optimal power factor in conjugated polymers is generally
obtained at a moderate carrier density.
The TE properties of several classes of conducting polymers
such as polyacetylenes,[97] polyanilines,[98] polypyrroles,[99,100]
polyphenylenevinylenes,[101] polythiophenes,[102] polycarba-
zoles,[103] and metallated polymers[104] have all been extensively
studied and reviewed.[105–107] The value of σ and S span a very
−
broad range: from 10 to 60000 S/cm and 10 to 1000 μV/K,
5 film could be further improved by adding ionic liquid into the
respectively.[108,109] Among various types of conducting polymers,
iodine-doped polyacetylene showed a very encouraging TE power
factor that approaches the best TE materials. The highest power
In the past decade, poly(3,4-ethylenediox-
ythiophene) doped with poly(styrenesulfonic
acid) (PEDOT:PSS) is the most commonly
studied and commercially available con-
ducting polymer that has been widely
applied as hole-transporting interfacial mate-
rials and conducting electrodes for various
organic electronic devices due to their con-
venient solution processibility and good sta-
bility.[110] TE performance of PEDOT:PSS
had also been explored extensively.[95,106,111]
It is obtained directly in the p-doped state
(PEDOT+) through oxidative polymerization
of ethylene dioxythiophene in an aqueous
emulsion in the presence of PSSH. PEDOT+
binds electrostatically to the polyanion PSS−,
while the presence of excess ionized PSS−,
+
A wide range of σ (from 10−6 to 103 S/cm)
can be achieved by changing the composi-
tional ratio between PEDOT and PSSH[112] and by processing
with additives[112–114] to modify the microstructure of the
PEDOT:PSS film. It was found that by adding small amounts
of dimethyl sulfoxide (DMSO) or ethylene glycol (EG) as
processing solvent for PEDOT:PSS film, its σ can be increased
by around one order of magnitude (Figure 13a) while S is only
slightly reduced (Figure 13b). As a result, an optimized ZT
of 0.01 could be achieved at 300 K and it decreased to 0.006
at 200 K (Figure 13c).[115] The TE performance of PEDOT:PSS
polymer solution, which resulted in simultaneously increased
σ and S. The maximum σ and S of such a PEDOT:PSS/ionic
liquid film could reach 174 S/cm and 30 μV/K, respectively. The

Figure 13. Temperature dependence of (a) electrical conductivity, (b) Seebeck coefficient and (c) ZT of PEDOT:PSS films prossessed with (䊏) no addi-
tive, (䊉) 5% DMSO, (䉱) 10% DMSO, (䉲) 5% EG and (䉬) 10% EG. Reproduced with permission.[[115]] Copyright 2010, Elsevier.

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Figure 14. (a) Schematic drawing of the de-doping mechanism of PEDOT-Tos film using TDAE reducing agent. (b) Thermoelectric properties versus
oxidation level of PEDOT-Tos film. Reproduced with permission. [116,117] Copyright 2011, Macmillan Publishing Group.
optimized power factor was found to be 9.9 μW/mK2, leading to
a ZT of 0.017 at RT for PEDOT:PSS film assuming a κ of 0.17
W/mK.[113]
A recent breakthrough of ZT in conducting polymers has
been reported where the tosylate (Tos) was used as counter
ion to replace polyanion (PSS−) in PEDOT film. This allows
better control of doping stoichiometry and interchain stacking
of PEDOT.[116,117] PEDOT-Tos can be polymerized directly by
mixing EDOT monomers with an oxidative solution of Fe(III)
p-toluenesulphonate. The σ, S, and power factor of the highly
doped PEDOT-Tos film at room temperature are 300 S/cm,
40 μV/K and 38 μW/mK2, respectively. The optimal power factor
for PEDOT-Tos could be achieved by carefully exposing the film
to the vapor of a reducing agent tetrakis(dimethylamino)eth-
ylene (TDAE) to de-dope the polymer.
By increasing the exposure time, doping level and σ will
decrease; however, the Fermi level of the conducting polymers
also moves away from the hole conduction band, resulting in a
significant increase in S. At the optimal doping level, a power
factor of 324 μW/mK2 could be achieved with a σ of ∼100 S/cm
and a S of ∼200 μV/K (Figure 14). Considering its low thermal
conductivity (0.37 W/mK), a record high ZT of 0.25 at room
temperature for PEDOT-Tos could be achieved. More impor-
tantly, the doped PEDOT-Tos is stable at temperatures from RT
up to 100 °C in air, which opens up possible practical applica-
tions for low temperature polymeric TE materials.
3.1.2. n-type Organic Thermoelectric Materials
For practical TE device applications, both p-type and n-type
materials are required. Despite there are significant advance-
ments in p-type organic TE materials, the development of n-type
organic TE materials is lagging behind due to great challenges
in developing efficient and stable n-type organic semiconduc-
tors and n-dopants.[118] Although n-doping of electron-trans-
porting materials have been vigorously explored to improve the
performance of organic light-emitting diodes and photovoltaic
cells,[119] there are only very few reports concerning the TE
properties of n-doped organic semiconductors.[120–122] Fullerene
is one of the best n-type semiconductors with electron mobility
higher than 10 cm2/Vs[123] which makes it an ideal candidate
for TE material.
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n-Doped C60 conducting films can be made through vacuum
deposition of several types of n-dopants including alkaline
metals,[124] metal complexes[121] and salts,[122] and molecular
dopants.[125] For example, Sumino et al. studied the TE effect
of Cs2CO3/C60 bilayer thin film device.[122] A buffer layer was
inserted between the C60 film and the substrate to improve the
morphology of C60 film, leading to a high electron mobility of
3 cm2/Vs. The Cs2CO3 functions as an n-dopant to dope the
interface of Cs2CO3/C60, creating a highly conductive channel
with a maximum σ of ∼10 S/cm, which is one of the highest σ
reported for C60 film. Bulk doping of C60 film usually results in
lower σ in the range of 0.05–5 S/cm.[109,125]
The highest power factor for the Cs2CO3/C60 bilayer device
was found to be 20.5 μW/mK2 at RT when the doping condi-
tions and the thickness of C60 film were optimized. Based
on the successful fabrication of n-type TE elements, the first
proof-of-concept organic p-n prototype TE device was also
demonstrated.[122]
The development of solution-processed n-type organic TE
materials represents another level of challenge since more
stringent requirements need to be met to develop both n-type
semiconductors and n-dopants with good processibility and
stability. Although significant progress has been made over the
past few years in developing air stable and high mobility n-type
conjugated polymers[126,127] and solution processible n-dopants
to improve the conductivity of the polymer films,[128,129] their
TE properties have never been studied.
Recently, a new class of polymers based on metal-coordi-
nated tetrathiolate have been shown to possess very prom-
ising p-type and n-type TE properties with their ZT over 0.01
and 0.1, respectively.[104] The polymers could be synthesized
by reacting 1,3,4,6-tetrathia- pentalene-2,5-dione (TPD) with
alkaline metal methoxide followed by adding metal salt to gen-
erate metal-coordinated polymers with the chemical formula of
poly(Ax[M-ett]) as shown in Figure 12.
It was found that the counter ions and center metals of the
polymers strongly affected their conductivity and charge car-
rier polarity. The TE properties of three polymers, poly(Nax[Ni-
ett]), poly(Kx[Ni-ett]), and poly(Cux[Cu-ett]) were systematically
studied and shown in Figure 15a-d. Both of the Ni-coordinated
polymers show n-type characteristics while the Cu-coordi-
nated polymer shows p-type characteristics. Since they all are
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Figure 15. Top: synthetic scheme and chemical structure of poly(Ax[M-ett]). Temperature
dependence of a) electrical conductivity, b) Seebeck coefficient, c) thermal conductivity and
d) figure of merit for poly(Nax[Ni-ett])(䊏), poly(Kx[Ni-ett]) (䊊) and poly(Cux[Cu-ett])(䉱). Repro- have received increased attention because
duced with permission.[104]
amorphous, their κ values are quite small (0.2 - 0.35 W/mK at
300K) which is favorable for improving ZT. Both poly(Nax[Ni-
ett]) and poly(Kx[Ni-ett]) have similar conductivity of ∼40 S/cm
at 300K while the latter shows a higher S of ∼120 μV/K at 300 K.
This results in a high ZT of 0.1 at 300K for poly(Kx[Ni-ett]) and it
reaches 0.2 at 440 K, which represents the highest ZT reported
for any n-type polymeric TE materials. The poly(Cux[Cu-ett]) also
shows a similar magnitude of S but with lower σ and higher κ,
leading to a lower ZT of 0.015 at 400 K. These encouraging TE
properties in metallated polymers open up a new direction for
the development of high ZT organic materials.
3.2. Organic/Inorganic Nanocomposites
TE systems based on organic/inorganic composites can be
potentially benefitted from combined advantages of low κ of
organic materials and high S and σ of inorganic materials while
able to mitigate some of their associated obstacles. According to
the Bergman’s theorem,[32] a homogeneous composite made of
components of different S, σ and κ functioning independently
of each other, cannot have a ZT higher than the highest ZT of
any single component. However, this conclusion is only valid
when different components in the composite do not interact
with each other or wherein one phase does not change the scat-
tering or the wave functions of the carriers in the other were
considered.
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REVIEW
In order to overcome this limitation on
the TE performance of composite materials,
new strategies to allow better manipulation
of the thermal and electrical properties of
the organic/inorganic composites through
nanostructure and interface engineering are
required. For example, interfacial charge
transport across hybrid nanocomposites
has to be carefully controlled by matching
the work function and band-gap of different
components to obtain both high σ and S. By
creating nanostructure of inorganic and/or
organic materials with proper dimensions
and morphologies to enhance phonon scat-
tering at the inorganic/organic interface,
it will reduce κ. The introduction of carrier
energy filtering effect by carefully control-
ling the energy barrier at organic/inorganic
interface to increase the mean carrier energy
relative to the Fermi level can also result in
improved S.[130] In this section, several impor-
tant design concepts employed to improve
the TE performance of organic/inorganic
nanocomposites are discussed.
3.2.1. Polymer–Inorganic Nanocomposites
Recently, TE nanocomposites based on con-
ducting polymers and inorganic nanocrystals
they can be potentially produced with low-
cost solution processing.[106] Despite reason-
ably high σ and low κ can be achieved in conducting polymers,
their low S severely limited their TE properties. By mixing
solution-processible high S inorganic nanocrystals with con-
ducting polymer, it may improve the overall TE properties of
the nanocomposites.
Polyaniline is one of the most investigated conducting poly-
mers for TE applications due to its good stability, high electrical
conductivity, and low thermal conductivity. The best TE per-
formance could be achieved in stretched multilayer polyaniline
films with a ZT of ∼0.01 at 423K.[131] Several polyaniline-based
nanocomposites have been targeted to improve overall TE
performance by incorporating high S inorganic nanocrystals
such as Bi2Te3,[132] Ag2Te,[133] and PbTe.[134] Several methods
such as physical mixing, solution mixing, and in-situ synthesis
of polymer and nanocrystals have all been used to prepare
polymer-inorganic nanocomposites but their TE properties are
very sensitive to the methods used for preparation.[106]
In order to maximize TE property, homogeneous mixing of
polymer and inorganic nanocrystals to form good interfacial
connection is required. For example, improved TE properties
of nanocomposites could be achieved by homogeneous mixing
polyaniline and Bi2Te3 (10 nm nanocrystals).[132] Although the
conductivity of the nanocomposite film decreased from 100 S/
cm to 60 S/cm (compared to the reference polyaniline film),
its S increased from 10 to 110 μV/K at 350 K. As a result, a
50-fold improvement of power factor of 51 μW/mK2 at 350 K
was achieved in the nanocomposite film.
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Highly conducting PEDOT:PSS is another promising can-
didate for nanocomposite TE materials. By adjusting the
PEDOT:PSS formulation, high σ of up to 1000 S/cm could be
achieved in commercially available Clevios PH1000. A respect-
able power factor of ∼47 μW/mK2 was reported earlier in an
optimized PH1000 film that has a σ of 945 S/cm and a S of
22 μV/K.[135] To further improve TE performance, porous com-
posite films with ball-milled particles (several micrometers in
size) of either p-type or n-type Bi2Te3 infiltrated with PH1000
was introduced.[135] The Seebeck coefficients of the optimized
composite films were found to be much higher compared to
that of the pure polymer with S value reaching ∼150 μV/K for
the p-type Bi2Te3/PH1000 film and −120 μV/K for the n-type
Bi2Te3/PH1000 film while σ for both cases are ∼ 60 S/cm.
As a result, a power factor of ∼130 μW/mK2 and an esti-
mated ZT of 0.08 were obtained in the p-type composite films.
The power factor of the n-type composite film is ∼80 μW/mK2,
which is slightly lower than that of the p-type film due to par-
tial cancellation of S by hole-conducting PH1000. Nonetheless,
this study demonstrated an efficient route to obtain n-type TE
polymer composites by loading high S, n-type inorganic parti-
cles into a widely accessible conducting polymer. A better TE
property is expected if n-type polymers can be used.
In-situ synthesis of inorganic nanocrystals in a conducting
polymer containing solution represents a simple method to
produce nanocomposite ink that can be directly cast at low
temperature for making TE films.[136,137] This method has been
demonstrated in the Tellurium/PEDOT:PSS system in which
the Te nanorods were synthesized in-situ in the PEDOT:PSS
(PH1000) aqueous solution.[137] Tellurium was chosen because
of its high S (∼400 μV/K), however, it has a relatively low σ and
high κ. While PEDOT:PSS has low S but high σ and low κ.
PEDOT:PSS can also serve as a structure directing agent during
the growth stage of the Te nanorods in addition to forming a
thin coating on the surface of the nanorods to enable the better
dispersion in water.
Figure 16a shows the synthetic scheme of the Te nanorods and
the nanocomposite film that was drop cast from solution. The
resulting film consists of uniformly distributed nanorods with a
diameter of ∼20 nm and a length of ∼1 μm that are bridged by
PEDOT:PSS (Figures 16b and 16c). Since the diameter of nano-
rods approaches the intrinsic mean-free-path of heat carrying
phonons, and the interface of organic/inorganic nanostructures
can also effectively scatter phonons, low thermal conductivity
(0.2–0.3 W/mK) could be achieved in the nanocomposite films,
which is comparable to that derived from the pure polymer film.
The small difference between the work function of PEDOT:PSS
and Te also allows good Ohmic contact at the organic/inorganic
interface, leading to a high σ of ∼ 20 S/cm, which is about 15
and 250 times higher than that of the pure polymer and nanorod
film, respectively. The nanocomposite film also exhibited a
high S of 163 μV/K and a maximum power factor of ∼70 μW/
mK2, resulting in a ZT of ∼0.1 at RT, which is the largest value
reported for an aqueous processed TE material.
3.2.2. Fullerene-Inorganic Nanocomposite
In addition to polymer–inorganic based nanocomposite,
fullerene-inorganic based nanocomposite have also been
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Figure 16. (a) Synthesis of PEDOT:PSS passivated Te nanorods, followed
by formation of smooth nanocomposite films during solution casting and
a picture of a typical drop-cast composite film. (b) SEM image of a drop-
cast composite nanorod film. (c) TEM image showing the crystalline Te
nanorod passivated with PEDOT:PSS. Reproduced with permission.[137]
Copyright 2010, The American Chemical Society.
explored for TE applications. Fullerene is one of the most
studied organic TE materials due to its high electron
mobility,[123] low thermal conductivity (∼0.4 W/mK),[138] and
excellent thermal stability (>750 K in ambient and >1250 K in
inert environment).[139] Good thermal and mechanical prop-
erties of fullerene allow it to be processed using similar high
temperature and high pressure processes for preparing inor-
ganic TE materials. Several TE composites based on C60/
skutterudite[140,141] and C60/BiSbTe[142] have been prepared by
mechanical alloying and spark plasma sintering to investigate
their TE properties.
In the former case, ZT of the nanocomposite could be
improved under an optimized C60 doping concentration due
to κL could be reduced as a result of scattering phonons from
defects in the presence of C60 clusters between the crystal grains
of CoSb3. In the case of C60/BiSbTe nanocomposite, a thin layer
(1–2 nm) of C60 film was formed at the interfaces between the
BiSbTe grain boundaries (Figures 17a and 17b). The C60-dec-
orated grain boundaries not only provide better thermal pho-
nons blocking to reduce thermal conductivity (Figure 17c) but
also act as an interfacial p-dopant to the BiSbTe alloy crystallite
because of its good electron-accepting property.
As a result, σ of the slightly doped (0.5% C60) nanocomposite
increases due to the increase of hole carrier density (Figure
17d). This also leads to a slightly decrease in Seebeck coefficient
when compared to the undoped BiSbTe at temperature lower
than 500 K, while a higher S was observed in the nanocom-
posite at temperature >500 K (Figure 17e). Therefore, a high
ZT of 1.15 at 450 K could be obtained in the nanocomposite,
which is ∼3 times higher than that of undoped starting mate-
rial (Figure 17f). These results further suggest that appropriate
engineered organic/inorganic composite can be a new class of
material with high TE FOM.
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Figure 17. High resolution TEM images of (a) a separate nanocrystal of C60-coated BiSbTe nanocrystal and (b) an agglomerate of the C60/BiSbTe
nanocomposites. The dependencies of (c) thermal conductivity, (d) electrical conductivity, (e) Seebeck coefficient, and (d) ZT of BiSbTe/C60 nanocom-
posites with different contents of C60 on termperature. Reproduced with permission.[142]

3.3. Carbon Nanotubes and Composites
Since the first discovery by Iijima about two decades ago,[143]
carbon nanotubes (CNTs) have attracted tremendous atten-
tion due to their superior electric, thermal, and mechanical
properties,[144,145] and many potential applications of CNT
had been explored.[146] In particular, the development of CNT-
based flexible electronics[147] and energy conversion and storage
devices[148] has attracted the most attention. The potential of
using CNT as TE materials had also been widely discussed and
the TE properties of CNT in different forms including indi-
vidual CNT,[149] bundle,[150] thin film,[151] and pellet[152] have all
been studied.
In general, these studies indicated that CNT is not an ideal
material for TE applications because of its low S (< 50 μV/K
for metallic CNT and ∼260 μV/K for semiconducting CNT)[149]
and high κ (> 3000 W/mK for individual CNT and 30–75 W/mK
for random CNT network film).[153] In spite of their high σ
(2 × 105 S/cm for individual CNT[154] and ∼1 × 103- 104 S/cm
for random CNT network),[155] the optimal ZT value for CNT
is only in the range of 0.001 to 0.01, which is much lower than
that of the best available TE materials.
Several strategies have been employed to improve TE prop-
erty of CNT-based materials. One is based on the use of con-
ducting polymer/CNT composite to take advantage of the high
σ of CNT and low κ of the polymer matrix. Since CNTs only
take up a small volume fraction in the polymer matrix, it does
not really affect their high κ. The TE property of composite
prepared by in-situ polymerization of polyaniline using single-
walled CNT as template has been studied.[156] Due to strong
molecular interaction between the surface of CNT and aniline
precursor, polyaniline grows along the CNT with improved
ordering, and forms a cable-like composite structure.
The mobility of the composite was found to be higher than
that of pure polymer, leading to a significantly increased σ.
The S of the composite also increased compared to the pristine
polymer film, which may be due to the energy-filtering effect
from the nanostructured PANI wrapping around the CNTs.[157]
Thermal conductivity of the composite only increased slightly
when the doping concentration of CNT was increased, possibly
due to the efficient phonon scattering at polymer/CNT inter-
face. At the optimized CNT loading concentration, the highest
ZT (0.004 at RT) was achieved, which is ∼2 orders of magnitude
higher than that of the pristine polyaniline.
Another possible way of improving TE property is to use a
polymer-CNT composite consists of a segregated CNT network
within the polymer matrix. The σ of composite can be signifi-
cantly improved due to the enhanced interconnection of the
CNT network while the S and κ can remain relatively insensi-
tive to the CNT concentration. This idea was first demonstrated
in poly(vinyl acetate)/CNT composite film in which different
concentrations of surfactant-stabilized CNT (0 to 20 wt%)
were studied.[158] It was found that once it reached the perco-
lation threshold, the composite’s σ was significantly enhanced
to 48 S/cm at a CNT concentration of 20 wt%. The κ slightly
increased from 0.2 W/mK in pure polymer film to 0.34 W/mK
in 20 wt% CNT doped film while the S (between 40–50 μV/K)
was quite insensitive to CNT concentrations.
As a result, a ZT of 0.006 was obtained at room tempera-
ture. One of the limiting factors of ZT for the composite film
is its relatively low σ. To circumvent this problem, the original
insulating gum arabic stabilizer for CNTs was replaced by

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Figure 18. (a) Schematic illustrations of segregated PEDOT:PSS coated

CNT network formation before (left) and after (right) the drying of water-
based polymer emulsions. Reproduced with permission.[159] Copy-
right 2010, American Chemical Society. (b) Nanotubes are coated by
PEDOT:PSS particles, making nanotube-PEDOT:PSS-nanotube junctions
in the composites. The presence of the junction is believed to give rise to
exceptional thermoelectric transport properties. Reproduced with permis-
sion.[160] Copyright 2011, American Chemical Society.

PEDOT:PSS (Figure 18a).[159,160] PEDOT:PSS particles can deco-

rate the surface of the CNTs and bridged the junctions between
them, forming a more conductive contact. This has led to an
improved σ (400 S/cm) at the optimal film composition. In
addition to the improved σ, thermal transport across the CNT
junctions may also be impeded due to the mismatch of vibra-
tional spectra between CNT and PEDOT:PSS (Figure 18b).
As a result, a higher ZT of 0.02 could be achieved at room
temperature.[159]
The third approach of improving TE property of CNTs is to
alter the intrinsic charge transport and thermal transport of
CNTs through structural modification. This concept was dem-
onstrated in a recent paper where Ar plasma irradiation was
applied to bulk CNT paper to intentionally introduce structural
defects in CNTs.[161] SEM and TEM images of these irradiated
samples reveal that the structural defects formed initially at the
crystalline wall of the CNTs when they were treated with plasma
for 10 s (Figure 19). By extending the irradiation time to 30 s, it
further increased the degree of structural disorder and eventu-
ally converted the crystalline CNTs into amorphous structure. It
was found that all the values of S, σ and κ changed dramati-
cally after the plasma treatment. The value of S improved sig-
nificantly from 50 μV/K in the pristine film to 350 μV/K at 670 K
after being treated with plasma for 20 s. The results from Hall
measurements revealed that carrier density in the plasma treated
sample decreased by ∼2 orders of magnitude, which was attrib-
uted to the removal of metallic species, leading to an improved
semiconducting property of the CNT film as well as the S.
The enhanced energy filtering due to structural disorder of
the CNT film may also play a role in improving S. Conductivity
Figure 19. FESEM images of CNTs (A) before and (B-C) after Ar plasma
treatment for (B) 10s and (C) 30s. HRTEM images of CNTs (D) before
and (E-F) after Ar plasma treatment for (E) 10s and (F) 30s. The defects in
(E) are marked by the arrows. Reproduced with permission.[161] Copyright
2011, The Royal Society of Chemistry.
of the plasma treated film decreased from ∼40 S/cm to ∼10 S/cm
at 670 K due to decreased carrier density and increased electron
scattering in the disordered CNT film. The κ value was also
found to decrease significantly from ∼1 W/mK to 0.3 W/mK
due to increased phonon scattering in disordered film. It is
worth to note that such a low κ value is comparable to that of
amorphous polymers. After the plasma treatment for 20 s, the
maximum power factor and ZT were ∼120 μW/mK2 and ∼0.4
at 670 K, respectively, which are among the highest values
reported for organic-based TE materials. Recently, the same
plasma treatment method has also been successfully applied to
improve the TE properties of graphene. This demonstrates the
general applicability of this strategy for structural modifications
of organic nanomaterials.[162]
4. Summary
New TE materials development can tremendously enhance the
spreading of technology for energy conversion. In this review,
we have highlighted the recent advances in inorganic- and

562 wileyonlinelibrary.com © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Energy Mater. 2013, 3, 549–565

www.MaterialsViews.com
organic-based TE materials. While the inorganic materials have
higher ZT values, we have witnessed significant progress made
in the past few years for organic materials. In particular, inor-
ganic/organic nanocomposites have shown great promise of
further enhancing ZT. From the practical point of view, bulk
nanocomposites are more interesting than nanowires, quantum
dots, or superlattice films. The former can alleviate the cost,
scale-up, and thermal management challenges normally associ-
ated with the later.
Two main physical mechanisms contribute to the improved
TE properties of nanocomposites. On one hand, the nanoscale
grain size or inclusion enhances phonon-boundary scattering
even at elevated temperatures, which reduces lattice thermal
conductivity of the nanocomposites. On the other hand, the
energy filtering effect of charge carrier at the boundary and/or
via enhanced ionized impurity scattering increases the power
factor.
Majority of the recent ZT improvements originated from
the lattice thermal conductivity even with somewhat minor
power factor deterioration. Power factors are usually difficult
to increase, especially for high ZT materials. Recent study
on conducting polymer/Bi2Te3 nanowire nanocomposites is
rather encouraging. An interfacial potential barrier of less than
0.10 eV could be engineered at the poly(3-hexylthiophene)/
Bi2Te3 boundary, leading to a factor of greater than 3 power factor
enhancement.[130] This increase was attributed to the enhanced
carrier energy filtering due to increased scattering parameter
(λ in Equation (4)) from the presence of the organic/inorganic
interfaces. It is conceivable that such interfacial energetics
design should be applicable to inorganic/inorganics nanocom-
posites that could be used for higher temperature applications.
Acknowledgements
The authors would like to thank the National Science Foundation (NSF)
for its support on this project through the GOALI program (award
number 1130606). J. Yang thanks the Kyocera Corporation for the
endowed support. A. K.Y. Jen thanks the Boeing-Johnson Foundation for
financial support.
Received: July 10, 2012
Revised: September 3, 2012
Published online: February 13, 2013
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