Review

pubs.acs.org/CR

Rationally Designing High-Performance Bulk Thermoelectric

Materials
Gangjian Tan,† Li-Dong Zhao,*,‡ and Mercouri G. Kanatzidis*,†
†
Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States
‡
School of Materials Science and Engineering, Beihang University, Beijing 100191, China

ABSTRACT: There has been a renaissance of interest in exploring highly efficient

thermoelectric materials as a possible route to address the worldwide energy generation,
utilization, and management. This review describes the recent advances in designing
high-performance bulk thermoelectric materials. We begin with the fundamental
stratagem of achieving the greatest thermoelectric figure of merit ZT of a given material
by carrier concentration engineering, including Fermi level regulation and optimum
carrier density stabilization. We proceed to discuss ways of maximizing ZT at a constant
doping level, such as increase of band degeneracy (crystal structure symmetry, band
convergence), enhancement of band effective mass (resonant levels, band flattening),
improvement of carrier mobility (modulation doping, texturing), and decrease of lattice
thermal conductivity (synergistic alloying, second-phase nanostructuring, mesostructur-
ing, and all-length-scale hierarchical architectures). We then highlight the decoupling of
the electron and phonon transport through coherent interface, matrix/precipitate electronic bands alignment, and
compositionally alloyed nanostructures. Finally, recent discoveries of new compounds with intrinsically low thermal conductivity
are summarized, where SnSe, BiCuSeO, MgAgSb, complex copper and bismuth chalcogenides, pnicogen-group chalcogenides
with lone-pair electrons, and tetrahedrites are given particular emphasis. Future possible strategies for further enhancing ZT are
considered at the end of this review.

CONTENTS 5.6. Chalcoantimonates with Lone-Pair Electrons 12139

5.7. Tetrahedrites 12141
1. Introduction 12123 6. Summary and Outlook 12141
2. Basic Stratagem of Optimizing ZT: Carrier Author Information 12142
Concentration Engineering 12124 Corresponding Authors 12142
3. Means of Increasing Maximum ZT 12126 Notes 12142
3.1. Enhancement of Carrier Effective Mass m* 12126 Biographies 12142
3.1.1. Increasing the Number of Band Extrema Acknowledgments 12142
NV 12126 References 12142
3.1.2. Increase of Carrier Effective Mass mb* 12127
3.2. Modulation Doping and Carrier Mobility
Improvement 12128
3.3. Reducing Lattice Thermal Conductivity 12129 1. INTRODUCTION
3.3.1. Atomic Scale: Synergistic Alloying 12129 With more than two-thirds of the worldwide utilized energy
3.2.2. Nanoscale: Nanostructuring with Sec- being wasted as heat releasing to the atmosphere in vain, it is of
ond Phases 12130 great economic and environmental benefit to capture this
3.3.3. Mesoscale Structuring 12130 largely untapped waste heat to generate emission-free renew-
3.3.4. All-Scale Hierarchical Architectures 12131 able power. Thermoelectric materials that are capable of
4. Decoupling of Electron and Phonon Transport 12131 directly and reversibly converting heat into electricity have thus
4.1. Strained Endotaxial Nanostructuring 12131 drawn increasing attention over the past several decades. The
4.2. Matrix/Precipitate Band Alignment 12132 key of promoting this promising power generation technology
4.3. Compositionally Alloyed Nanostructures 12133 into massive application is to increase the low conversion
5. Discoveries of New Thermoelectric Materials with efficiency of current thermoelectric materials, which is
Intrinsically Low Thermal Conductivity 12133 technically evaluated by the dimensionless figure of merit ZT
5.1. Layered SnSe 12134 = S2σT/κ. A good thermoelectric material should have a large
5.2. BiCuSeO Oxyselenides 12136 Seebeck coefficient (S) that is usually present in semi-
5.3. Half-Heusler MgAgSb 12137
5.4. Copper Chalcogenides 12138
Received: April 21, 2016
5.5. Complex Bismuth Chalcogenides 12139
Published: August 31, 2016

© 2016 American Chemical Society 12123 DOI: 10.1021/acs.chemrev.6b00255

Chem. Rev. 2016, 116, 12123−12149
Chemical Reviews
conductors, high electrical conductivity (σ) just like metals, and
in the meantime poor thermal conductivity (κ) as in glasses. It
is knotty to combine all of these features in a single material,
enabling its high performance. Experimentally, to improve ZT,
one can increase the numerator S2σ (also known as power
factor) and/or decrease the denominator κ (thermal con-
ductivity) by rational band structure and microstructure
designs.1−7
Since the historic discoveries of thermoelectric phenomena
by Seebeck and Peltier in the first half of the 19th century,
many materials have been explored and considered useful to
generate thermoelectricity, including metals,8−11 ceramics,12−14
and ultimately semiconductors.15−17 It needs to be emphasized
that almost all these materials were initially obtained empirically
through countless attempts based on personal experience.
Therefore, the growth of the thermoelectric community was
very slow in the beginning until the 1950s, the decade when the
basic science of thermoelectric effects was established and
heavily doped semiconductors were widely recognized as
excellent thermoelectric materials.15−18 Since then the field of
thermoelectrics advanced rapidly, especially in the past two
decades, relying on the development of new concepts, better
intuitive thinking and theoretical ideas relating to size
effects,1−5,19−22 and band structuring engineering.3,23−28
Figure 1 shows the primary milestones achieved for ZT
values of bulk materials over the last two decades as a function
Figure 1. Current state-of-the-art bulk thermoelectric materials: the
thermoelectric figure-of-merit ZT as a function of temperature and
year illustrating important milestones. Green cylinders represent the p-
type materials, while red cylinders represent the n-type ones.
CsBi4Te6,29 BiSbTe,2 AgPbmSbTe2+m,1 Ba8Ga16Ge30,30 Tl−PbTe,23
In4Se3,31 CuxBiTeSe,32 (BaLaYb)xCo4Sb12,33 MgAgSb,34 BiSbTe+Te
arrays,22 PbTe−SrTe,4 DDyFe3CoSb12,35 Mg2Si0.3Sn0.7,24 Cu2−xSe,36
Na2+xGa2+xSn4−x,37 GeTe−Bi2Te3,38 Pb(Te,Se,S),39 PbS−CdS,27
SnSe,40 Cu2−xS,41 PbTe−PbS,42 SnTe−CdS,43 and Pb1−xSbxSe.44
of both year and temperature. Great achievements have been
achieved with both n- and p-type materials with the greatest
ZTs around or above 2, especially since the year 2010.4,39,40,42
Traditional thermoelectric materials, namely, bismuth tellur-
ide2,22 and lead chalcogenides,1,3,4,23,25,27,39,42,44 remain the top
performing ones in their respective working temperature region
and attract strong attention. On the other hand, because of
concerns of the scarceness of tellurium and the perceived
toxicity of lead in lead chalcogenides, researchers also explore
the possibility of Te- and Pb-free compounds, among which
MgAgSb,34 skutterudites,33,35 and copper and tin chalcoge-
nides36,40,41,43 appear as most promising. Particularly, single-
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crystalline SnSe, a simple binary compound containing no toxic
or scarce elements, displays an excitingly record high ZT of
∼2.6 at 923 K along the b axis of the room-temperature
orthorhombic unit cell.40 This can be achieved because of the
giant anharmonic and anisotropic bonding of SnSe which gives
rise to an extremely low thermal conductivity.40 Thus, the
search for new compounds with intriguing physical properties is
a necessary activity to achieve high thermoelectric performance
in addition to optimizing the known systems.
Although in the past decade breakthroughs have been
constantly made in the thermoelectric field, systematic and in-
depth analysis and new perspectives on the applied approaches
and concepts are valuable. There were previously a few nice
introductory reviews on thermoelectric materials, which could
be a nice starting point for the readers who are interested in
thermoelectrics. Typical examples are summarized by Wood,45
Disalvo,46 Snyder,47 and Kanatzidis.48 Interested readers are
also encouraged to refer to some outstanding review articles
that focus on some topics, e.g., nanostructuring,20,49,50 band
structure engineering,26,51 or nanopolycrystalline compo-
sites,52,53 and some others that focus on several specific
materials, such as clathrates,54 Zintl phase compounds,55
oxides,56,57 organic materials,58,59 and others.47,60−62 A recent
review discusses issues of charge and phonon transport in
thermoelectric compounds from the chemical bonding point of
view.63 This review aims to summarize the most recent state-of-
the-art approaches of designing high-performance bulk thermo-
electric materials which are most likely to enable the devices for
large-scale power generation application. It covers all aspects,
from improving the electrical properties in the manner of band
structure and microstructure manipulations to decreasing the
thermal conductivity by composition and microstructure
designs and to decoupling the electron and phonon transport
through matrix/precipitates band alignment and composition-
ally alloyed nanostructures. The advances in finding new
compounds with intrinsically low thermal conductivity are also
highlighted. Future potential strategies universally applicable to
all compounds aimed at enhancing the performance are
discussed. They can be a comprehensive guide to designing
and exploring advanced bulk thermoelectric materials.
2. BASIC STRATAGEM OF OPTIMIZING ZT: CARRIER
CONCENTRATION ENGINEERING
The fundamental challenge of designing high-ZT thermo-
electric materials stems from the strong correlation of S, σ, and
κ through carrier concentration n which can be adjusted by
controlling the doping level. For a degenerated semiconductor
with parabolic band dispersion, assuming that dopant does not
change the scattering or band structure significantly, S is given
by64
8π 2kB2 ⎛ π ⎞2/3
S= m*T ⎜ ⎟
3eh 2 ⎝ 3n ⎠ (1)
where kB is the Boltzmann constant, e the electron charge, h the
Plank constant, and m* the density of states effective mass of
carriers. Apparently, high S is usually found in low-n
semiconductors or insulators, and with increasing n, S drops
rapidly, Figure 2a. On the contrary, to ensure a large σ, n should
be as high as possible, see eq 2 and Figure 2a
σ = neμ (2)
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Figure 2. (a) Schematic diagram showing how ZT and its related
parameters (electrical conductivity σ, Seebeck coefficient S, power
factor S2σ, electrical thermal conductivity κele, lattice thermal
conductivity κlat, and total thermal conductivity κ) change as a
function of carrier concentration n. (b) Strategies for stabilizing the
optimal carrier concentration (n*, denoted by the red line, usually
shows a (T)3/2 dependence66). For most conventional dopants, the
resultant carrier concentration (denoted by orange dotted line) is
almost temperature independent, functionally graded doping67−69
(green lines) by use of samples with dissimilar n, and use of
temperature-dependent-solubility dopant,71,72 namely, n has a strong
temperature dependence (purple line). (c) Comparison of different
doping methods: (1) conventional doping, (2) graded doping, and (3)
T-dependent doping. (d) Enhancement of ZT values over a broad
temperature range through stabilizing n* in comparison to the
conventional doping approach.69,71,75
where μ is the carrier mobility. Only within the proper carrier
concentration range (e.g., 1019−1020 cm−3 for most semi-
conductors47) can the power factors be maximized by balancing
S and σ.
The thermal conductivity κ comprises two major compo-
nents: the electronic contribution κele and the lattice
contribution κlat (among all ZT-related physical parameters,
κlat is the only one with little dependence on n (Figure 2a) and
potentially can be minimized to the amorphous limit through
independent crystal structure and/or microstructure design4,55)
κ = κele + κlat
(3)
and κele is influenced by n through the Wiedemann−Franz
relation65
κele = LσT = LneμT
(4)
where L is the Lorenz number. Equation 4 links the electrical to
thermal transport and makes the optimization of ZT even
tougher: there is a trade-off between high σ and low κ (κele),
Figure 2a. Nonetheless, as shown in Figure 2a, one can always
achieve a maximum ZT at a given temperature by finely tuning
n to an optimal level using an aliovalent substitution approach.
However, the optimal carrier concentration (n*) of a
thermoelectric semiconductor is not constant at all temper-
atures and usually increases rapidly with rising temperature,
roughly obeying the power law of (T)3/2,66 as shown by the red
line in Figure 2b. In the case of conventional doping, the carrier
concentrations are generally irrelevant to temperature, see the
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orange line in Figure 2b and 2c. The consequence of this is that
the theoretically maximum performance cannot be fully realized
at every working temperature. One way to deal with this issue is
to use functionally graded doping67−69 by integrating two or
multiple segments with dissimilar n, see green lines in Figures
2b and 3c. One common approach developed in the late 2000s
Figure 3. (a) Band convergence effect by forming solid solution
A1−xBxC between AC and BC: evolution of band structure with
increasing doping fraction; Eg and ΔEL−Σ represent the band gap and
energy separation between L and Σ bands, respectively. (b) Seebeck
coefficient, (c) power factor, and (d) ZT values as a function of both
temperature and doping fraction of Sn1−xMnxTe.89 The temperature-
dependent Seebeck coefficient of SnTe-3%CdTe92 is included in b for
comparison. (Inset of c) Reduction of lattice thermal conductivity with
increasing Mn doping concentration.89
of preparing such a graded material is the so-called spark
plasma sintering or hot pressing a compacted stack of powder
layers, each of which has different carrier concentrations.67,69
However, after extended duration in service the initial carrier
concentration gradient in the graded material may fade or
vanish due to the diffusion-induced homogenization effect,
thereby deteriorating the conversion efficiency.69,70
Alternatively, by making use of the temperature-dependent
solubility71,72 of some specific dopants (Figure 2c), one can
create a gradient of n within a single material controlled only by
temperature and its gradient (see purple line in Figure 2b and
2c). A well-known example is that of Cu, Ag, and excess Pb,
which have negligible solubility within PbTe around room
temperature but are highly soluble at elevated temper-
atures.73,74 This temperature-dependent doping is reversible
in the heating−cooling process and gets rid of the diffusion
problem with graded doping, making it a better candidate for
actual application.4,71
Figure 2d compares the temperature-dependent ZT values of
n-type PbTe using different doping methods. The green and
orange dotted lines represent A and B materials of conventional
n-type PbTe with n = 5 × 1018 and 3 × 1018 cm−3, respectively,
and the dotted purple line is for the graded doping by
integrating the two components.69 A has small n and thus high
ZT at low temperatures, while B with larger n has significantly
higher ZT at high temperatures. Graded doping makes the ZT
fall between A and B but can achieve a much larger average ZT
in the entire working temperature range. The solid black line
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Chemical Reviews
shows the theoretically optimal ZT for n-type PbTe.71
Conventional doping approaches, such as by heavy La doping75
in PbTe (solid navy line), can make the maximum ZT approach
the optimal value around 750 K but cannot achieve high
performance at all temperatures. The temperature-dependent
solubility limit of Ag in the PbTe+Ag2Te composite (T-
dependent doping, solid green line) enables an increase in n
with increasing T and pushes ZT values close to the optimal
levels over the entire temperature range.
The T-dependent doping approach has also been successfully
applied in many other systems including p-type Na-doped
PbTe.4,42,72,76 It was demonstrated that the Na-rich precipitates
residing at the grain boundaries at low temperature are
redissolved into the PbTe matrix at T > 600 K.4,42 This gives
rise to the enhancement of hole density, contributing to the
increase of electrical conductivity and power factor and
suppression of bipolar conduction at elevated temperature
achieving superior performance. The modifications to the
conventional doping method to include temperature-dependent
doping behavior are helpful to acquire larger average ZT values
which are especially important in technological applications.
3. MEANS OF INCREASING MAXIMUM ZT
Maximum performance of a given thermoelectric material is
generally achieved by carrier concentration optimization, as we
elaborated above. However, to increase the maximum ZT to
much higher levels, one needs to carefully tailor the electronic
structures and microstructures. Previous studies indicate that
the dimensionless merit factor (β) of thermoelectric materials
can be characterized by77,78
U ⎛ T ⎞
5/2
⎜ ⎟
β=9
κlat ⎝ 300 ⎠ (5)
2 −1 −1
where U is the weighted mobility (in cm V s , a measure of
the electrical properties) that can be written as79
U = (m*)3/2 μ (6)
In eq 6, m* is the effective mass of carriers (in me, me is the free
electron mass) and relates to the band effective mass mb*
through the number of equivalent degenerated valleys of the
band structure (NV)26,80
m* = (NV )2/3 mb* (7)
Thus, to increase the maximum ZT, one needs to maximize NV,
mb*, and μ and minimize κlat concurrently to achieve higher S
and σ but lower κ at a constant n (according to eqs 1−4).
Below we discuss the possible approaches.
3.1. Enhancement of Carrier Effective Mass m*
3.1.1. Increasing the Number of Band Extrema NV. Nv
is closely related to the crystal structure symmetry and can be
large when the crystal structures are highly symmetric. For
example, PbTe with its cubic rocksalt structure has NV of 4 and
12 at the L and Σ points of the valence band, respectively.46,81
Other good thermoelectric materials, such as SiGe alloys,
CoSb3, Mg2Si, and half-Heusler alloy, also feature NV > 1.26
Currently, strategies on how to increase the asymmetry-
related Nv are in their infancy. One illuminating attempt was
recently carried out on tetragonal chalcopyrite compounds.82
By mixing two types of chalcopyrite compounds (c/2a > 1 for
one but <1 for the other; a and c represent the lattice
parameters, c > a) in a proper ratio to form solid solutions, the
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noncubic lattice of either of the chalcopyrite compounds can be
distorted to be cubic-like (c = 2a) on average. This
reconstructed pseudocubic structure was perceived to be
responsible for the lower energy-splitting parameter (or larger
NV) and higher performance obtained in the solid solutions.
More work is needed, however, in order to better understand
just how much of the net ZT enhancement comes from the
increase of NV since lattice thermal conductivity reduction
through forming the solid solution is also contributing.82
Another attractive way to increase the effective NV is to
converge different bands in the Brillouin zone within a few kBT
in energy of each other. For example, both experimental and
theoretical investigations suggest the presence of two valence
bands in lead chalcogenides: one at the L point with NV = 4 and
the other at the Σ point of the Brillouin zone with a much
larger NV of 12.81 Normally, the two bands are separated by an
energy ΔEL−Σ that is sufficiently large to make the Σ band
irreverent to charge transport, Figure 3a. However, upon
proper alloying with specific elements (for example, Mg,83
Cd,84 Sr,85 or Mn86 in PbTe; Sr in PbSe87), ΔEL−Σ can be
significantly lowered, and the two valence bands become
converged gradually. In that case, the effective NV becomes
larger than 12, and higher performance can be achieved.25,26,87
Likewise, notable conduction band convergence was demon-
strated to be effective in enhancing the n-type thermoelectric
performance of Mg2Si by alloying with Sn at the Si site.24 We
note that the mobility of carriers is nominally unaffected by NV,
but there may be some reduction because of intervalley
scattering.25
Recently, such a band convergence concept has also been
extended to p-type SnTe,43,88−92 which is an analogue of lead
chalcogenides but is supposed to be more environmental
friendly. Pristine SnTe is not a good thermoelectric material
because of high lattice thermal conductivity and the
unavailability of its Σ valence band. Specifically, ΔEL−Σ is
∼0.35 eV for SnTe at 300 K,93 much larger than in PbTe
(∼0.17 eV)94 or PbSe (∼0.24 eV).95 This means that a
considerably larger amount of dopant is needed to produce the
same band convergence effect as in PbTe or PbSe, because the
doping-induced band convergence is dependent on the amount
of dopant,96 Figure 3a. Cd43,92 and Hg90 are good alloying
elements from the perspective of decreasing ΔEL−Σ in SnTe.
However, because of their low solubility limit (∼3 mol %),90,92
the resultant ΔEL−Σ is still too high to reach the level of PbTe.
For example, 3 mol % CdTe-alloyed SnTe92 has the highest
Seebeck coefficient of ∼200 μV/K at ∼900 K, which is
significantly larger than that of pristine SnTe but is far below
that of p-type PbTe83 at the same hole concentration, Figure
3b. Most recently, Mn was explored as a valence band
convergence producer in SnTe with a high solubility of >9 mol
%.89,97,98 This gives rise to a much lower ΔEL−Σ that is
comparable to that of PbTe.89 Correspondingly, the Seebeck
coefficients and power factors of Sn1−xMnxTe are remarkably
improved with increasing Mn doping fraction,89 Figure 3b and
3c. Notably, the 12 mol % Mn-doped SnTe89 displays the
highest Seebeck coefficients (∼80 and ∼230 μV/K at 300 and
900 K, respectively), similar to PbTe83 with comparable hole
densities, Figure 3b. Moreover, the higher doping fraction of
Mn also facilitates the decrease of lattice thermal conductivity
as a result of stronger point defect scattering,89 inset of Figure
3c. Concurrently, ZTs of SnTe are steadily improved upon Mn
doping with a highest value approaching 1.3 at 900 K,89 a 120%
increase over pristine SnTe. The above examples demonstrate
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Chemical Reviews
the feasibility of turning poor thermoelectric materials into
excellent ones by energetically converging multiple bands.
3.1.2. Increase of Carrier Effective Mass mb*. Physically,
the effective mass mb* in a band is related to the curvature of
the bands and can be modified by distorting the band. This can
increase the density of states in the vicinity of Fermi level.23,51
Two commonly adopted approaches of enhancing mb* include
band flattening99,100 and resonant levels23,91,101,102 through
chemical doping, Figure 4a. It should be emphasized that in
Figure 4. (a) Schematic representation of the density of states of a
single valence band (blue line) contrasted to that of band flattening
(purple line) and the introduction of resonant states (red line). (b)
Power factors as a function of carrier concentrations for various of
compounds (n-type PbTe, ZrNiSn, CoSb3 and p-type NbFeSb) with
different effective masses (m*) at 800 K.107 (c) Seebeck coefficient,
and (d) power factor as a function of temperature for SnTe with
resonance levels by In doping and/or valence band convergence by
alloying with Cd.43
most cases the increase of mb* will result in the decrease of
carrier mobility and through it the electrical conductivity,
according to the relationship46
eτ
μ=
ml* (8)
where ml* is the inertial mass along the transport direction
(and equal to mb* for an isotropic band) and τ is the scattering
time which decreases with increasing mb* so long as the carriers
are scattered predominately by phonons.26
Band flattening effects can be achieved through the adoption
of dopants containing highly localized orbitals which can
decrease orbital overlap. For instance, both theoretical and
experimental studies suggest that La103−106 or Nd103,106
substitution for Sr significantly flattens the conduction band
of SrTiO3 perovskites for largely improved density of states
effective mass of electrons, thereby leading to higher power
factors and thermoelectric figure of merits. Likewise, in La-
doped PbTe,99,100 because of the hybridization between La f
states (or d states if f states are fully localized) and Pb p states,
the conduction band at the L point can be affected,
contributing to the increase of mb* by band flattening.100 In
comparison, iodine-doped n-type PbTe shows negligible
changes in the conduction band structure, consistent with the
rather broad I d states.100 For equal carrier concentrations (n =
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1.8 × 1019 cm−3), the La-doped PbTe displays lower ZT value
than that of I-doped samples.99 This is because despite the
former’s larger mb* and higher Seebeck coefficient, there is a
decline of μ leading to a net decrease of power factor.
Nonetheless, at a higher doping level of n, La-doped PbTe
samples can have comparable or even better power factors than
I-doped PbTe samples, as demonstrated by both experimental
results and theoretical predictions.99
Indeed, to make best use of the benefits of larger mb*
through band flattening for power factor enhancement it
generally requires a much higher optimal n to reach the same
Fermi level as the one with smaller mb*. Figure 4b plots the
power factor as a function of carrier concentration at 800 K for
several state-of-the-art thermoelectric materials with different
effective masses.107 It is clearly evident that the maximum
power factor values of these heavy bands compounds (e.g., n-
type CoSb3) are significantly higher than those with small mb*
(for example, n-type PbTe). Moreover, the optimal n increases
systematically with increasing mb*.
Band flattening can increase not only mb* but also the band
gap Eg, according to the Kane-band model.108 This model is
widely accepted to describe the band dispersion of most
excellent thermoelectric materials (for example, CoSb3109 and
PbTe71,75)
ℏ2k 2 ⎛ E⎞
= E⎜⎜1 + ⎟⎟
2mb* ⎝ Eg ⎠ (9)
In eq 9, ℏ is the reduced Plank’s constant, k the crystal
momentum, and E the energy of electron states. Intuitively, this
additional band gap enlargement effect by band flattening can
help to suppress the detrimental effect of bipolar diffusion on
the thermoelectric properties.83,92
The concept of resonant levels was first proposed in metals
in 1950s.110,111 Resonance levels originate from the coupling
between electrons of a dilute impurity with those of the
conduction or the valence band of the host solid. This creates
excess density of states near the resonant energy and can give
rise to improved mb* and enhanced Seebeck coefficient if the
Fermi level can be brought close in energy.51 However,
resonant levels are generally effective at low temperature, and
their effect tends to diminish at high temperatures where the
relaxation time of acoustic phonon scattering is much shorter
than that of resonant impurity scattering.43,51
The most well-known examples of resonant levels are
associated with the group-III impurities in IV−VI semi-
conductors. For example, Al was reported to form resonant
levels in the conduction band of PbSe,102 while In43,91 and Tl23
create resonant levels in the valence bands of SnTe and PbTe,
respectively. In addition to IV−VI semiconductors, resonant
levels are also observed in Sn-doped Bi2Te3.101
Recently, the synergy of resonant levels and band
convergence to strongly increase performance has been
demonstrated in In- and Cd-codoped SnTe,43 Figure 4c and
4d. In forms resonant levels in the valence band of SnTe and
therefore strongly improved the Seebeck coefficient and power
factors of SnTe below 500 K. However, with increasing
temperature, this enhancement becomes less significant because
of the diminished resonant scattering at elevated temperatures.
On the other hand, Cd substitution92 creates valence band
convergence in SnTe that works most efficiently at higher
temperatures where two valence bands approach each other,
enabling a clear enhancement of the Seebeck coefficient, Figure
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4c. The introduction of Cd does not extinguish the favorable

resonance effect of In below 500 K but improves the Seebeck
coefficients and power factors over the entire temperature
range. We believe this codoping concept can improve the
average ZT over a broad temperature range for many
thermoelectric materials.
In summary, as indicated by eq 7, the effective mass (m*) can
be enhanced by increasing the valley number (NV) or by
increasing local DOS effective mass (mb*) through distorting
DOS. It is well known that the carrier mobility is inversely
proportional to the effective mass, but the carrier mobility will
be less deteriorated by increasing valley number (NV) than by
increasing the local effective mass (mb*).86
3.2. Modulation Doping and Carrier Mobility Improvement
Most state-of-the-art thermoelectric materials are heavily doped
semiconductors with the carrier concentrations on the order of
1019−1021 cm−3, Figure 2a. The high population of free carriers
in these heavily doped semiconductors leads to a decrease of
carrier mobility with respect to the lightly doped or undoped
ones, because of the increased ionized impurity scattering. For
example, Hilsum112 found that at room temperature, the
mobility is inversely proportional to [1 + (nD/1017)1/2] for a
number of important semiconductors, where nD is the donor
concentration (in cm−3).
Three-dimensional (3D) modulation doping has been
recently demonstrated to be effective in increasing the ZT
values of several important thermoelectric materials by carrier Figure 5. Schematic representation of (a) nondoped semiconductor,
mobility enhancement.113−116 Modulation-doped samples (b) heavily doped semiconductor where dopants are uniformly
(Figure 5b) actually are two-phase composites made of dispersed in the host matrix, and (c) modulation doping where two
undoped (Figure 5a) and heavily doped (Figure 5c) counter- types of grains consisting of nondoped and heavily doped semi-
parts. The undoped pristine sample has low carrier conductors are spatially separated. Red arrows show how carriers are
concentration but high carrier mobilities, while the uniformly scattered when mobilizing across the material. Fermi level positions in
and heavily doped sample has high carrier concentrations but undoped, uniformly doped, and modulation-doped semiconductors:
low carrier mobilities. The Fermi level of the undoped sample (d) n-type doping and (e) p-type doping. The Fermi level imbalance
between the undoped and the heavily doped grains prompts the
usually locates at the middle of the energy gap and would move
carriers to diffuse from the latter to the former. (f) Comparison of
deep into the conduction band (n-type doping, Figure 5d) or power factors of p-type SiGe alloys113 and p-type BiCuSeO116 in the
the valence band (p-type doping, Figure 5e) in the case of cases of uniform doping and modulation doping, respectively. At
heavily doped sample. Because of the Fermi level imbalance comparable carrier concentration, materials with modulation doping
between the undoped and the heavily doped phases, the carriers clearly show much higher power factors than those by uniform doping,
in the modulation-doped sample spill over from the heavily due to the much larger carrier mobilities.
doped region to the undoped region (Figure 5d and 5e). This
process results in carrier mobility enhancements relative to materials with anisotropic structures. In these anisotropic
uniform doping because of avoidance of ionized impurity compounds, carrier mobility may be higher in certain
scattering. crystallographic directions. In polycrystalline sample, the
The spatial separation of carriers and impurity scattering random orientation of grains weakens the anisotropy of carrier
centers in 3D modulation doping enables higher carrier transport and the carrier mobility is a statistical mean value
mobility without deteriorating the Seebeck coefficient, Figure along different crystallographic directions. To take advantage of
5b. For example, under the same carrier concentrations, the 3D the anisotropy and maximize carrier mobilities, it is desirable to
modulation-doped p-type SiGe alloys113 and BiCuSeO produce grains that orient along a certain direction, so as to
compounds116 possess considerably larger carrier mobilities approach the character of the single crystals. For instance,
and power factors than the uniformly doped materials, Figure single crystals of SnSe40 feature a high carrier mobility of ∼250
5f. Recently, this 3D modulation doping approach has also been cm2 V−1 s−1 at 300 K, along the b axis of the orthorhombic unit
successfully applied to several other bulk thermoelectric cell, which is about 5 times larger than in its polycrystalline119
systems (e.g., p-type ZnSb117 and n-type FeSb2118) with largely form with equal hole concentrations. The significantly higher
improved thermoelectric performance. mobility of SnSe single crystal is the main reason for its much
One concern of modulation-doped structures is that they superior thermoelectric performance as compared with its
may functionally fail when operating at high temperature for polycrystalline samples. However, as single-crystal growth is
long periods of time, due to element diffusion and highly dependent on the equipment and is time consuming,
thermodynamic equilibration. Therefore, modulation doping simpler methods to realize highly oriented polycrystalline
could be more promising at relatively lower temperatures. samples by hot deformation (thermoforging) technique are
Aside from modulation doping, texturing could be another being developed.120 Such methods have been extensively
feasible approach to increase the carrier mobility, especially for utilized to improve the thermoelectric performance of many
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layer structured materials; for example, Bi 2 Te 3 , 121,122
Ca3Co4O9,123,124 and BiCuSeO.116 Texturing is not sensitive
to temperature, so it can be applied to high-temperature
thermoelectric materials.
3.3. Reducing Lattice Thermal Conductivity
In solids, the interaction between atoms creates displacements
from their equilibrium positions leading to a set of vibrational
waves with various wavelengths, so-called phonons. These
phonons are heat carriers that propagate through the lattice,
contributing to the lattice thermal conductivity κlat. At crystal
defects (e.g., point defects, dislocations, interfaces, precipitates,
etc.), phonon waves can be scattered, giving rise to additional
thermal resistance and a reduction of κlat. For example, atomic
point defects formed by elemental substitution and nanoscaled
precipitates created by second-phase nucleation and growth can
significantly scatter the short- and medium-wavelength
phonons, respectively. Mesoscaled grains can also scatter
phonons but are more effective for long-wavelength pho-
nons.4,125 Below we will elaborate on these mechanisms.
3.3.1. Atomic Scale: Synergistic Alloying. Introduction
of lattice imperfections (point defects, at the length scale of
angstroms) in the host lattice (by doping or alloying) is a well-
established approach of decreasing the lattice thermal
conductivity. According to the thermal conductivity model
developed by Klemens126 and Callaway,127,128 this reduction of
κlat is a result of combination of mass contrast and strain field
fluctuations. The degree of reduction can be evaluated by the
scattering parameter (Γ) that is written as129
⎡ ⎛ adisorder − a pure ⎞2 ⎤
⎢ ⎛ ΔM ⎞2
Γ = x(1 − x) ⎜ ⎟ + ε⎜
⎜ ⎟⎟ ⎥
⎢⎝ M ⎠ ⎝ a ⎠ ⎥⎦
⎣ pure
(10)
where x is the doping fraction, ΔM/M is the rate of change of
atomic mass, adisorder and apure represent the lattice constants of
disordered and pure alloys, respectively, and ε is an elastic
properties related adjusting parameter.129
From eq 10, one can conclude that to maximize Γ and
achieve the lowest κlat it is necessary to have (1) a high doping
fraction x, (2) a large mass difference between the dopant and
the host element (ΔM/M) creating disorder in the lattice, and
(3) a significant lattice mismatch between the disordered phase
and the host phase (adisorder/apure). Requirements 1 and 3 can be
conflicting in many cases, since large lattice and size mismatch
generally renders the dopant insoluble.
Figures 6a−c schematically represent the typical doping
approaches frequently used in thermoelectric materials
research, namely, single-element doping, cross-substitution,
and formation of lattice vacancies. In the case of single doping,
the dopant could be either isovalent with the host element to
generate lattice disorder or aliovalent to control the carrier
concentration, Figure 6a. However, due to charge imbalance,
singly aliovalent doping is limited by the low doping fraction
possible which prevents the further decrease of κlat. To promote
a large solubility limit of aliovalent elements, cross-substitution
is used.
Cross substitution means replacing one or more of the host
elements by pairs from other groups of the Periodic Table
while keeping the overall valence electron counts constant,
Figure 6b. For example, in PbTe, when the divalent Pb is
simultaneously substituted by half monovalent Ag and half
trivalent Sb, one could obtain AgPbmSbTe2+m, also known as
LAST.1 In CoSb3, one Co3+ and one Sb1− can be replaced by
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Figure 6. Schematic representation of various types of point defects:
(a) single doping, (b) cross-substitution, and (c) lattice vacancy
formation. (d) Comparison of lattice thermal conductivities as a
function of temperature for SnTe with different point defects.43,140,141
one Fe2+ and one Te2− concurrently, thus forming an
isoelectronic compound FeSb2Te.130−132 Cross-substituted
compound can have a significantly larger solubility limit of
dopants than by single doping, and one could expect a much
lower κlat, according to eq 10. It should be noted that cross-
substitution not only considerably impacts the phonon
transport but may modify the electronic structure (band gap
mostly),131,133 providing other avenues to tune the thermo-
electric properties of the host material. Because only when the
two aliovalent elements are present together in a specific ratio
do they enter the matrix in larger amounts (than each alone
can) we refer to this effect as synergistic alloying.
In addition to a high doping fraction, increasing the atomic
mass contrast between the guest and the host atoms can lead to
low lattice thermal conductivity. However, the maximum mass
contrast (ΔM/M = 1) seems unattainable by conventional
doping but is possible when the guest or host atom represents a
disordered vacancy, Figure 6c. For instance, in partially filled
skutterudites FyCo4Sb12 (F and y represent the filler atom and
filling fraction, respectively; y < 1), the lattice thermal
conductivity is unexpectedly low, which has been rationally
explained by the strong point defect scattering between the
filler F in fully filled FCo4Sb12 and the structural vacancy □ in
unfilled □Co4Sb12, a 100% mass difference.134 Other examples
include clathrate compounds135 with void cages, La3−δTe4
materials136,137 with intrinsically high concentration of cationic
vacancies, and InSb/GeTe/SnTe−In2Te3 solid solutions138−140
(note: one-third of the cationic sites are vacant in In2Te3)
where very low lattice thermal conductivity is observed.
Figure 6d compares the temperature-dependent lattice
thermal conductivities of SnTe with different types of point
defects: (A) single In doping,43 (B) cross-substitution by Ag
and Bi,141 and (C) formation of lattice vacancies by
introduction of In2Te3.140 It is clear to see that cross-
substitution and vacancy formation are superior ways of
frustrating the phonon propagation in SnTe compared to
single doping, as we discussed above. This synergistic alloying
approach to thermal conductivity reduction is applicable to
most kinds of thermoelectric materials.
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3.2.2. Nanoscale: Nanostructuring with Second
Phases. Nanoscaled defects in crystals help scatter the
phonons with wavelengths on the nanometer scale. To make
this scattering effective, the geometric length of the nanoscaled
defects should be small enough, typically on the order of several
to dozens of nanometers, and the nanostructures should be
uniformly distributed for maximal interface density over a large
material volume.3,4,142
There are several approaches to achieving nanoscale
inhomogeneity, including ex-situ additions of guest phase by
mechanical or chemical mixing143,144 and in-situ second-phase
precipitation through thermodynamically/kinetically driven
processes.1,3,4,145,146 While both have been reported to create
nanostructures in thermoelectric materials, the latter is more
favorable for charge transport because they can afford better
dispersion and yield coherent interfaces between precipitate
and matrix.3,4
Nucleation and growth of a second phase is the most
common in-situ approach of producing nanostructures in bulk
crystals,147 and its mechanism is schematically presented in
Figure 7a. This works well when the second phase is completely
Figure 7. (a) Schematic ternary diagram, which indicates a strong
temperature-dependent solubility of the second-phase B within the
matrix A. (b) Typical TEM image that shows B nanostructures
embedding in the A matrix, as grown by the nucleation and growth
mechanism. (c) Comparison of lattice thermal conductivities between
pristine and nanostructured lead chalcogenides.4,27,150 Strong reduc-
tion of lattice thermal conductivity is achieved through nano-
structuring.
soluble in the parent material when molten (region I) but has
very low solubility in the solid state (region II). When the
molten mixture (region I) is rapidly cooled to form a solid, the
second phase precipitates (region III) since the solid solution
limit is exceeded. Moreover, to ensure a fine distribution and
good thermal stability, the second phase should have a
comparable or higher melting point than the host material.
Figure 7b displays typical nanostructuring created by the
nucleation and growth mechanism under the observation of
transmission electron microscopy (TEM). The sample is
PbTe−SrTe composite and features ubiquitous nanocrystals
of second-phase SrTe coherently dispersed in the host material
of PbTe. This good interface originates from the homogeneous
dispersion of SrTe in PbTe enabled by fast cooling as well as
their very small lattice mismatch.
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This nanostructuring approach has been successfully applied
to numerous thermoelectric materials with a great reduction of
lattice thermal conductivity. Typical examples include PbTe−
MTe (M = Ag, Ca, Sr, Ba, Cd, and Hg),3,4,71,75,148,149 PbSe−
MSe (M = Ca, Sr, Ba, Zn, Cd, Sb, and Bi),28,44,150 PbS−MS (M
= Bi, Sb, Ca, Sr, Zn, and Cd),27,151,152 SnTe−MS (M = Cd and
Zn),43,92 CoSb3−MSb (M = In, Ga, and Zn),153−156 and
Bi2Te3−M (M = Cu, Zn, and Te).22,32 A specific example is
shown in Figure 7c. When only ∼4% (mole fraction) of
strontium chalcogenides is added as second phase to the parent
lead chalcogenides, the lattice thermal conductivities are
strongly decreased. Unlike point defect scattering where high
alloying fraction is always pursued to achieve the lowest thermal
conductivity, in the case of nanostructuring, a relatively low
volume fraction of the second phase (usually a few moles %) is
optimal to achieve the strongest phonon scattering. In fact, at
higher fractions, the nanostructures can aggregate or coalesce
into larger structures with lower interface area, weakening their
scattering efficiency.130,151
Despite the numerous successes described above, we must
note that nanostructuring is not always successful in scattering
the heat-carrying phonons. As an example, Pb and Bi
nanostructures appear to exert little influence on the lattice
thermal conductivity of PbTe.157 In fact, the phonon
propagation inside the nanostructures is rather complicated
and usually unpredictable. One should always bear this in mind
when designing materials. Moreover, at elevated temperatures
where diffusion becomes more active, nanoscale precipitates
may coarsen and grow, reducing their effectiveness. This
challenge needs to be overcome and will require further
investigations in this direction, and new insights and techniques
already employed in preparing metallurgical nanostructured
alloys.158
3.3.3. Mesoscale Structuring. Low- and medium-wave-
length phonons carry most of the heat and can be effectively
scattered by point defects and second-phase nanostructures,
respectively. There are still many long-wavelength phonons
remaining, however, and they also contribute to the lattice
thermal conductivity. To scatter more of these phonons as well,
crystal defects and structure features at the length scale of
micrometers or submicrometers is necessary. This is the so-
called mesoscale, and it can be engineered into materials through
careful powder processing. Typically, the single crystals or cast
ingots (Figure 8a) have grains that are rather large (typically >
10 μm in geometric size). A mesoscale sample typically has
grain sizes from 0.1 to 3 micrometers, Figure 8b.
Rowe et al.159 investigated the thermal conductivities of SiGe
alloys with different grain sizes and compared them with that of
their single crystals, Figure 8c. They showed that large grain
sizes (light blue region where cast ingots locate) are ineffective
in decreasing the thermal conductivities. Only grains with
relatively small sizes (5 μm and below, light red area where the
polycrystalline samples locate) could scatter phonons strongly
(∼20% reduction of thermal conductivity with respect to the
single crystal). This work highlights the importance of
mesoscale grains in impeding the phonon transport of bulk
materials and points to further research to better understand
mesoscale effects.
To fabricate polycrystalline bulk thermoelectric materials,
one usually needs to first produce mesoscopic particles and
then densify them by either hot pressing or spark plasma
sintering. There are two general routes of obtaining the
mesoscopic particles, namely, top-down and bottom-up ap-
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Figure 8. Schematic diagrams of microstructures of (a) single crystals
or cast ingots without grain boundaries or with rather coarse grains
(>10 μm in size) and (b) polycrystalline samples with mesoscale
grains (hundreds of nanometers to several microns). (c) Experimental
study of the thermal conductivity of SiGe alloys (green circles) with
different grain sizes as compared to the single crystal.159 Solid line is a
guide to the eyes. Light blue and red areas denote where the grain sizes
of cast ingot and polycrystalline samples locate, respectively.
proaches.160 In the top-down approach, the mesoscopic particles
are acquired by pulverizing the coarse-grained crystals to fine
powders with the aid of hand grinding, mechanical alloying, etc.
Alternately, as developed by Tang’s group, using one-pot melt
spinning or self-propagation high-temperature synthesis (SHS),
one could obtain the products with fine grains or small particle
size. This has proven to be particularly effective in producing
high-performance bulk thermoelectric materials in a very short
period.161−164 Inversely, the bottom-up approach means direct
control of the mesoscopic particles growth by, such as, solution
chemistry methods including hydro- and solvothermal syn-
thesis,165 electrochemical deposition,166 sonochemical syn-
thesis,167 and so on. These solution chemistry methods have
been widely used to synthesize a wide variety of thermoelectric
semiconductors (e.g., skutterudites,168 metal chalcogenides,167
zinc antimonides169) with controllable size and morphology.
3.3.4. All-Scale Hierarchical Architectures. When point
defects, nanostructuring, and mesoscale structuring are all
combined into a single thermoelectric material, we call this as
an all-scale hierarchical architecture.4 While the thermal
conductivity in crystalline materials is limited by the Umklapp
scattering process, it can be decreased by defects at different
length scales with a broad range of wavelengths and mean free
paths (MFP, defined as the average distance traveled by
phonons between successive scatterings). Theoretical calcu-
lations125 suggest that, in PbTe, over 50% of the κlat value
comes from the contribution by phonons with MFP less than 1
nm, which can be ascribed to scattering by atomic-scale point
defects, Figure 9c. The remaining contribution to κlat is almost
equally divided between phonon modes with MFP of 1−10 nm
and phonon modes with MFP 10−1000 nm, Figure 9c), which
can be notably impeded by nanoscale precipitates and
mesoscale grains, respectively. Similar trends are found in
PbTe1−xSex170 and Si.171
All-scale hierarchical architectures achieve the strongest
phonon scattering,83,148,155,172 see Figure 9a. All-scale hier-
archical architectures were successfully created in lead
chalcogenides, have led to significantly enhanced thermoelectric
performance, and now have been applied to other lead-free
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Figure 9. Schematic diagram of the integration of multisized defects:
(a) atomic-scale point defects, (b) nanoscale precipitates, and (c)
mesoscale grains in one single material for all-scale hierarchical
architectures of phonon scattering.4 (d) Contributions of phonons
with different mean free paths to the cumulative κlat value for PbTe.125
(e) Temperature dependence of lattice thermal conductivity for the
all-scale hierarchical architecture SnTe system.88,92 Green color depicts
the mesostructuring, red color depicts the approach of solid solution
point defects, and blue line depicts the approach of nanostructuring.
materials, including SnTe, 43,92 GeTe, 38 AgSbSe 2 , 173
AgCrSe2,174 CoSb3,155,164 Bi2Te3,175 and In2O3.176 Figure 9e
shows a comparison of the lattice thermal conductivity of SnTe
samples with different defects: mesoscale grains by SPS
treatment,88,92 atomic-scale point defects of Cd substitution
for Sn,92 and nanoscale CdS precipitates.92 It is apparent that
mesostructuring lowers the lattice thermal conductivity of SnTe
ingot by about 22% at room temperature, from ∼2.7 to ∼2.1 W
m−1 K−1. The atomic point defects and nanoscale precipitates
contribute additional phonon scattering, leading to further
reduction of κlat by ∼25% and ∼20%, respectively. In all, a total
reduction of κlat by more than 50% is achieved by all-scale
hierarchical architectures of phonon scattering.
4. DECOUPLING OF ELECTRON AND PHONON
TRANSPORT
We highlighted above that nanostructuring in bulk materials
dramatically reduces the thermal conductivity. However,
simultaneously it can also increase the charge carrier scattering
due to the additional energy barrier caused by crystallographic
mismatch and/or electronic bands misalignment at the
interfaces.4,43,83 This has detrimental effects on the carrier
mobility and power factor. Therefore, to avoid the mobility loss
in nanostructured thermoelectric materials, both coherent
interfaces (endotaxy) and energy-matched electronic bands
are required. To some extent this situation achieves a
decoupling of electron and phonon transport. Below we
discuss approaches of decoupling electron and phonon
transport in nanostructured bulk thermoelectric materials.
4.1. Strained Endotaxial Nanostructuring
In a high-performing nanostructured thermoelectric material,
the phonons should be scattered as much as possible by the
nanoprecipitates while the electrons should flow across the
interfaces without much scattering, Figure 10a. The electron
and phonon scattering are strongly affected by the interface
(endotaxy), which is usually determined by the degree of lattice
misfit (ε) between the nanoprecipitates and the matrix.157
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Figure 10. Schematic diagram of electron and phonon transport
decoupling in nanostructured bulk materials: phonons (depicted by
blue arrows) are strongly scattered by nanoprecipitates, while the
electrons (depicted by red arrows) travel across the interfaces without
restriction. (b) Schematic of phonons scattered by three possible types
of interfaces (coherent, semicoherent, and incoherent) between matrix
and nanoprecipitates. Reprinted with permission from ref 157.
Copyright 2010 American Chemical Society. (c) High-resolution
TEM phase contrast image of several SrTe nanoprecipitates (i, ii, iii,
and iv) embedded in the PbTe matrix. (d) Enlarged image of
nanoprecipitate i showing coherency at the boundary highlighted by
the dotted line. (e) Inverse first Fourier transform image of precipitate
i, indicating the absence of dislocations at the grain boundary. (f)
Shear strain map profiles for the four nanoprecipitates shown in d.
There are elastic strains at and around all precipitates and also plastic
strain at and around dislocation cores in precipitates iii and iv. (c−f)
Reprinted with permission from ref 3. Copyright 2011 Nature
Publishing Group.
There are generally three types of precipitate−matrix interfaces
in light of their coherency: coherent (ε < 1%), semicoherent
(1% < ε < 25%), and incoherent (ε > 50%).157,177 These three
scenarios embody different atomic configurations and asso-
ciated local interfacial relaxation mechanisms,157 Figure 10b. In
the case of semicoherent or incoherent interfaces, the
surrounding atomic order is strongly disrupted, leading to
significant scattering of both electrons and phonons. The direct
consequence is limited ZT improvement. When the nano-
precipitates and the matrix are coherently (endotaxially)
connected but have a certain degree of strain around their
interfaces, we call it strained endotaxial nanostructuring. This
interface is supposed to facilitate charge transport across it but
strongly block/scatter phonon propagation.
The presence of strained endotaxial interfaces has been
observed in a number of nanostructured materials. In
pioneering work by Hsu et al.,1 coherent nanostructured bulk
thermoelectric materials LAST were synthesized with a
measured ZT of ∼1.7 at 700 K. They contained Ag−Sb-rich
nanoprecipitates embedded within the PbTe matrix. Sub-
sequently, the nature of the LAST materials was analyzed in
detail by several groups.178−181 Later, other examples were
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Review
demonstrated, including PbTe−GeTe,38 PbTe−PbS,42 PbTe−
MTe (M = Mg, Ca, Sr, Ba),3,4,83,148 PbSe−MSe (M = Ca, Sr,
Ba),150 and SnTe−MnTe.89,97 Figure 10 c−f show strained
endotaxial nanostructuring present in the PbTe−SrTe system.
Figure 10c is a typical phase contrast high-resolution TEM
image showing several 2−4 nm SrTe precipitates (depicted by
the white arrows, marked as i, ii, iii, and iv, respectively) within
the PbTe matrix. An enlarged high-resolution TEM image of
precipitate (i) shown in Figure 10d clearly suggests the absence
of any dislocations at the boundary highlighted by the dotted
line. In Figure 10e, the inverse first Fourier transform
reconstructed image of the precipitate (i) depicts a perfect
interface endotaxy (coherency) between the precipitate and the
matrix. The shear strain map profiles based on geometric phase
analysis conducted on the four nanoprecipitates shown in
Figure 10c are displayed in Figure 10f.3 Elastic strain is
pervasive in and around all precipitates, and there is also plastic
strain around the dislocation cores in precipitates iii and iv. The
coherent but strained interfaces between the matrix and the
nanoprecipitates lead to strong phonon scattering but minimal
electron scattering. Strained endotaxial nanostructuring is now
becoming a popular approach of designing high-performance
bulk thermoelectric materials.
4.2. Matrix/Precipitate Band Alignment
Though the scattering of electrons can be minimized by
improving the interface coherency in nanostructured materials,
the additional energy barrier from misalignment of electronic
bands can hinder electron flow. Previous studies on GaAs/InAs
(001) heterojunctions indicated that charge carriers can
transmit freely when the band offsets are minimal.182 Recently,
a similar approach has been developed in three-dimensional
bulk nanostructured thermoelectric materials by minimizing the
energy offsets of electronic bands between the nanoprecipitates
and the matrix.3,4,27,28
The concept of electronic band alignment is illustrated in
Figure 11a. The dotted lines depict the energies of the
conduction band minimum (CBM) and the valence band
maximum (VBM) of two different second phases and a host
matrix. Phase A has good valence band alignment with the
matrix (an energy difference that is comparable to the
magnitude of thermal energy at elevated temperatures of kBT
is considered band alignment). Therefore, the matrix/A system
Figure 11. (a) Schematic representation of the alignment of the
valence band (VB) and conduction band (CB) energies of A and B
second phase in the matrix. ΔEC and ΔEV denote the energy offsets of
CB and VB between the second phase and the matrix, respectively.
The small band offsets allow seamless carrier transmission. (b)
Temperature dependence of carrier mobilities and lattice thermal
conductivity for the PbTe−SrTe system doped with 2% Na.3,4 All
samples have similar doping level. The endotaxially nanostructured
SrTe with small valence band offsets has negligible effect on the hole
mobility while blocking heat-carrying phonons at the matrix/
nanostructure interface.
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is expected to enable seamless hole transmission across the
interface. Likewise, phase B has negligible energy difference of
CBM with that of the matrix, and it is expected to allow facile
electron transmission.
p-Type PbTe embedded with well-dispersed SrTe nano-
crystals is a well-known example of valence band alignment.3,4
As shown in Figure 11b, the lattice thermal conductivity of
PbTe is remarkably decreased upon the addition of SrTe
second phase but the hole mobility is largely unaffected.
Specifically, under similar hole doping, the room-temperature
lattice thermal conductivity of the control sample (containing
no SrTe) is ∼1.8 W m−1 K−1, and it is decreased to ∼1.5 and
∼1.3 W m−1 K−1 by introducing 1% and 2% SrTe, respectively.
In contrast, the carrier mobility is almost constant in this
process, stabilizing between 340 and 350 cm2 V−1 s−1 at room
temperature. The reason for this is 2-fold:3 (1) endotaxial
alignment of SrTe and PbTe phases with coherent interfaces, as
we elaborated in the previous section, and (2) the alignment of
the energies of the two valence bands in the two materials
where the band offset is very small at T > 300 K.
Actually, the generality of the matrix/precipitate band
alignment concept is also evident in the PbS system
nanostructured with various metal sulfides (CdS, ZnS, CaS,
and SrS).27 Though all these nanostructures are equally
effective in achieving a very low lattice thermal conductivity
(∼0.6 W m−1 K−1 at 923 K), only CdS helps maintain a high
hole mobility due to its smallest valence energy offsets with PbS
(∼0.13 eV at 0 K). This is the main reason for the superior ZT
of the CdS-containing samples (∼1.3 at 923 K in 2.5% Na-
doped PbS with 3% CdS), a record value for PbS.27
4.3. Compositionally Alloyed Nanostructures
The ideal nanostructuring case is when the electronic bands of
matrix and the second phase are perfectly aligned in energy. In
practice it is not easy to find such an appropriate combination
of second phases. The CBM or VBM of the possible candidates
lie either higher or lower in energy with respect to those of the
matrix. In this case we can use the concept of “compositionally
alloyed nanostructures”28 to achieve electronic band alignment.
The concept is schematically presented in Figure 12a. The
CBM of the second phases AB and AC is too high or too low
with respect to the matrix to achieve effective conduction band
alignment on their own. However, if one could mix them in a
proper ratio to form a solid solution (AB1−xCx) then this alloy
may have minimal energy offsets with the matrix. Similarly,
valence band alignment can be achieved by alloying a proper
amount of second-phase XZ in XY as nanostructures
(XY1−mZm). In this regard, compositionally alloyed nanostruc-
ture is a universal concept of matrix/precipitate band
alignment.
A good example of applying this idea is p-type PbSe
compositionally alloyed with CdS or ZnS.28 As shown in Figure
12b, based on the theoretical band calculation results, the
VBMs of CdS (∼0.27 eV) and ZnS (∼0.30 eV) are far below
that of PbSe, while those of CdSe (∼0.06 eV) and ZnSe (∼0.13
eV) are higher than that of PbSe. Therefore, none of them
could be directly used to align the valence bands. However,
when CdS or ZnS is added to PbSe, the following alloying
reactions are expected to occur
PbSe + CdS → PbSe1 − xSx + CdS1 − x Sex (11)
PbSe + ZnS → PbSe1 − xSx + ZnS1 − x Sex (12)
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Figure 12. (a) Schematic representation of how compositionally
alloyed nanostructures can achieve aligned electronic bands. (b)
Valence band alignment by compositionally alloyed nanostructuring in
p-type PbSe system.28 (c) Room-temperature carrier mobility of 2%
Na-doped PbSe nanostructured with CdSe, ZnSe, CdS, and ZnS as a
function of second-phase mole fraction.28 (d) Temperature-dependent
lattice thermal conductivity of 2% Na-doped PbSe nanostructured with
3% CdSe, ZnSe, CdS, and ZnS.28
These happen via an interfacial reaction between the selenide
matrix and the sulfide second phase and are confirmed by the
chemical composition analysis using high-resolution energy-
dispersive spectroscopy (EDS).28 The compositionally alloyed
new phases CdS1−xSex and ZnS1−xSex then have different band
energies and can be employed to create minimal energy offsets
with VBM of PbSe, Figure 12b.
Because of the good band alignment the compositionally
alloyed nanostructures have almost no detrimental effect on the
carrier mobility, Figure 12c. In contrast, a decreasing trend of
mobility with increasing second-phase fraction is observed for
the CdSe- or ZnSe-containing PbSe samples due to incorrect
band alignment with PbSe, Figure 12b. Of course, the
embedded nanostructures continue to scatter phonons to
produce large reductions in lattice thermal conductivity, Figure
12d. Therefore, the compositionally alloyed nanostructuring
samples feature superior performance, e.g., Pb0.98Na0.02Se−3%
CdS has ZT of ∼1.6 at 923 K, the highest value ever reported
for PbSe.28
5. DISCOVERIES OF NEW THERMOELECTRIC
MATERIALS WITH INTRINSICALLY LOW THERMAL
CONDUCTIVITY
From the above it is apparent that a number of useful concepts
have emerged, which can be integrated in a synergistic manner
in bulk materials to greatly enhance thermoelectric perform-
ance.183 Clearly, we are in a new era for thermoelectric
materials research.
In a very special group of materials, high thermoelectric
performance can be found in pristine compounds with
intrinsically low thermal conductivity. The intrinsically low
thermal conductivity means that the most complex approaches
to reduce thermal conductivity could be avoided. Below we
introduce some promising thermoelectric materials with
intrinsically low thermal conductivity, which may arise from
an anharmonic and anisotropic bonding,40,56 lattice vibra-
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tions,184,185 atomic disorders induced by ion migrations,185
copper ion liquid-like behaviors, 36,186 large molecular
weight,55,187 complex crystal structure,188 lone-pair elec-
trons,189,190 etc.
5.1. Layered SnSe
Recently, a record high ZT of 2.6 in a single binary crystal of
SnSe was observed.40 SnSe has an unusual layered structure
that derives from a three-dimensional distortion of the NaCl
structure. SnSe has two-atom-thick SnSe slabs (along the b-c
plane) with strong Sn−Se bonding within the plane of the
slabs, which are then linked with weaker Sn−Se bonding along
the a direction, see Figure 13a. The two-atom-thick SnSe slabs
Figure 13. (a) SnSe crystal structure viewed along the b axis: gray, Sn
atoms; red, Se atoms. Blue box represents a unit cell. (b) ZT values as
a function of temperature for SnSe single crystals along different axial
directions and polycrystalline SnSe pellets along radial and axial
directions.40
are corrugated, creating a zigzag accordion-like projection along
the b axis. The easy cleavage in this system is along the (l00)
planes.40 The special crystal structure results in impressively
low thermal conductivities of 0.7 (300 K) and 0.4 W m−1 K−1
(700 K) for SnSe crystals (b axis). To probe the origin of the
intrinsically low thermal conductivity of SnSe, the phonon and
Grüneisen dispersions, which reflect an anharmonicity of
chemical bonds, have been calculated using first-principles
density-functional theory (DFT). The results show that the
average Grüneisen parameters along the a, b, and c axes are 4.1,
2.1, and 2.3, respectively. Along the a axis, the maximum
longitudinal acoustic Grüneisen parameter is extraordinarily
high at ∼7.2. In contrast, the Grüneisen parameters for known
low thermal conductivity materials is 2.05 for AgSbTe2,191 3.5
for AgSbSe2,189 and 1.45 for PbTe.191 These materials have
lattice thermal conductivities at room temperature of 0.68, 0.48,
and 2.4 W m−1 K−1, respectively.
The anomalously high Grüneisen parameter of SnSe is a
reflection of its crystal structure which contains much distorted
SnSe7 polyhedra (due to the lone pair of Sn2+) and the zigzag
accordion-like geometry of slabs in the b-c plane. This implies a
very soft lattice, in which if mechanically stressed along the b
and c directions would not directly change the Sn−Se bond
lengths, but instead the zigzag and geometry would allow it to
be deformed like a retractable spring. In addition, along the a
direction the weaker bonding between SnSe slabs makes it a
good stress buffer or a “cushion”, thus dissipating phonon
transport laterally. The anomalously high Grüneisen parameter
is therefore a consequence of “soft” bonding in SnSe, which
presumably leads to the very low thermal conductivity and the
surprising thermoelectric performance of the single crystals.40
Single crystals of SnSe show a ZT value of approximately 2.6
at 923 K along the b axis and 2.3 along the c axis, whereas a
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moderate ZT value of approximately 0.8 was measured along
the a axis, Figure 13b. These high ZT values observed in SnSe
single crystals are not observed in polycrystalline samples of
SnSe, which exhibit a ZT peak of ∼1.2 at 973 K. The reason is
the big differences in carrier mobility and thermal conductivity
between SnSe single- and polycrystalline samples where the
three different crystallographic directions are averaged but in a
difficult to control manner because of the varying degrees of
preferential orientation, Figure 14a.
Figure 14. (a) Carrier mobility and (b) power factor as a function of
temperature for undoped SnSe single crystals40 along different axial
directions and polycrystalline SnSe pellets119 along radial and axial
directions. (c) Thermal conductivities as a function of temperature of
undoped SnSe single crystals40 and polycrystalline SnSe prepared in air
and a glovebox.192
The carrier mobility along the b axis for SnSe single crystals
is 10 times higher than along the a axis. This strong anisotropic
character diminishes the carrier mobility in polycrystalline
SnSe, as also observed by Chen et al.119 For example, at room
temperature, the hole mobility of polycrystalline SnSe is ∼50
cm2 V−1 s−1 with a carrier density of 3 × 1017 cm−3;119 however,
the hole mobility in single crystals is about 250 cm2 V−1 s−1 (at
similar carrier density of 3 × 1017 cm−3). At 750 K, at the carrier
density of 4 × 1018 cm−3, the hole mobility of polycrystalline
SnSe sample is about 10 cm2 V−1 s−1, which is only one-fifth of
∼50 cm2 V−1 s−1 for the SnSe single crystals.40 The low carrier
mobility of polycrystalline SnSe results in an electrical
conductivity that is five times lower than that of SnSe single
crystals. This results in a one-fifth of the power factor (Figure
14b) and lower ZT values (Figure 13b). We expect this number
to change from report to report and from sample to sample
since the degree of polycrystalline orientation may vary across
samples and laboratories. For this reason we suggest such
reports of transport properties of polycrystalline SnSe to be
accompanied with detailed X-ray and microscopic character-
ization of the degree of preferential orientation.
Very recently, Zhang et al.192 reported a similar thermal
conductivity in polycrystalline SnSe to that of SnSe single
crystals.40 The maximum power factor in polycrystalline SnSe
achieved to date is ∼4 μW cm−1 K−2 at 773 K and a ZT of
1.0.192 Correspondingly, the maximum power factor is ∼6 μW
cm−1 K−2 at 773 K, resulting in a ZT of 1.5 at 773 K in undoped
SnSe single crystals.40 It should be noted that both these
reports have samples of similar carrier concentration and
Seebeck coefficient. Therefore, the differences in power factor
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and ZTs come from the carrier mobility and from the strong
anisotropic character of the SnSe crystal structure.
Apart from the carrier mobility in some reports,90,119,193−196
the ZT differences between SnSe single crystals and polycrystal-
line SnSe samples also come from thermal conductivity
deviations. Indeed, the explanations of strong anharmonic
chemical bonding given for the low thermal conductivity of
SnSe single crystals also apply to polycrystalline SnSe
samples.40,107 However, accurately measuring the thermal
conductivity of SnSe even in single-crystal samples seems to
be a challenge. It has been found that polycrystalline samples
are more difficult to work with because of surface oxidation and
preferential orientation. It is possible that the surface oxidation
yields SnO2 second phase, which has a thermal conductivity of
∼98 W m−1 K−1, about 140 times higher than SnSe.197 If the
polycrystalline samples are prepared or handled in air this could
give higher thermal conductivity values. In our experience
polycrystalline samples protected from oxidation have low
thermal conductivities similar to single-crystal samples.192
Recently, He et al. gave the same explanation for the thermal
conductivity issue.198 They found that the thermal conductivity
of polycrystalline SnSe will decrease when the SnSe powders
are processed in a glovebox and will closely approach the 0.30
W m−1 K−1 value at 773 K, which is comparable to 0.30 (c axis)
and 0.35 W m−1 K−1 (b axis) of SnSe single crystals.40 This
oxidation could lead to a thin layer of tin oxides on the surface
of the micrometer-sized powders. Indeed, a similar low thermal
conductivity of 0.30 W m−1 K−1 at 773 K was observed in
polycrystalline SnSe strictly prepared in a glovebox,192 as shown
in Figure 14c.
To investigate this hypothesis, a series of control experiments
was carried out. We find that the thermal conductivity of
polycrystalline SnSe is very low when the SnSe powders are
processed in a glovebox compared to processing in air and
closely approaches the 0.36 W m−1 K−1 value at 773 K, which is
comparable to 0.30−0.35 W m−1 K−1 of SnSe single crystals.40
Interestingly, when we processed the SnSe powders with a
small added amount of SnO2 (e.g., the SnO2 addition ranged
from 0.0038 to 0.02 g of SnO2 per 5 g of SnSe, 0.1−0.6% by
weight), the thermal conductivities of the polycrystalline SnSe
samples showed a significant increase even though the powders
were processed in a glovebox. Besides the preparation
conditions, stoichiometric composition is also crucial to the
thermal conductivity of SnSe. Serrano-Sanchez et al. confirmed
the intrinsically low thermal conductivity of SnSe and provided
insights into the stoichiometric ratio and the sample processing
conditions.199 The microscopic neutron powder diffraction
analysis demonstrated a nearly ideal stoichiometry and a high
amount of anharmonicity of the chemical bonds of SnSe, and
the lowest thermal conductivity value is close to 0.1 W m−1 K−1
at room temperature for the polycrystalline SnSe.199
As an analogue of SnSe, the thermoelectric properties of SnS
are also receiving attention. Experimentally, Tan et al. reported
that the low thermal conductivity falls below 0.5 W m−1 K−1 at
873 K and leads to a high ZT of 0.6 in Ag-doped polycrystalline
SnS, pointing out that the low-cost SnS is a promising
candidate for thermoelectric investigations.200,201 The exper-
imental results are well supported by first-principles theoretical
calculations, which indicate that SnS could possess a high
Seebeck coefficient and a very low thermal conductivity.202
Bera et al. suggested that SnS is potentially a good
thermoelectric material if it can be suitably doped.203
Considering the poor electrical transport properties of SnS, a
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high thermoelectric performance could be expected in perfect
SnS single crystals with heavy doping.
Apart from the intrinsically low thermal conductivity of SnSe,
the electronic band structure is also very impressive. It is well
known that the Seebeck coefficients could be enhanced through
manipulating multiple valence or conduction bands, which are
highly sought features in thermoelectric materials. Figure 15a
Figure 15. (a) Schematic of the electronic band structure of SnSe
indicating nonparabolic, complex multiband valence states. The Fermi
level (green dash line) is moving into the multiband structure after
heavily doping. Electrical transport properties as a function of
temperature for undoped SnSe and hole-doped SnSe along different
crystallographic directions: (b) electrical conductivity; (c) Seebeck
coefficients (inset shows the room-temperature Seebeck coefficients
comparisons for the lead and tin chalcogenides with similar carrier
concentration of ∼4 × 1019 cm−3); (d) power factors including those
of the optimized Bi2−xSbxTe3 and PbTe−4SrTe−2Na plotted for
comparison.2,4
shows multiple valence bands for SnSe, and it is rare to find a
system that exhibits this enhancement while also exhibiting
extremely low thermal conductivity and a high electrical
conductivity.204,205 Hole doping increases the electrical
conductivity from ∼12 to ∼1500 S cm−1 as the carrier
concentration increases from ∼1017 to ∼1019 cm−3 at 300 K, as
shown in Figure 15b. Meanwhile, the Seebeck coefficient
decreases from ∼+500 μV K−1 for undoped SnSe to ∼+160 μV
K−1 at 300 K in doped while still keeping a large value of
∼+300 μVK−1 at 773 K. The inset of Figure 15c indicates that
the Seebeck coefficient for hole-doped SnSe is clearly much
higher than ∼+70 μV K−1 for PbTe,206 ∼+60 μV K−1 for
PbSe,207 ∼+50 μV K−1 for PbS,27 and ∼+25 μV K−1 for SnTe92
at similar doping levels. The observed Seebeck coefficient
enhancements of hole-doped SnSe can be attributed to the
multiband character of the electronic structure.204,205 The
combination of vastly increased electrical conductivity and high
Seebeck coefficient results in a large power factor of ∼40 μW
cm−1 K−2 for hole-doped SnSe (b axis) at 300 K, Figure 15d.
The power factors obtained in hole-doped SnSe are as high as
those of optimized Bi2−xSbxTe3 materials2 near room temper-
ature and are higher than those of the high-performance
hierarchically architectured p-type PbTe−SrTe system in the
range of 300−500 K.4
The temperature dependence of total thermal conductivities
(κtot) for undoped and hole-doped SnSe are shown in Figure
16a. At room temperature, the values of κtot for undoped SnSe
are ∼0.46, 0.70, and 0.68 W m−1 K−1 along the a, b, and c axis
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Figure 16. (a) Total thermal conductivities, (b) lattice thermal
conductivities and (c) ZT values as a function of temperature for
undoped SnSe and hole-doped SnSe along different crystallographic
directions; (d) ZT values comparisons of hole doped SnSe (b axis) and
the current state-of-the-art p-type thermoelectrics, BiSbTe, 2
MgAgSb,34 NaPbmSbTem+2 (SALT),208 PbTe-4SrTe-2Na4 and SnSe
(b axis).40
directions, respectively. These already low values continue to
decrease with rising temperature, and all fall in the range 0.25−
0.28 W m−1 K−1 at 773 K. After hole doping, the total thermal
conductivities are higher due to a large contribution from
electronic thermal conductivities. To derive the lattice thermal
conductivity, the Lorenz number of 1.5 × 10−8 V2 K−2 was used
for the undoped SnSe since it is a nondegenerate semi-
conductor. To more accurately obtain an estimate of the lattice
thermal conductivity of hole-doped SnSe, the Lorenz number L
has to be calculated based on a multiband model. Using more
appropriate Lorenz numbers, one can see that the lattice
thermal conductivity of hole-doped SnSe is comparable to or
even lower than undoped SnSe, Figure 16 b. After hole doping,
one can find a vast increase in ZT from 0.1-undoped to 0.7-
hole-doped along the b axis at 300 K while obtaining the ZTmax
of 2.0 at 773 K, Figure 16 c. The hole-doped SnSe (b axis)
outperforms most of current state-of-the-art p-type materials at
300−773 K, such as Bi2−xSbxTe3,2 MgAgSb,34 NaPbmSbTem+2
(SALT),208 PbTe−4SrTe−2Na4 and SnSe (b axis),40 as shown
in Figure 16 d.
5.2. BiCuSeO Oxyselenides
Since BiCuSeO oxyselenides have been reported as potential
thermoelectric materials in 2010 by Zhao et al.,209 they have
attracted everincreasing attention and have been extensively
studied. BiCuSeO crystallizes in a layered ZrCuSiAs structure
type, with the tetragonal unit cell a = b = 3.9273 Å, c = 8.9293
Å, Z = 2, and the space group P4/nmm (No.129, PDF 45-
0296).56 Figure 17a shows that BiCuSeO exhibits a two-
dimensional structure containing fluorite-like Bi2O2 layers
alternatively stacked with Cu2Se2 layers along the c axis. The
coordination of Bi can also be considered as a distorted square
antiprism with four O atoms in one base and four Se atoms in
the other. The Bi−Se bond length ∼3.2 Å is longer than the
Bi−O bond length ∼2.33 Å, which implies its layered feature.
The Cu2Se2 layers consist of slightly distorted CuSe4 tetrahedra
with shared Se−Se edges. The Cu2Se2 layer could be
considered as a reversed version of Bi2O2 layer, because Cu
atoms occupy the Bi sites while Se atoms occupy the O
sites.210,211 As shown in Figure 17b, the maximum ZT of
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Figure 17. BiCuSeO crystal structure and ZT values. (a) Crystal
structure along the a axis: yellow, Cu atoms; red, Se atoms; purple, Bi
atoms; blue, O atoms. Blue box represents a unit cell. (b)
Dimensionless figure-of-merit ZT vs temperature of selected typical
current thermoelectric materials: CsBi 4 Te 6 , 29 Bi−Sb−Te, 2
AgPbmSbTem+2 (LAST),1 Mg2SiSn,24 PbTe−SrTe−Na,4 skutteru-
dite,33 BiCuSeO,116,213 half-Heusler,214 SiGe,6 and Zintl phase.55,187
Green lines are p-type, blue lines are n-type materials, and thick red
line is BiCuSeO.
BiCuSeO exceeds 1.0 above 650 K and monotonously increases
up to 1.4 at 923 K.116,212,213 The average ZT, quantitatively
represented by the area under the ZT vs temperature curve, is
the property used to estimate the performance in real
application conditions. It can be seen that the average ZT of
BiCuSeO outperforms several conventional thermoelectric
materials. Moreover, compared to conventional heavy-metal-
based thermoelectric materials,5,50,56,96 BiCuSeO oxyselenides
are earth abundant and can thus be regarded as promising
candidates for vehicle waste heat recovery and solar thermal
engine replacement.
The promising ZT of the oxyseleneide compound BiCuSeO
is mainly due to its intrinsically low thermal conductiv-
ity.215−218 Ding et al. calculated the thermal conductivity of
BiCuSeO using the lattice thermal conductivity obtained by the
Grüneisen parameter and the electronic thermal conductivity
using the Wiedemann−Franz relation.185 As shown in Figure
18a, at low temperature the experimental data are far below the
calculated results, even after the addition of scattering
contributions from the defects. This indicates an extra
mechanism may be responsible for the low thermal
conductivity of BiCuSeO. Figure 18b shows the heat capacity
of BiCuSeO as a function of temperature; the heat capacity at
room temperature shows good agreement with the Dulong−
Petit law.
Saha184 proposed an atomic displacement pattern for the
respective lowest frequency optical mode of BiCuSeO, as
shown in Figure 18c. In this pattern the arrows are proportional
to the amplitude of the atomic motions, since the Bi atoms
exhibit a significantly large displacement, indicating higher
anharmonic effects.184 Assuming the heat is conducted only by
acoustic and quasiacoustic phonons via umklapp scattering
processes, the calculations suggest an average Grüneisen
parameter of 2.9. Additionally, the calculated thermal
conductivity in the out-of-plane direction of BiCuSeO is
about two times smaller than that in-plane one, indicating that
BiCuSeO has an large anisotropy of heat flow between the in-
plane and the out-of-plane directions.184
Ding et al. also calculated the phonon spectrum and mode
Grüneisen parameters of BiCuSeO.185 First-principles calcu-
lations provide direct evidence of the structural in-layer and
interlayer off-phase vibration modes, which contribute to the
anharmonic vibrations and structural scattering of phonons and
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Figure 18. (a) Thermal conductivity as a function of temperature for
pristine BiCuSeO, the blue line is the calculated total thermal
conductivity, and the black line the experimental data.185,215 (b) Heat
capacity as a function of temperature for BiCuSeO; the red line is the
data based on the Dulong−Petit law.215,216 (c) Atomic displacement
patterns for BiCuSeO; arrows are proportional to the amplitude of the
atomic motions.184 (d) Mode Grüneisen parameters of BiCuSeO. Red
squares correspond to the mode Grüneisen parameters of acoustic
branches, black circles correspond to the frequencies between 2.5 and
6 THz, and the blue diamond represents the phonon modes of O
above 6 THz.185
result in a low thermal conductivity for BiCuSeO. As shown in
Figure 18d, the mode Grüneisen parameters vary between 0.08
and 6.74. The average Grüneisen parameter is approximately
2.5, which is considerably larger than the experimental value of
1.5 estimated from the average sound velocity in polycrystalline
BiCuSeO.219 It is believed that the presence of the heavy
element Bi contributes to the large Grüneisen parameter due to
its large valence shell formed by lone-pair electrons.56,219 As can
be seen from Figure 18 d, the Grüneisen parameters of the low-
frequency modes are very large, which indicates the strong
interaction between acoustic phonons and optical phonons.185
These phonon−phonon Umklapp processes can significantly
scatter acoustic phonons carrying heat and reduce the lattice
thermal conductivity. The anomalously high Grüneisen
parameters of BiCuSeO also reflect its crystal structure, which
contains distorted edge-sharing CuSe4 tetrahedra and a layered
structure with zigzag geometry. This implies a soft lattice, which
can scatter phonons easily.
5.3. Half-Heusler MgAgSb
Materials with the half-Heusler structure can possess excellent
electrical transport properties that make them of strong interest
for thermoelectric applications.220 MgAgSb is compositionally
and structurally related to many other half-Heusler materials,
whose thermoelectric properties along with ab initio determi-
nation of crystal structures were extensively investigated.221
MgAgSb exists in three different crystal structures at 300−700
K, taking the half-Heusler structure at 630−700 K (γ-phase
with space group F4̅3m), a Cu2Sb-related structure at 560−630
K (β-phase with space group P4/nmm), and a tetragonal
structure at 300−560 K (α-phase with space group I4̅c2). The
low Seebeck coefficient of ∼70 μV/K and high electrical
conductivity of ∼2.5× 104 S/cm indicate that β-MgAgSb shows
a metallic transport behavior; therefore, most reports focus on
the thermoelectric properties at 300−560 K of α-MgAgSb. As
shown in Figure 19a, the α-MgAgSb phase consists of a
distorted Mg−Sb rocksalt lattice, rotated by 45° about the c
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Figure 19. (a) α-MgAgSb crystal structure: light blue, Ag atoms; red,
Sb atoms; light purple, Mg atoms. (b) ZT values as a function of
temperature for doped samples of MgAgSb.34,223
axis, with one-half of the Mg−Sb pseudocubes filled with Ag.
The unit cell of the α-MgAgSb phase is doubled (distorted
Mg−Sb rocksalt lattice) along both axes to accommodate a
different ordering of the Ag atoms. In the pattern of filling of
the Mg−Sb cubes (distorted Mg−Sb rocksalt lattice), the Ag-
filled sites form one-dimensional chains, running in all three
primary directions.
The presence of complicated phase transitions makes it
difficult to obtain pure α-MgAgSb phase when the samples are
cooled from 1250 K to room temperature and the impurities
degrade the thermoelectric performance. For example, a α-
MgAgSb sample with high content of secondary phase of Ag3Sb
(∼19%) shows a maximum ZT of only ∼0.5 at 425 K.221 To
eliminate the impurity phase, Ying et al. carried out a 2-week
annealing treatment at 553 K,222 which led to a maximum ZT
of ∼0.8 at 525 K. After optimizing the carrier density using In
doping on the Sb site, a maximum ZT value of ∼1.1 was
achieved at 525 K at an optimized carrier density of 8−9 × 1019
cm−3, Figure 19b.
Compared with conventional melting techniques, mechanical
alloying has been widely used in the thermoelectric field to
nanostructuring grain sizes and purifying material phases.2 Zhao
et al. recently used a two-step mechanical alloying method and
successfully obtained α-MgAgSb single phase, which shows a
ZT of ∼0.9 at 450 K.34 Figure 19b shows that the
thermoelectric performance of α-MgAgSb can be significantly
enhanced through doping, namely, the maximum ZT values can
be achieved ∼1.2, ∼1.4, ∼1.3, and ∼1.3 for MgAg0.97Sb0.99,34
MgAg 0.965 Ni 0.005 Sb 0.99 , 34 MgAg 0.963 Cu 0.007 Sb 0.99 , 223 and
Mg0.9925Na0.0075Ag0.97Sb0.99,223 respectively. Experimentally, a
high thermoelectric conversion efficiency of 8.5% was reported
with a single leg based on α-MgAgSb-based compound
operating between 300 and 520 K. Within the temperature
range of 300−450 K, the efficiency of a MgAgSb-based device
can match that of a Bi2Te3-based device.224 Considering the
abundantly available constituent elements, α-MgAgSb is
promising for power generation at 300−550 K.
The promising thermoelectric properties of MgAgSb are
ascribed to the low thermal conductivity. As shown in Figure
20a, the thermal conductivities show a decreasing trend up to
400 K and then increase with rising temperature because of
bipolar diffusion. The minimum thermal conductivities at ∼373
K are ∼0.98 and ∼0.95 W m−1 K−1 for MgAgSb and
MgAg0.97Sb0.99In0.01, respectively, and can be further reduced
by point defects scattering through doping,222 namely, the
minimum thermal conductivities at ∼373 K are ∼0.74, ∼0.66,
∼0.71, and ∼0.77 W m −1 K −1 for MgAg 0.97 Sb 0.99 , 34
MgAg 0.965 Ni 0.005 Sb 0.99 , 34 MgAg 0.963 Cu 0.007 Sb 0.99 , 223 and
Mg0.9925Na0.0075Ag0.97Sb0.99,223 respectively.
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Figure 20. (a) Thermal conductivity as a function of temperature for
samples of MgAgSb.34,223 (b) Ag+ migration model from Ag site to Mg
vacancy and (c) Mg2+ migration model from Mg site to Ag vacancy in
α-MgAgSb.185 (b and c) Reprinted with permission from Li et al. Adv.
Funct. Mater. 2015, 25, 6478−6488. Copyright 2015 WILEY
Publishing.
Li et al. found that unique Ag and Mg ion migrations in α-
MgAg0.97Sb0.99 cause significant local atomic disorder which is
believed to be the main origin of the low thermal
conductivity.185 DFT calculations indicate that the activation
energy for Ag+ migration from the Ag2 site to the Mg vacancy
is ∼0.202 eV, as shown in Figure 20b. The respective activation
for Mg2+ migration from the Mg site to the Ag2 vacancy is
∼0.485 eV, as shown in Figure 20c. This reveals a unique type
of ion migration between the Ag site and the Mg site in α-
MgAg0.97Sb0.99, which weakens the chemical bonds, consistent
with the softening transverse phonon modes, the low Debye
temperature (160 K), and the low mean phonon velocity of
1276 ms−1.
5.4. Copper Chalcogenides
Copper sulfides and selenides have been recognized as
interesting thermoelectric materials. The history of copper
chalcogenides goes back 1827, when Becquerel observed that
burning some sulfur powder atop the copper wire significantly
enhanced the generation of electricity.225,226 They were also
studied in the 1960s;227 then the general interest waned only to
re-emerge in recent years. Ge et al. reported a maximum ZT
value 0.5 at 673 K for polycrystalline Cu1.8S fabricated using a
combined process of mechanical alloying and spark plasma
sintering,228 and then Liu et al.36 and Yu et al.229 independently
reported high ZT values of 1.5−1.6 at ∼1000 K for Cu2Se.
Interested readers are encouraged to refer to a relevant review
by Dennler et al.,186 summarizing the long history of copper
chalcogenides as thermoelectric materials.
Cu2Se undergoes a phase transition at ∼400 K, where during
the cooling process β-Cu2Se turns into α-Cu2Se and this
transition is reversible.230 Figure 21a shows the β-Cu2Se crystal
structure, where the Se atoms are in a simple face-centered-
cubic packing in the space group Fm3̅m, but the Cu ions are
Figure 21. (a) β-Cu2Se crystal structure: yellow, Cu atoms; red, Se
atoms. (b) ZT values as a function of temperature for copper
chalcogenides.36,41,229,232,233
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disordered throughout the structure, and the disordered Cu
ions are superionic mobile.231 Figure 21b shows the temper-
ature dependence of ZT values for copper chalcogenides. Yu et
al. described Cu2Se as a thermoelectric material with an ordered
selenium layer and a disordered copper layer, with a maximum
ZT value of ∼1.6 at 973 K.229 Liu et al. described Cu2Se a
copper ion liquid-like thermoelectric material with a maximum
ZT value of ∼1.5 at 1000 K.36 Following these reports, Zhong
et al.232 supposed that Cu1.94Al0.02Se would show anisotropic
transport properties and created a highly aligned large lamellae
in bulk Cu1.94Al0.02Se using the direct-current hot-pressing
process. A high ZT of 2.62 at ∼1030 K was reported in
Cu1.94Al0.02Se with lamellar structure, supposing that the
superionic properties were concentrated on one direction,
and a ZT of 1.4 at ∼1030 K along the direction perpendicular
to lamellar structure was reported. Meanwhile, Zhong et al.
mentioned that a big spread of ZT values among 50 samples
raised concerns about repeatability.232 Surprisingly, Cu1.97S also
exhibits an impressive high ZT of 1.7 at 1000 K,41 which was
further enhanced to ZT of 2.1 at 1000 K in Cu2S0.52Te0.48.233
The high ZT obtained in Cu2S0.52Te0.48 is attributed to a special
microstructure involving mosaic crystals which exhibit the good
electrical properties of single crystals and the low thermal
conductivity of polycrystalline or nanocrystalline samples.
Unlike the random orientation in ordinary polycrystalline
materials, blocks in a so-called mosaic crystal exhibit a nearly
identical orientation; thereby the bulk appears like a single
crystal from a macroscale point of view but contains a number
of small angle boundaries.
The apparent high performance in copper chalcogenides
mainly comes from the intriguing thermal transport properties,
especially in the thermal conductivity. As shown in Figure 22a,
Figure 22. (a) High-temperature thermal conductivity of Cu2Se as a
function of temperature.36,41,229,232,233 (b) Specific heat capacity as a
function of temperature for copper chalcogenides.36 Dashed blue line
shows the expected value of the specific heat at constant pressure Cp in
a solid crystal Cu2Se without liquid-like properties, which is usually
beyond the Dulong−Petit limit at high temperatures owing to the
extra contributions by carriers (Ce) and lattice thermal expansion. B is
the bulk modulus, V is the volume per atom, and α is the thermal
expansion coefficient.
the thermal conductivities are ultralow at high temperatures,
namely, the minimum thermal conductivities at ∼1000 K can
reach as low as ∼0.71, ∼0.60 , ∼0.48, and ∼0.39 W m−1 K−1 for
Cu2Se,36,229 Cu1.94Al0.02Se,232 Cu1.97S,41 and Cu2S0.52Te0.48,233
respectively. Figure 22b shows that these materials exhibit an
unusual heat capacity.36 The theoretical value (Dulong−Petit
law) for the high-temperature specific heat at constant volume
Cv is 3NkB in a solid crystal, where N is the number of particles
and kB is the Boltzmann constant. The lowest Cv theoretical
value in a liquid is 2NkB. Cu2Se shows a reduced Cv,
approaching 2NkB at high temperatures, which is a typical ion
liquid-like behavior,36 as in an ionic battery.234 However, the
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Chemical Reviews
physical explanation of this ion liquid-like behavior phenom-
enon is not clear yet.
In an ion liquid-like semiconductor, the lattice thermal
conductivity can be reduced below that of a glass by reducing
not only the mean free path of phonons but also eliminating
lattice vibrations. The idea of using the liquid-like behavior of
superionic conductors may be considered an extension of the
phonon-glass electron-crystal concept, and such materials could
be considered phonon-liquid electron-crystal (PLEC) thermo-
electrics.
The very property that makes copper chalcogenides exhibit
good thermoelectric performance may also be its Achilles heel
when it comes to moving these materials to device fabrication
and ultimate technological applications, namely, the very low
thermal conductivity achievable in these systems is due to the
very high mobility of Cu ions in the lattice causing great
disorder and strong phonon scattering. Because thermoelectric
devices are low-voltage high-current devices operating in a dc
model, massive and rapid migration of Cu ions from one end of
the sample to the other and severe Se/S vaporization will cause
decomposition and massive polarization issues rendering the
materials unstable for application. The realization is likely the
reason that these materials were not pursued further in the first
phase of their investigation in the 1960s. Incidentally, in the
photovoltaic field the same issue of strong Cu ion migration
and rapid instability during device operation caused the
promising and good photovoltaic properties of Cu2S to be
abandoned. These issues have been reviewed and comprehen-
sively discussed in recent publications.186,235
5.5. Complex Bismuth Chalcogenides
Since the solid solutions of Bi−Sb−Te−Se were established as
the leading thermoelectric materials near room temper-
ature,66,79 there have been continuing efforts to find better
thermoelectric materials with these elements, and ternary alkali
metal−bismuth−chalcogenides are typical ones that have been
found.29,236−240 Compared to Bi−Sb−Te−Se solid solutions,
ternary alkali metal−bismuth−chalcogenides possess more
complex crystal structures such as β-K2Bi8Se13 and CsBi4Te6.
As shown in Figure 23a, β-K2Bi8Se13 has a low-symmetry
Figure 23. (a) β-K2Bi8Se13 crystal structure: blue, Bi atoms; pink, Se
atoms; gray, Ag atoms. Red box represents a unit cell. (b) Typical
CsBi4Te6 crystal structure: blue, Bi atoms; pink, Cs atoms; dark
reddish, Te atoms. Red box represents a unit cell.
monoclinic structure that consists of two Bi/Se building blocks
(NaCl type and Bi2Se3 type) connected at the K/Bi mixed site
(blue); the K atoms are in the channels. These two Bi/Se
blocks are infinitely extended along the crystallographic b axis
and connected to each other at special mixed-occupancy K/Bi
sites. It has a highly anisotropic structure, and it grows along
the b axis with a needle or columnar structure.240 CsBi4Te6
features a strong anisotropic structure that contains both
formally Bi3+ and Bi2+centers.29 The unusual reduced Bi2+
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Review
centers form Bi−Bi bonds of 3.238 Å. The compound has a
lamellar structure with slabs of [Bi4Te6]− alternating with layers
of Cs+ ions, Figure 23b.
Complex bismuth chalcogenides show very low thermal
conductivities. Compared to the state-of-the-art thermoelectric
Bi−Sb−Te241 and Bi−Sb,242 it can be readily seen that the
thermal conductivity of β-K2Bi8Se13 is low, ranging from 1.0 to
1.5 W m−1 K−1, at temperatures below room temperature. The
thermal conductivity of CsBi4Te6 decreases with rising
temperature and reaches ∼1.5 W m−1 K−1 at room temper-
ature, Figure 24a. No reports are available that deal rigorously
Figure 24. (a) Thermal conductivity comparisons of complex bismuth
chalcogenides, and current state-of-the-art low-temperature thermo-
electrics.29,236,240−242 (b) ZT values comparisons of complex bismuth
chalcogenides, and current state-of-the-art low-temperature thermo-
electrics.29,236,240−242
with origins of the intrinsically low thermal conductivity of
these complex bismuth chalcogenides. Clarke reported
materials selection guidelines for low thermal conductivity
thermal barrier coatings.243 According to those guidelines, a
material will have a low thermal conductivity if it satisfies these
principal conditions: A large molecular weight, a complex
crystal structure, nondirectional bonding, and a large number of
different atoms per molecule. Complex bismuth chalcogenides
fulfill these conditions. Electrical transport properties and
thermal conductivity measurements on β-K2Bi8Se13 single
crystals showed a relatively high power factor (∼10 μW cm−1
K−2) at room temperature, giving ZT of 0.22 at room
temperature,240 Figure 24b. Extensive doping experiments on
CsBi4Te6 give high values of power factor (>30 μW cm−1 K−2)
at 100−220 K. The highest power factors of 40−60 μW cm−1
K−2 at 150−180 K were obtained through doping with Sb, Bi,
SbI3, and BiI3. A ZT value of 0.8 at 225 K was obtained for
0.06% SbI3-doped CsBi4Te6, which is record high at a
temperature gap of 150−275 K.29
5.6. Chalcoantimonates with Lone-Pair Electrons
Just as the so-called lone pair of electrons in Pb2+, Sn2+, Ge2+,
Bi3+ and Sb3+ plays a role in defining the thermoelectric
properties of the various materials described above (and
particularly the thermal conductivity), so do they define the
properties of the compounds in the Cu/Sb/Se system. In this
class we have three members which allow one to more clearly
appreciate the role of the lone pair of electrons on the thermal
conductivity, Cu3SbSe4, Cu3SnSe3, and CuSbSe2. The first
member is a Sb5+ species and has no lone pair of electrons,
while the latter two contain Sb3+ with an active lone pairs of
electrons. As shown in Figure 25a, Cu3SbSe4 shows a tetragonal
structure with the space group I42m. It derives from the
diamond structure in which all atoms have tetrahedral
coordination geometry.244 CuSbSe2 has an orthorhombic
structure with the space group Pnma190,245 and Cu3SbSe3 a
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Chemical Reviews
Figure 25. Typical crystal structures for (a) Cu3SbSe4, (b) CuSbSe2,
and (c) Cu3SbSe3: yellow, Cu atoms; red, Se atoms; gray, Sb atoms.
Schematic representation of the local atomic environment of Sb in (d)
Cu3SbSe4, (e) CuSbSe2, and (f) Cu3SbSe3. Shaded lines represent Sb−
Se bonds; dashed lines illustrate the approximate morphology of the
Sb lone-pair 5s electron orbital.
different orthorhombic structure with the space group Pnma,244
Figure 25b and 25c.
In Cu3SbSe4, the Sb5+ centers are coordinated by 4 Se atoms
with tetrahedral Se−Sb−Se bond angles of 109.5°, Figure 25d,
suggesting sp3 hybridization of the Sb valence electron orbitals.
In CuSbSe2, however, Sb is in a 3+ formal oxidation state and
coordinated by 3 Se atoms in a trigonal pyramidal geometry
and an average Se−Sb−Se bond angle of 95.24°, as shown in
Figure 25e. In this arrangement only the Sb 5p electrons form
bonds with Se, leaving the Sb 5s2 electrons “free” to orient
along the missing vertex of the tetrahedron. The configuration
is similar for Cu3SbSe3 except the average Se−Sb−Se bond
angle is 99.42°. Once again the Sb 5s2 lone pair helps the Sb3+
to form an imperfect tetrahedron if we consider that is occupies
the fourth coordination site, Figure 25f.
From a structural point of view, one may expect these three
compounds to have similar thermal conductivity since their
average atomic masses are nearly the same and none of them
possess an overly complex crystal structure; this however is not
the case. As shown in Figure 26a, Cu3SbSe4, CuSbSe2, and
Cu3SbSe3 possess vastly different thermal conductivity.190 In
Cu3SbSe4, the thermal conductivity decreases rapidly with
rising temperature due to strong phonon−phonon interactions
(typical for a crystalline material). In CuSbSe2, thermal
conductivity shows the same decreasing trend with temper-
ature, but it is only one-half that of Cu3SbSe4. Remarkably,
Cu3SbSe3 has a very low and temperature-independent thermal
conductivity even at cryogenic temperatures. The reason for the
large thermal conductivity differences is the different intrinsic
phonon scattering mechanisms acting in Cu3SbSe4, CuSbSe2,
and Cu3SbSe3. These mechanisms are related to the role of the
lone pair of s electrons in the Sb3+ centers in CuSbSe2 to
Cu3SbSe3.
The nature of the lone pair in heavy main group atoms and
its chemical and physical properties have been the subject of
much study and debate over many decades and remains topical
today.246−248 We can say that understanding the behavior of
these lone pairs and how they influence the electronic
properties is still incomplete. The relationship between lone-
pair electrons and low thermal conductivity involves the
enhancement of anharmonicity in the lattice by the overlapping
12140
Review
Figure 26. (a) Temperature dependence of the thermal conductivity
of Cu3SbSe4, CuSbSe2, and Cu3SbSe3.190 (b) Temperature depend-
ence of the thermal conductivity of two I−V−VI2 cubic semi-
conductors AgSbTe2 and AgBiSe2, of single-crystal PbTe, and of the
chalcopyrite compound AgInTe2.191 Electronic contributions to the
thermal conductivity are negligible in all samples; thus, the data shown
represent the lattice thermal conductivity. Solid line represents the
calculated minimum thermal conductivity for AgSbTe2. (c) Temper-
ature dependence of ZT values for Cu3SbSe4 and Cu3SbSe3.249−251 (d)
Temperature dependence of ZT values for I−V−VI2 cubic semi-
conductors.233,253−257
wave functions of the lone-pair electrons and nearby valence
electrons which induces nonlinear repulsive electrostatic forces.
This is well supported by the density functional theory
calculations by Zhang et al.,245 showing that Cu3SbSe3 has
larger Grüneisen parameters, smaller Debye temperatures, and
lower phonon velocities than Cu3SbSe4. The highest degree of
anharmonicity should thus be achieved when the lone-pair
electron is far removed from the Sb nucleus and not
participating in bonding. Therefore, it is reasonable that the
thermal conductivity of CuSbSe2 is higher than that of
Cu3SbSe3, since the lone electron pair is farther removed
from the Sb nucleus in Cu3SbSe3.
Another interesting comparison is the case of AgInTe2 versus
AgSbTe2,191 where the thermal conductivity of AgInTe2
(lacking lone pair of electrons) is “normal” while that of
AgSbTe2 (Sb3+ 5s2 pair) is glasslike, approaching the calculated
minimum thermal conductivity value, Figure 26b.
Wei et al.249,250 extensively investigated the electrical and
thermal transport properties of Cu3SbSe4 between 300 and 673
K. They found that the maximum ZT at 673 K increases from
0.4 for undoped Cu3SbSe4 to 0.7 when Sn doping is used on
the Sb site, Figure 26c. For Cu3SbSe3 an extremely low thermal
conductivity (0.25−0.30 W m−1 K−1) was observed, a
maximum ZT of 0.25 was obtained at 650 K.251
AgSbTe 2 is well known for its very low thermal
conductivity.190,191,252 Wang et al.253 investigated the poly-
crystalline AgSbTe2, which was fabricated using a combined
process of mechanical alloying and spark plasma sintering. It
was found that stoichiometric AgSbTe2 is a promising
thermoelectric material, whose ZT reaches 1.6 at 673 K,
benefiting from its extremely low thermal conductivity of 0.30
W m−1 K−1, Figure 26 d. Nielsen et al.189 reported that lone-
pair electrons also could minimize the lattice thermal
conductivity of AgSbSe2, as in AgSbTe2, since the Grüneisen
parameter (3.5) of AgSbSe2 is much larger than that (2.05) of
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Chemical Reviews
AgSbTe2; however, it was found that the electrical transport
properties of AgSbSe2 are inferior to AgSbTe2. By improving
the electrical transport properties, the ZT values have been
enhanced from ∼0.4 for undoped AgSbSe2 to ∼1.0 through
introducing Sb vacancies,254 Na doping,233 and Pb doping.255
As an analogue of AgSbSe2, AgBiSe2 is a n-type semiconductor
and exhibits very low thermal conductivity; ZT values could be
achieved in 0.9−1.0 through Nb doping on the Ag site256 and I
doping on the Se site.257
5.7. Tetrahedrites
Recently, some natural mineral tetrahedrites were reported as a
possible direct source of thermoelectric materials, led by the
independent groups of Morelli and Suekuni.258−260 The
tetrahedrite phase with general formula Cu12Sb4S13 is one of
the most widespread sulfosalt minerals on Earth. It can
accommodate a variety of substitutions onto Cu and Sb sites;
thus, natural tetrahedrite is commonly written as (Cu,
Ag)10(Cu, Zn, Fe, Co, Ni, Cd, Hg)2(Sb, Te, Bi, As)4(S, Se)13.
Interest in studying the thermoelectric properties of tetrahe-
drites has surged because they consist of environmentally
benign elements copper and sulfur.261 Figure 27a shows the
Figure 27. (a) Crystal structure of tetrahedrite Cu12Sb4S13; (b) ZT
values as a function of temperature for doped samples of tetrahedrite
Cu12Sb4S13.258,262−265
crystal structure of tetrahedrite Cu12Sb4S13. It possesses a cubic
sphalerite-like structure of I-43m symmetry with 6 of the 12 Cu
atoms occupying trigonal planar 12e sites and the remaining Cu
atoms distributed on tetrahedral 12d sites. The Sb atoms also
occupy a tetrahedral site but are bonded to only three S atoms,
leading to a void in the structure presumably occupied by the
lone pair of electrons. In terms of a simple crystal chemical
formula, 4 of the 6 tetrahedral sites are thought to be occupied
by monovalent Cu while the other 2 are occupied by Cu2+ ions;
the trigonal planar sites are occupied solely by monovalent Cu.
Lu et al. found that pure synthetic Cu12Sb4S13 exhibits a ZT
value of 0.56 at 673 K,258 as shown in Figure 27b. After
optimizing and substituting on Cu or Sb sites, the ZT at 723 K
could be further increased to 0.76 for Cu10.5Ni1.5Sb4S13, 0.90 for
Cu12Sb3Te4S13, 0.92 for Cu11.5Zn0.5Sb4S13, and 1.1 for
Cu10.5Ni1.0Zn0.5Sb4S13.262−265
The promising thermoelectric performance of Cu12Sb4S13 is
ascribed to the intrinsically low thermal conductivity. As shown
in Figure 28a, the thermal conductivity of Cu12Sb4S13 shows an
increasing trend up to 723 K. After doping and alloying, the
thermal conductivities are reduced in the entire temperature
range; some samples even show the glass-like and temperature-
independent thermal transport behaviors. It seems that the
phonon mean free path approaches one interatomic spacing,
and the thermal transport reaches the “minimal” thermal
conductivity, namely, the thermal conductivity ranges from 0.40
W m−1 K−1 at 300 K to 0.45 W m−1 K−1 at 723 K for
Cu10.5Ni1.5Sb4S13.265 The low thermal conductivity of tetrahe-
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Review
Figure 28. (a) Thermal conductivity as a function of temperature for
samples of tetrahedrite Cu12Sb4S13. (b) Sb[CuS3]Sb trigonal
bipyramid. (c) Valence electron density map projected onto a (101)
plane showing the coordination of Cu12e, Sb, S2a, and S24g atoms.
Space group of Cu12Sb4S13 is I-43m and features two Cu sites (12d and
12e), two S sites (2a and 24g), and one Sb site (8c), blue for Cu12e,
green for S2a, yellow for S24g, and brown for Sb.251 (b and c)
Reprinted with permission from ref 251. Copyright 2015 WILEY
Publishing.
drites may result from the synergistic effects of local bonding
asymmetry and anharmonic rattling modes.251 As shown in
Figure 28 b, a strong local bonding asymmetry is identified
inside a Sb[CuS3]Sb atomic cage, in which Cu (blue) forms
strong covalent bonding with S (green and yellow) and weak
covalent bonding with one of the Sb atoms (brown). The
bonding asymmetry of Cu12e causes the low thermal
conductivity of tetrahedrites, as indicated in Figure 28c. In
addition, the localized anharmonic rattling modes enabled by
the lone-pair electrons of Sb also can contribute to resonant
scattering of phonons, which is the as same to that of pnicogen-
group chalcogenides with lone-pair electrons. Skoug and
Morelli identified a correlation between minimal thermal
conductivity and the existence of an Sb lone s2 pair in Sb-
containing ternary semiconductors.190 Lone-pair electrons of
Sb induce strong lattice anharmonicity;191 the “crescent-moon”
shape around Sb is a clear indicator of the existence of electron
lone pairs, as shown in Figure 28c.
6. SUMMARY AND OUTLOOK
The past two decades have witnessed the rapid growth and
several exciting conceptual and performance breakthroughs in
thermoelectric research. The development of better and more
accessible physical property and thermoelectric measurement
techniques and commercially available robust instrumentation
especially for reliable high-temperature measurements have
played an important role in facilitating in the growth of the
thermoelectric community. Furthermore, the power of
synthetic solid state chemistry in its ability to deliver new
materials and new processing techniques has been critical in
this regard. New concepts make it possible to invent new
strategies on how to decouple the strong interrelation of
thermoelectric transport parameters, raising the ZT values
steadily from the historical threshold of around unity to well
above 2. As there are no theoretical or thermodynamic limits to
the maximum value of ZT, much higher performance can be
anticipated for the next generation of thermoelectric devices.
Given the many materials yet to be investigated, there is
certainly much work ahead and promise for developing higher
efficiency thermoelectric materials and devices.
As we discussed above, there are generally two main
directions to achieving high-performance thermoelectrics: (1)
optimizing the known materials by band structure and
microstructure manipulation and (2) exploring new com-
pounds with peculiar physical properties that may lead to
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Chemical Reviews
unexpectedly high ZTs. For the former it is highly desirable to
integrate all advanced performance-enhancing concepts in one
single material. The latter is also appealing given the power of
intuitive thinking63 and the elements of surprising discoveries.
In principle, the materials selection process can be accelerated
using high-throughput computational techniques to perform
initial screenings of the search space and identify the best
candidates to be investigated experimentally, namely, the so-
called materials genome approach. The materials with intrinsi-
cally very low thermal conductivity are also of strong interest,
especially when they simultaneously feature unique band
structures (for example, the conducting bands are composed
of multicarrier pockets) that allow high power factors.
Of course, considering the complexity of thermoelectric
materials, their future development would benefit greatly from
close collaborations between chemists, physicists, and materials
scientists. Given the need for alternative energy technologies
and materials to ultimately replace the shrinking supply of fossil
fuels or extend its duration, energy-related research and the
study of clean and reliable thermoelectric energy conversion
technology will play an important role.
AUTHOR INFORMATION
Corresponding Authors
*E-mail: zhaolidong@buaa.edu.cn.
*E-mail: m-kanatzidis@northwestern.edu.
Notes
The authors declare no competing financial interest.
Biographies
Gangjian Tan received in 2013 his Ph.D. degree in Materials Science
from Wuhan University of Technology, China, under the supervision
of Professor Xinfeng Tang, with a focus on nanostructured
skutterudite compounds as advanced thermoelectric materials by
melt spinning. In June of 2013, he joined Professor Mercouri
Kanatzidis’s group at Northwestern University as a postdoctoral
research fellow, where his research extends to the development of new
thermoelectric chalcogenides. He is interested in the understanding of
charge and phonon transport behavior in solids associated with
thermoelectric effects.
Li-Dong Zhao is a Professor of Materials Science and Engineering at
Beihang University, China. He received his B.E. and M.E. degrees in
Materials Science from the Liaoning Technical University and his
Ph.D. degree in Materials Science from the University of Science and
Technology Beijing, China, in 2009. He was a postdoctoral research
fellow in the LEMHE-ICMMO (CNRS-UMR 8182) at the University
of Paris-Sud from 2009 to 2011 and continued as a postdoctoral
research fellow in the Department of Chemistry at Northwestern
University from 2011 to 2014. He holds the fellowship of
“Recruitment Program for Young Professionals”. His research interests
include thermoelectric materials, superconductors, and thermal barrier
coatings.
Mercouri G. Kanatzidis is a Professor of Chemistry and of Materials
Science and Engineering at Northwestern University in Evanston, IL.
He also has a senior scientist appointment at Argonne National
Laboratory. His interests include the design and synthesis of new
materials with emphasis on systems with highly unusual structural/
physical characteristics or those capable of energy conversion, energy
detection, environmental remediation, and catalysis. After obtaining
his B.Sc. degree from Aristotle University in Greece, he received his
Ph.D. degree in Chemistry from the University of Iowa and was a
12142
Review
postdoctoral research fellow at the University of Michigan and
Northwestern University. He holds a Charles E. and Emma H.
Morrison Professor Chair at Northwestern University.
ACKNOWLEDGMENTS
This work was supported in part by a Department of Energy
grant to the Revolutionary Materials for Solid State Energy
Conversion, an Energy Frontier Research Center funded by the
U.S. Department of Energy, Office of Science, and Office of
Basic Energy Sciences under Award Number DE-SC0001054.
Currently, work at Northwestern is supported by the
Department of Energy, Office of Science Basic Energy Sciences
grant DE-SC0014520. We also acknowledge the use of the
transmission electron microscope from the NUANCE Center
at Northwestern University. This work was also supported by
the “Zhuoyue” program of Beihang University, the Recruitment
Program for Young Professionals, and NSFC under Grant No.
51571007 (L.D.Z). We thank especially Professors C. Uher, C.
Wolverton, and V. P. Dravid, whose collaboration has been
critical to our understanding of many aspects of our novel
materials in our laboratory. We also thank Professors D. N.
Seidman, T. P. Hogan, J. P. Heremans, E. D. Case, X. F. Tang,
H. B. Xu, S. K. Gong, J. Q. He, and Y. L. Pei for plentiful
discussions and fruitful collaborations. Of course, most of all,
we are grateful to the numerous dedicated graduate students
and postdoctoral fellows who have contributed to our
thermoelectric research efforts. Their names appear in the
various publications cited in this article.
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12149 DOI: 10.1021/acs.chemrev.6b00255

Chem. Rev. 2016, 116, 12123−12149