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SnSe: a remarkable new thermoelectric material

Li-Dong Zhao,*a Cheng Chang,a Gangjian Tanb and Mercouri G. Kanatzidis*b
Published on 05 September 2016. Downloaded by Tufts University on 24/03/2018 11:33:13.

Cite this: Energy Environ. Sci.,

2016, 9, 3044
Received 17th June 2016,
Accepted 5th September 2016
DOI: 10.1039/c6ee01755j
www.rsc.org/ees
The deceptively simple material SnSe has surprised the scientific community by showing an unexpectedly
low thermal conductivity and high power factor and it has become a very promising thermoelectric material.
Both the electrical and thermal transport properties of SnSe are outstanding. It is remarkable that a binary
compound exhibits strong anharmonic and anisotropic bonding, and after hole doping it shows an
exceptionally high power factor because of a high electrical conductivity and a strongly enhanced Seebeck
coefficient. The latter is enabled by the contribution of multiple electronic valence bands. In this perspective,
we discuss the natural features of SnSe, including crystal structures, electronic band structures, and physical
and chemical properties. We also compare the electrical transport properties of single crystals and
polycrystalline SnSe. The thermal conductivities of polycrystalline samples show wide variation from laboratory
to laboratory, with some values being higher than those of single crystals and some lower, which has caused
confusion and controversy. To address the issues regarding the thermal transport properties of SnSe, we
systematically summarize the reports for SnSe variants, discuss them along with some of our own new results,
and offer possible explanations. Finally, some possible strategies are proposed toward future enhancements of
the thermoelectric figure of merit of SnSe.

Broader context
To date, several approaches to enhance thermoelectric performance have emerged including enhancing the power factor through modifying the electronic
structure, reducing the thermal conductivity through all-scale phonon scattering, or both simultaneously. It is highly exceptional to find a new system that
exhibits a high power factor as well as extremely low thermal conductivity. This extraordinary combination of electrical and thermal transport properties is
precisely what we have found in SnSe; the physics of thermal and charge transport in SnSe is unusual and fascinating. It is remarkable that an ultralow thermal
conductivity can be realized in a simple compound such as SnSe, which does not have a high molecular weight, nanostructuring, a complex crystal structure or
a large unit cell. It is also remarkable that an ultra-high power factor can be achieved in a not-so-narrow bandgap semiconductor with only orthorhombic crystal
symmetry. In this perspective, we discuss the natural features of SnSe, including the peculiar crystal structure that results in an impressively low thermal
conductivity, in combination with a unique electronic structure that gives it a high power factor and outstanding thermoelectric properties.

1. Introduction thermal conductivity), and absolute temperature, respectively.1,3

In the past two decades, we have witnessed a surge of interest in
the development of alternative renewable energy technologies.1
In particular, thermoelectric materials have drawn strong attention
because thermoelectric effects enable direct conversion between
thermal and electrical energy, and provide an alternative for power
generation from heat as well as being used for refrigeration.2
The efficiency of thermoelectric materials is determined by the
dimensionless figure of merit (ZT), defined as ZT = (S2s/k)T, where
S, s, k and T are the Seebeck coefficient, electrical conductivity,
total thermal conductivity (sum of electron kele and lattice klat
a
School of Materials Science and Engineering, Beihang University, Beijing 100191,
China. E-mail: zhaolidong@buaa.edu.cn
b
Department of Chemistry, Northwestern University, Evanston, Illinois 60208, USA.
E-mail: m-kanatzidis@northwestern.edu
Therefore, high thermoelectric performance requires both a high
power factor (S2s) and a low thermal conductivity (k). Although it
is quite difficult to control the above parameters independently
due to their complex interrelationships, thermoelectric perfor-
mance records have been broken continuously in the past decade,
thanks to the development of new concepts and/or mechanisms.4–7
To date, several approaches to enhance ZT have emerged
including enhancing the power factor, reducing the thermal
conductivity or both simultaneously. The strategies to enhance
the power factor include band structure engineering (resonant
levels and band convergence)8–10 and microstructure manipu-
lations (modulation doping and texturing).11–14 The most effective
approaches to reduce thermal conductivity include nanostruc-
turing (matrix and second phase nano-precipitates)15–17 and
all-scale hierarchical architecturing.18 In addition, new concepts
such as band alignment and compositionally alloyed nanostructures

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Perspective
provide clever means to maintain a high power factor and reduce the
lattice thermal conductivity at the same time.19,20 In addition to the
above nanocomposite-based strategies, one can seek high perfor-
mance in single phase compounds with low thermal conductivity.
Low thermal conductivity means that the most complex procedures
Li-Dong Zhao was born in
Harbin, China in 1979. He is a
Published on 05 September 2016. Downloaded by Tufts University on 24/03/2018 11:33:13.
Professor of Materials Science
and Engineering at Beihang
University, China. He received
his BE and ME degrees in
Materials Science from Liaoning
Technical University, and his PhD
degree in Materials Science from
the University of Science and
Technology Beijing, China in
2009. He was a postdoctoral
Li-Dong Zhao 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 is a recipient of
‘‘the Thousand Talents Plan’’ 2015. His research interests include
thermoelectric materials, superconductors and thermal barrier
coatings.
Gangjian Tan received his PhD
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 2013. In June of
2013, he joined Professor Mercouri
Kanatzidis’s group at Northwestern
University as a postdoctoral
Gangjian Tan research fellow, where his research
extended to the development of
novel metal chalcogenides for possible applications in energy
conversion, particularly in the field of thermoelectrics. He is
interested in the understanding of charge and phonon transport
behavior in solids associated with the thermoelectric effect.
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to reduce the thermal conductivity can be avoided and allow one to
focus mainly on increasing the power factor. Low thermal conduc-
tivity may arise from an anharmonic and anisotropic bonding,21–25
very large unit cells,26 atomic disorders induced by mobile ions
such as copper and silver ions and their liquid-like behaviors,27–29
Cheng Chang is a PhD candidate
in the School of Materials Science
and Engineering at Beihang
University. He received his BE
degree in Materials Science and
Engineering from Beihang
University in 2014. He started
his doctoral research as a
member of Li-Dong Zhao’s group
in 2014. His main research
interests focus on the fabrication
and properties of thermoelectric
Cheng Chang materials with layered structures.
Mercouri Kanatzidis was born
in Thessaloniki, Greece in 1957.
After obtaining a BSc degree from
Aristotle University in Greece,
he received his PhD degree in
Chemistry from the University of
Iowa in 1984. He was a post-
doctoral research associate at
the University of Michigan and
Northwestern University from 1985
to 1987 and is currently Charles E.
and Emma H. Morrison Professor
Mercouri G. Kanatzidis of Chemistry at Northwestern
University. He also holds an
appointment at Argonne National Laboratory. His research areas
include: inorganic chemistry, solid state and coordination
chemistry of chalcogenide compounds, design of new materials,
exploratory synthesis, thermoelectric materials, nanostructured
materials, intermetallics, mesoporous semiconductors, phase-
change materials, conducting and porous polymers. He is the
recipient of the Royal Chemical Society DeGennes Prize 2015;
Elected Fellow of the Royal Chemical Society 2015; the ENI
Award for the ‘‘Renewable Energy Prize’’ category; the ACS
Award in Inorganic Chemistry 2016; and the American Physical
Society 2016 James C. McGroddy Prize for New Materials. He has
over 950 papers and 22 patents to his merit.
Energy Environ. Sci., 2016, 9, 3044--3060 | 3045

Energy & Environmental Science
large molecular weight,30 complex crystal structure,31 lone-pair
electrons,32–34 etc. Examples of previously studied materials of
this type include SnSe,35–40 BiCuSeO,41,42 MgAgSb,28 Cu2Se,27,43
Yb14MnSb11,30 Ag9TlTe5,31 K2Bi8Se13,44,45 CsBi4Te6,26 I–V–VI2
compounds,33,46 and tetrahedrites.47–49
SnSe is a long known semiconductor with an energy gap of
0.86 eV and a large optical absorption coefficient.50 It typically
behaves as a p-type material with a hole concentration in
the range 1017–1018 cm 3 and a room temperature electrical
resistivity between 101–105 O cm.51 Given this huge electrical
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resistivity, it has been regarded as of no apparent relevance to
thermoelectrics but more useful for applications in solar cells,
optoelectronics and other electronic devices.51–54 Recently, SnSe
surprised the scientific community as a new promising thermo-
electric material, exhibiting one of the lowest lattice thermal
conductivities known for crystalline materials (o0.4 W m 1 K 1
at 923 K) and even without doping, achieving high ZTs 4 2.3 at
723–973 K along the b- and c-crystallographic directions.35,36
Since the initial report of single crystal SnSe as a high
performance thermoelectric material in 2014,35 there have been
many reports on this compound focusing mostly, however, on
polycrystalline SnSe samples.24,29,55–71 Compared to single crystals
of SnSe, lower power factors are observed in polycrystalline
compactions of SnSe.24,29,55,57,58,63–67 In contrast, there is a range
of thermal conductivity values (even though all deal with poly-
crystalline SnSe samples), with some groups55,59,72–75 reporting
extremely low thermal conductivity similar to or lower than those
of single crystals SnSe while others have reported higher
values.58,64 Therefore, there seems to be an unsettled issue
regarding the low thermal transport properties of SnSe, and
this motivates us to systematically summarize the existing
reports for the SnSe system and discuss them critically along
with our own new results. In this perspective, we discuss the
natural features of SnSe, including the special crystal structure
that results in an impressively low thermal conductivity, as
well as a special electronic structure that gives it a high power
factor and outstanding thermoelectric properties. We also
Fig. 1 (a) SnSe crystal structure Pnma at room temperature (Sn atoms are shown in gray and Se atoms in red) along the a axis and (b) highly distorted
SnSe7 coordination polyhedron with three short and four long Sn–Se bonds; (c and d) SnSe crystal structures along the b axis (showing the accordion like
character) and c axis. Reproduced with permission from ref. 35. Copyright 2014 Nature Publishing Group.
3046 | Energy Environ. Sci., 2016, 9, 3044--3060
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attempt to summarize and put into perspective our current
understanding of this compositionally simple but evidently
innately complex material and discuss possible sources
and reasons for the differences in the reported thermal
conductivity properties. Possible strategies are proposed
aimed at further enhancing the thermoelectric figure of
merit of SnSe.
2. Crystal structure
SnSe adopts a simple layered orthorhombic crystal structure
at room temperature, which can be derived from a three-
dimensional distortion of the NaCl structure.35 Alternatively,
the SnSe layers in the structure can be described as that of
black phosphorus.76 Perspective views of the room tem-
perature SnSe crystal structure along the crystallographic a,
b, and c axes are shown in Fig. 1(a), (c) and (d). There are 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. The struc-
ture contains highly distorted SnSe7 coordination polyhedra
with three short and four very long Sn–Se bonds and a lone
pair (5s2) from the Sn2+ atoms sterically accommodated in
between the four long Sn–Se bonds, see Fig. 1(b). The two-
atom-thick SnSe slabs are strongly corrugated creating a
zig-zag folded accordion-like projection along the b-axis. The
easy cleavage in this system is along the bc-plane because of
the weak cross-plane Sn


Se bonding interactions. While
cooling from its high temperature higher symmetry phase
(space group Cmcm, #63) SnSe undergoes a displacive (shear)
phase transition at B800 K, resulting in a lower symmetry
Pnma (#62) space group that necessitates a transformation of
its crystallographic axes. The Pnma structure has an expanded
volume compared to the Cmcm high temperature form by
2.5% and this can cause the silica tube breakage and sample
damage during crystal growth.
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3. Electronic band structure and DOS
effective mass
Despite its stoichiometric simplicity, SnSe happens to possess a
surprisingly complex electronic structure as indicated by first-
principles theoretical electronic structure calculations. This
complexity lies at the heart of the enhanced thermoelectric
performance of this material. The electronic structures of the
low-temperature Pnma SnSe phase are calculated using density
functional theory (DFT).39 As shown in Fig. 2(a), the DFT valence
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even approaches the 4th, 5th and 6th valence bands when the
doping levels in the material are as high as 5  1020 cm 3.
Another illustration of the complex band structure is shown
in the Fermi surface, which has multiple types of pockets (or
valleys) coming from the numerous valence bands all within a
small energy window, Fig. 2(b)–(d).
From the DFT band structure of the Pnma phase, the first
valence band maximum (VBM) is at (0.0, 0.0, 0.35) along the
G–Z direction of the first Brillouin zone. There is also a local
valence-band maximum at (0.0, 0.0, 0.44) that lies 0.06 eV lower

band maximum (VBM) lies in the G–Z direction (band 1),
but another valence band is located just below the VBM (band 2).
A third band also exists with its band maximum along the
U–X direction (band 3). The calculation shows a very small
energy difference of B0.06 eV between the first two valence
band edges in the G–Z direction. Such a small energy gap is
easily crossed by the Fermi level as the hole doping approaches
B4  1019 cm 3. In addition, the energy difference between the
first and the third band edges (i.e. the maximum of U–X to
the maximum G–Z) is only 0.13 eV. This value is similar to the
0.15 eV spacing between the first and the second valence band
edges of PbTe, in which the heavy hole band contribution is
significant as the carrier density exceeds B5  1019 cm 3.77
Interestingly, the electronic valence bands of SnSe are much
more complex than those of PbTe, and the Fermi level of SnSe
in energy than the first VBM. For these two maxima, the
effective masses are calculated by fitting the E–k bands around
the VBM for the different directions. The SnSe effective masses
at each valence band extremum are also anisotropic. Due to the
2D nature of the material, the effective mass has a larger value
along the kx direction (a axis) than along either of the in-plane
directions ky and kz (b and c axes). For the first valence
maximum along G–Z, the effective masses are mkx* = 0.76 m0,
mky* = 0.33 m0, and mkz* = 0.14 m0. For the second maximum
along G–Z, mkx* = 2.49 m0, mky* = 0.18 m0, and mkz* = 0.19 m0.
A crystalline material exhibiting multiple extrema in its
valence or conduction bands has a correspondingly enhanced
Seebeck coefficient. This is a highly sought after electronic
structure feature in the search for exceptional thermoelectric
materials. The enhancement in the power factor comes from

Fig. 2 (a) Electronic band structure of SnSe indicates non-parabolic, complex multi-band valence states. The red dotted lines from top to bottom
represent the Fermi levels with carrier concentrations of 5  1017 cm 3, 5  1019 cm 3, 2  1020 cm 3, and 5  1020 cm 3, respectively, indicating that
heavy doping pushes the Fermi level deep into the multi-band structure. (b–d) The Fermi surfaces of SnSe (Pnma) at 5  1019 cm 3, 2  1020 cm 3 and
5  1020 cm 3, respectively. The Fermi surface also illustrates the multiple types of pockets (or valleys) coming from the numerous valence bands all
within a small energy window.39 Reproduced with permission from ref. 39. Copyright 2016 The American Association for the Advancement of Science.

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the additional contributions of the conductivity-weighted See-
beck coefficient (see below). If there are multiple Fermi surface
pocket electron/hole states accessible through doping, these
can collectively contribute to the overall Seebeck coefficient and
the power factor. The multiple pockets can be due to symmetry
(i.e., if the pocket is not at a high symmetry point (e.g. G) in the
Brillouin zone of the band structure), or can come from multi-
ple bands that are close enough in energy to contribute to the
transport at a given temperature. This is the case, for example,
in PbTe’s valence band and in SnSe. Although the Seebeck
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coefficient enhancement in multi-band systems is well known
as a general concept,78 what is highly exceptional is to find
a system that exhibits this enhancement while also exhibiting
an extremely low thermal conductivity and a high electrical
conductivity. This extraordinary combination of properties is
precisely what we have in hole-doped SnSe.39 As we will see
below, these electronic structure features are at the origin of the
high power factors that can be achieved in this material.
4. Electrical transport properties
For undoped SnSe crystals the electrical conductivities along
different crystallographic directions show a similar temperature-
dependence,35 Fig. 3(a). When undoped the carrier concentration
does not exceed B1017 cm 3, and in the electrical conductivity
plot the upturn above 525 K is attributed to the thermal excitation
of carriers. Hole doping increases the electrical conductivity from
B12 S cm 1 to B1500 S cm 1 as the carrier concentration
Fig. 3 Electrical transport properties of undoped SnSe35 and hole-doped SnSe39 as a function of temperature along different crystallographic directions:
(a) electrical conductivity; (b) carrier concentration; (c) Seebeck coefficient and (d) power factors, with those of the optimized Bi2 xSbxTe3 and PbTe–
4SrTe–2Na plotted for comparison.16,18 In the figures, SnSe represents undoped SnSe.35 Reproduced with permission from ref. 39. Copyright 2016 The
American Association for the Advancement of Science.
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increases from B1017 cm 3 to B1019 cm 3 at 300 K, Fig. 3(b).
After heavy hole doping, the temperature dependence of
the electrical conductivity changes from a semiconductor-like
transport behavior to a metal-like behavior.39 It can be readily
seen from the figure that the electrical conductivities along the
b and c directions are higher than that along the a direction. This
anisotropy reflects the much higher carrier mobility within the
bc-plane of SnSe compared to that perpendicular to it. For the
undoped SnSe, the Seebeck coefficients show an almost isotropic
behavior and are independent of the crystallographic direction,
Fig. 3(c). The gradual decrease of the Seebeck coefficients above
525 K is consistent with the trend in the electrical conductivity
and indicative of bipolar conduction. This behavior reflects the
band gap (Eg) narrowing from 0.61 eV (Pnma) to 0.39 eV (Cmcm),
and thus bipolar conduction is expected with rising temperature.
For hole-doped SnSe, the Seebeck coefficient is B+160 mV K 1 at
300 K, and increases to B+300 mV K 1 at 773 K.
Compared to other state-of-the-art thermoelectrics, the
power factors obtained in undoped SnSe crystals are very low
at room temperature and only moderate at high temperature.
After hole doping, however, the combination of vastly increased
electrical conductivity and still high Seebeck coefficient results
in a large power factor of B40 mW cm 1 K 2 for hole-doped
SnSe (b axis) at 300 K, Fig. 3(d). The power factors remain high,
i.e., B14 mW cm 1 K 2 around 773 K for hole-doped SnSe
(b axis), which is two times higher than the value of
B6.4 mW cm 1 K 2 at 773 K for undoped SnSe (b axis). The
high power factors obtained in hole-doped SnSe rival those of
the optimized Bi2 xSbxTe3 materials near room temperature,16,79
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and are much higher than those of the high performance
hierarchical architectured p-type PbTe–SrTe system in the range
of 300–500 K.18
5. Origin of the ultra-high power
factor
The power factors achieved in hole-doped SnSe are much higher
than those in rock-salt PbTe8,18,20 and SnTe,5,42,80,81 especially in
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observed value for this carrier concentration, +160 mV K 1.
In contrast, a single band model gives a much lower Seebeck
coefficient and cannot reproduce the experimental values. A SPB
model with a DOS effective mass (0.47 m0) from the first valence
band maximum yields a Seebeck coefficient of only +84 mV K 1 at
4  1019 cm 3; an estimated SPB effective mass of 0.75 m0, gives a
Seebeck coefficient of B+110 mV K 1 at 4  1019 cm 3. Even the
single-band Seebeck coefficients based on a larger effective mass
md* = 1.20 m0 (Fig. 4(b), red circle line) are still lower than the
experimental Seebeck coefficients. Therefore, the observed experi-

the 300–500 K range. These high power factors derive from the
much larger Seebeck coefficient since the electrical conductivity of
hole-doped SnSe (b axis) is comparable to those of rock-salt
chalcogenides. As shown in Fig. 4(a), similar to a Pisarenko plot,
the room temperature Seebeck coefficients of rock-salt chalco-
genides plotted with a similar carrier concentration of B4 
1019 cm 3 offer further insight into the enhanced Seebeck
coefficients. The Seebeck coefficient for hole-doped SnSe
B+160 mV K 1 is clearly much higher than B+70 mV K 1 for
PbTe,8,18 B+60 mV K 1 for PbSe,19 B+50 mV K 1 for PbS,82 and
B+25 mV K 1 for SnTe.5
Generally, Seebeck coefficients can be calculated based on
the single parabolic band (SPB) model with different effective
masses.39 As shown in Fig. 4(b), the Seebeck coefficient calcu-
lated using the full multi-valley DFT band structure is +168 mV K 1
at 4  1019 cm 3, which is very close to the experimentally
mental Seebeck coefficient enhancements of hole-doped SnSe
can be attributed to the multi band character of the electronic
structure, as shown by the schematic diagram of Fig. 4(c).
The DFT calculations suggest a very small energy gap of
B0.06 eV between the first two valence bands, the energy gap
between the first and the third band is only 0.13 eV, and the
Fermi level of SnSe approaches very close to the 4th, 5th and
6th valence bands for doping levels of B5  1020 cm 3. By
comparison, in heavily hole-doped PbTe and PbSe, the Fermi
level is pushed downward towards the heavy valence band,
enhancing the Seebeck coefficient because of the contribution
of this second valence band to transport especially as the
temperature rises. In fact, this enhancement only appears at
high temperatures as the extra contribution of the heavy
valence band requires a carrier density of B5  1019 cm 3
and 2  1020 cm 3 at 300 K, because the energy difference

Fig. 4 (a) Comparison of room temperature Seebeck coefficients of the lead and tin chalcogenides with a similar carrier concentration of
B4  1019 cm 3; (b) calculated Seebeck coefficients as a function of the carrier density at 300 K. The black square line is calculated using the full
multi-valley DFT band structure. Single band calculations yield lower Seebeck coefficients, and even for larger effective masses cannot fit the measured
values; (c) a schematic diagram showing the multiple valence bands of SnSe; (d) ln[RH(T) RH(0)]/RH(0) as a function of 1/T with the solid line being the
best linear fit to the data; the slope ( DE/kB) of 214 K 1 yields an energy gap of B0.02 eV between the first two valence bands; the inset shows the Hall
coefficient for hole-doped SnSe as a function of temperature.39 Reproduced with permission from ref. 39. Copyright 2016 The American Association for
the Advancement of Science.

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between the two valence bands in PbTe (0.15 eV) and PbSe
(0.25 eV) is higher than that in SnSe, but decreases at high
temperatures.5,6 The energy difference between the two bands
in PbS and SnTe is even larger (40.3 eV), resulting in decreased
Seebeck coefficients (these systems are essentially SPB systems),
Fig. 4(a).
Based on the above results, the large Seebeck coefficients for
the hole-doped SnSe arise from the contribution of more than
one valence band.77 This is strongly supported by the Hall effect
measurements. The Hall coefficient (RH) is consistent with
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nearly equivalent in energy. This near degeneracy of the bands
accounts for the much higher Seebeck coefficients and power
factors observed at room temperature. As the temperature
increases, the carriers are thermally distributed over several
bands of similar energy, resulting in multi band transport and
enhanced Seebeck coefficients.
6. Ultralow thermal conductivity:
single crystals versus polycrystalline

multi-valley transport as it shows a continuous increase with samples

temperature in the range 10–300 K (inset of Fig. 4(d)). Single
band transport would have produced a temperature-constant
Hall coefficient. The values of RH in hole-doped SnSe are
temperature dependent, thus ruling out the single band model
of transport. The Hall data imply that the convergence of
multiple band maxima of hole-doped SnSe has already happened
below room temperature, consistent with the notion that the
energy difference between the relevant valence bands in SnSe is
much lower than that in PbTe.
The energy gap (DE) between the first two bands is esti-
mated using the slope ( DE/kB) of the ln[RH(T) RH(0)]/RH(0)
vs. 1/T plot, which yields a DE B 0.02 eV at 0 K, assuming that
DE varies linearly with temperature,77 Fig. 4(d). This energy gap
between the first two valence bands of SnSe is much smaller
than that in PbTe (0.15 eV), PbSe (0.25 eV), PbS (0.45 eV) and
SnTe (0.35 eV).5,6,77 The DE B 0.02 eV estimate is consistent
with the DFT calculated value of B0.06 eV, and comparable to
kBT at room temperature, suggesting that the valence bands are
The temperature dependence of the total thermal conductivity (ktot)
for undoped and hole doped SnSe is shown in Fig. 5(a). At room
temperature, the values of ktot for undoped SnSe are B0.46, 0.70
and 0.68 W m 1 K 1 along the a, b and c axis directions,
respectively. Compared to state-of-the-art thermoelectrics,83,84 these
thermal conductivity values are exceedingly low, and surprisingly,
they decrease even further with rising temperature. At 773 K, they
all fall in the range 0.25–0.28 W m 1 K 1.3 It should be noted that
the thermal conductivity of SnSe is lower than that of the hier-
archical architectured p-type PbTe–SrTe system,18 as shown in
Fig. 5(b). The low thermal conductivity in single phase SnSe is
therefore believed to derive from the very high anharmonicity of
its chemical bonds, but other factors may also play a role such as
non-stoichiometry, defects, etc.59,72 These factors will have to be
investigated in detail in future studies.
After hole doping, the total thermal conductivities are
higher because of the contribution from electronic carriers.39

Fig. 5 (a) Total thermal conductivities of undoped SnSe35 and hole-doped SnSe39 as a function of temperature along different crystallographic
directions; (b) comparison of the lattice thermal conductivity of SnSe along the b axis and hierarchical architectured PbTe–4SrTe–2Na;18 (c) the
calculated Lorenz number derived from a multi-band model; (d) comparison of the lattice thermal conductivity of undoped SnSe35 and hole-doped
SnSe.39 Reproduced with permission from ref. 39. Copyright 2016 The American Association for the Advancement of Science.

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To derive the lattice thermal conductivity, the precise Lorenz
number should be used, which is approximately equal to
1.5  10 8 V2 K 2 since undoped SnSe is a nondegenerate
semiconductor. However, after hole doping, because of the
complex electronic band structure of SnSe, the standard SPB
model used to derive the Lorenz number is not appropriate.77
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 multi-band model, as shown in Fig. 5(c).
Using more correct Lorenz numbers, one can see that the lattice
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preferential orientation effects which will be difficult to control
from sample to sample.
To clearly indicate the thermal conductivities of SnSe
reported so far, we have collected and listed them in Table 1.
Clearly, while some groups have reported higher thermal
conductivities,58,62,64,66 others55,59,72–75,95 have reported very
low thermal conductivities comparable to (or even lower than)
that of SnSe single crystals.35,39 At room temperature, 61% have
reported higher thermal conductivities than single crystals,
19% reported similar thermal conductivities and 20% reported

thermal conductivity of hole-doped SnSe is comparable to or
even lower than that of undoped SnSe, Fig. 5(d).
The reports on the SnSe single crystals were quickly followed
by many reports on polycrystalline SnSe samples.29,55,58,59,63–66,68,72
Generally, polycrystalline samples are expected to exhibit equal
or lower thermal conductivity than single crystals because of
the extra grain boundary phonon scattering. Even though grain
boundary scattering is an effective way to lower the thermal
conductivity in some materials with intrinsically high thermal
conductivity, such as Si,5,42,85–90 the effect is diminished in
materials with low thermal conductivity.32,71,91,92 In the case of
SnSe, with its low thermal conductivity (o1% than that of Si),
most of its heat carrying phonons have very small mean free
paths, below tens of nanometers. Therefore, the grain bound-
aries of SnSe are too big to affect thermal conductivity.93,94
In strongly anisotropic samples, moreover, such as SnSe, it
is difficult to compare the directional thermal conductivity
values of the single crystals to the average values of the poly-
crystalline samples, which are likely to be subject to significant
lower thermal conductivities. At 800 K, 14% have reported higher
thermal conductivity than single crystals, 78% reported similar
thermal conductivities and 8% reported lower higher thermal
conductivities. Apparently, there is a range of thermal conductivity
values reported by some research groups. Therefore, it seems to
be an unsettled issue regarding the low thermal transport proper-
ties of SnSe. Below we introduce and summarize these results
including some of our own.
6.1 Stoichiometry sensitive thermal conductivity
A recent neutron powder diffraction study demonstrated an
exceptionally high anharmonicity of the chemical bonds of
SnSe, and reported an ultralow thermal conductivity value
o0.2 W m 1 K 1 at room temperature for polycrystalline
SnSe0.98.59 This is much lower than that of the SnSe single
crystals, which we presume may have had a slightly different
stoichiometry.105 Bera et al. also reported a very low thermal
conductivity of B0.21 W m 1 K 1 at room temperature for
SnSe0.95 by introducing Se deficiency.72 Experimentally, for

Table 1 Comparisons of the total thermal conductivities for SnSe samples reported in the literaturea

References Single/ingot/polycrystalline k (W m 1
K 1) at B300 K k (W m 1
K 1) at B800 K
Zhao et al., Nature (2014)35 Single 0.46–0.70 0.23–0.34
Zhao et al., (this work) Polycrystalline 0.52–0.62 0.29–0.40
Chen et al., Adv. Funct. Mater. (2016)95 Polycrystalline 0.6–0.7 0.2–0.3
Serrano-Sanchez et al., Appl. Phys. Lett. (2015)59 Ingot 0.1 0.1–0.2 (at B400 K)
Bera et al., arXiv:1601.00753v1 (2016)72 Polycrystalline 0.2 0.24 (at B400 K)
Ju et al., Ceram. Int. (2016)74 Polycrystalline 0.65
Kim et al., J. Alloys Compd. (2016)75 Polycrystalline 0.61–0.76 0.3–0.4
Gharsallah et al., Sci. Rep. (2016)73 Ingot Ge–SnSe 0.2–0.5 0.2–0.5 (at B400 K)
Zhang et al., Adv. Energy Mater. (2015)55 Polycrystalline 0.49–1.1 0.25–0.51
Wei et al., Phys. Chem. Chem. Phys. (2015)29 Polycrystalline 0.7–1.3 0.4–0.6
Leng et al., J. Electron. Mater. (2016)62 Polycrystalline 0.7–1.1 0.4–0.5
Sassi et al., Appl. Phys. Lett. (2014)58 Polycrystalline 0.75–1.25 0.4–0.6
Han et al., J. Mater. Chem. A (2015)66 Polycrystalline 0.5–1.26 0.3–0.65
Li et al., New J. Phys. (2015)24 Polycrystalline 0.9–1.2 0.3–0.4
Chen et al., J. Mater. Chem. A (2014)64 Polycrystalline 0.9–1.35 0.5–0.8
Leng et al., RSC Adv. (2016)96 Polycrystalline 0.7–1.0 0.3–0.4
Chere et al., J. Mater. Chem. A (2016)65 Polycrystalline 0.85–1.0 0.4–0.5
Peng et al., Energy Environ. Sci. (2016)97 Single Na–SnSe 1.2–2.0 0.4–0.45
Zhao et al., Science (2016)39 Single Na–SnSe 0.45–0.7 0.2–0.3
Li et al., J. Mater. Chem. C (2016)98 Polycrystalline 1.0 0.35
Popuri et al., J. Mater. Chem. C (2016)99 Polycrystalline 0.6–1.5 0.38–0.71
Wasscher et al., Solid-State Electron. (1963)100 b Single (c-axis) 1.9
Wei et al., J. Am. Chem. Soc. (2016)101 Polycrystalline 1.2–1.4 0.4–0.5
Gao et al., J. Alloys Compd. (2016)102 Polycrystalline 1.2–1.4 0.3–0.4
a
It is reasonable to compare the lattice thermal conductivity of SnSe due to the varied carrier contributions to the electronic thermal conductivity.
However, some lattice thermal conductivities are unavailable in the above listed papers. Moreover, the Lorenz number could not be precisely
calculated due to the complex electronic band structure of SnSe. b The thermal conductivity measured using an absolute steady state method in the
1960s, which turned out to be severely overestimated.103,104

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undoped SnSe and hole-doped SnSe, EDS analysis indicates
that the composition of SnSe is SnSe0.97, while that of
Sn0.98Na0.02Se is Sn0.98Na0.015Se0.96. We surmise that the low
thermal conductivity may be related to the exact stoichiometry
of SnSe. To address such an issue, we will need to measure the
thermal conductivity of a series of samples with stoichiometries
of Sn1+xSe1 x and Sn1 xSe1+x where we can look for trends in
the thermal conductivity as a function of x.
6.2 Adventitious cracks in the single crystals and effects
on thermal conductivity
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As mentioned above, SnSe undergoes a strong phase transition
from Pnma to Cmcm at B800 K. As a consequence, cooling
melts of SnSe almost always causes a breakage of the silica tube
and loss of the sample. A double tube (tube inside tube) seems
to solve the problem. The outer silica tube is used to prevent the
crystal from oxidation by air when the inner tube breaks owing
to the considerable thermal expansion caused by the phase
transition. The high stress associated with this transition,
however, can cleave the sample along the bc-plane, especially
when the forces exerted on the inner tube are strong enough to
break it or damage it. After a SnSe crystal ingot is obtained by
such a procedure, the samples must be carefully handled for
polishing and cutting. The most challenging measurement
specimens are the ones that are cut to measure the thermal
diffusivity along the two directions of the bc-plane. The reason
is that the thin dimension of the sample is the bc-easily cleaving
direction. This can result in complete breakage of the sample
during handling or microcracks. These can also form from the
phase transition and tube cracking and can cause visible and
invisible microgaps in the specimen. These microgaps are
parallel to the direction of thermal diffusivity, and thus it is
possible that these microgaps can ‘‘shorten’’ the measurement
time leading to artificially high values as we have observed.
Fig. 6 (a–c) Microcracks in SnSe crystals propagating along the bc-plane; (d) schematic diagram shows how the laser flash goes through cracks;
(e) thermal diffusivities are higher when samples contain an increasing number of cracks, especially after phase transition around 800 K. To exclude the
effects of heat capacity and sample density on the total thermal conductivity, we directly observed thermal diffusivities.
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Supporting this notion is the fact that repeating the measurements
from 300–900 K several times causes the samples to undergo the
phase transition repeatedly, and this gives higher thermal diffu-
sivities with each subsequent measurement cycle. This is presum-
ably due to the widening of the existing gaps and the creation of
new gaps.
The scanning electron micrographs shown in Fig. 6(a)–(c)
display examples of such cracks in different magnification sections.
During measurements, energy can travel non-diffusively through
these cracks and cause the thermal diffusivity of the samples
to appear higher than it actually is, Fig. 6(d). The effects of these
cracks on the thermal diffusivities of SnSe samples are shown in
Fig. 6(e) where one can see that the thermal diffusivity can be
doubled for samples with these artificial cracks.
6.3 Polycrystalline samples: exposure to air and thermal
conductivity
Although the explanations of strong anharmonic chemical
bonding can qualitatively account for the low thermal conduc-
tivity of SnSe, in practice, as we mentioned above, measuring
the thermal conductivity accurately along the two directions of
the bc-plane is complicated. It has been found that polycrystal-
line samples prepared in air are even more difficult to work
with because of surface oxidation. The single crystals do not
seem to have a severe oxidation problem because of their very
low surface area. For selenides, extended exposure to air can
result in some oxidation.106,107 Surface oxidation in polycrystal-
line SnSe samples yields SnO2 which itself has about 140 times
higher thermal conductivity of B98 W m 1 K 1.107,108 More-
over, SnO2 is humidity sensitive, and thus results in some extra
high thermal conductivity products.109,110 Therefore, if samples
are ground or handled in air, the measurements will result in
higher thermal conductivity values. When protected from
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oxidation, polycrystalline samples have thermal conductivities
comparable to single crystals.59,73–75
Recently, Chen et al. offered this oxidation explanation for
the discrepancies in thermal conductivity.95 They found that
the thermal conductivity of polycrystalline SnSe will decrease
when the powders are processed in an inert atmosphere glove
box and will closely approach the 0.25 W m 1 K 1 value at
773 K, which is comparable to or even lower than the values of
0.30 W m 1 K 1 (c axis) and 0.35 W m 1 K 1 (b axis) of SnSe
single crystals.35 This phenomenon could be explained by the
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0.1–0.6% by weight) is added to the SnSe powders, the thermal
diffusivities of these polycrystalline SnSe samples showed a signi-
ficant increase even though they were processed in a glove box.
Heat capacity data for SnSe from different reports are all
consistent, Fig. 8(a). If the heat capacity is measured every 50 K,
the phase transition (within 50 K width) is jumped over,
Fig. 8(b). Because the phase transition at high temperature
causes an anomalous jump in the heat capacity, an interpola-
tion was used during this narrow range of 773–823 K to remove
the effect of the transition.35 This is appropriate and a standard

formation of a thin coating of tin oxides on the surface of
the micron sized powders. Indeed, a similar low thermal
conductivity of 0.30 W m 1 K 1 at 773 K was also observed in
polycrystalline SnSe strictly handled in an inert atmosphere
glove box. To test the SnO2 explanation, we carried out a series of
control experiments. As shown in Fig. 7, we found that the thermal
diffusivity of polycrystalline SnSe is very low when the powders are
processed in a glove box (compared to processing in air) and
closely approaches the 0.26 mm2 s 1 value at 773 K, which is
comparable to the value of 0.25 mm2 s 1 of SnSe single crystals.
Interestingly, when a very small amount of SnO2 (e.g., the
SnO2 addition ranges from 0.005–0.03 g SnO2 per 5 g SnSe,
practice in the thermoelectric community when such phase
transitions are encountered.91,92 More detailed studies of the
heat capacity and thermal behavior of SnSe near the high
temperature transition, of course, should obtain closely spaced
measurements during the phase change event.
7. Anharmonic bonding and low
thermal conductivity
The intriguing question is what gives rise to the ultralow
thermal conductivity of SnSe? Although the two-dimensional

Fig. 7 Thermal diffusivities of polycrystalline SnSe with and without SnO2 as a function of temperature. Single crystals SnSe samples are also plotted for
comparison. To exclude the effects of heat capacity and sample density on the total thermal conductivity estimation, we directly compared thermal
diffusivities.

Fig. 8 (a) Temperature-dependent heat capacity for SnSe obtained from different reports;111 (b) temperature-dependent heat capacity for SnSe (black
line), SnSe0.9S0.1 (red line) and SnSe0.7S0.3 (blue line) measured using a differential scanning calorimetry thermal analyzer (Netzsch DSC 404 C)55 and the
heat capacity (thick green line with red dot) of SnSe derived using a standard sample (Pyroceram 9606, Netzsch LFA457) with every 50 K steps, the phase
transition (within 50 K width) observed on a Netzsch DSC 404 C was jumped over when using a Netzsch LFA457. (a) Reproduced with permission from
ref. 39. Copyright 2016 The American Association for the Advancement of Science. (b) Reproduced with permission from ref. 55. Copyright 2015 Wiley.

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Fig. 9 Schematic representations of harmonicity and anharmonicity (F(r),
a0 and r are the potential energy, lattice parameter and distance between
two adjacent atoms, respectively); anharmonicity is the deviation from a
linear relationship between displacement and restoring force.36,38
(2D) character of the structure can be one factor, clearly this is
not a sufficient reason since 2D Bi2Se3 and the related 2D
material SnSe2 have a much higher thermal conductivity. As we
will discuss below, the 5s2 lone electron pair of Sn2+ and its
tendency to stereochemically express itself by occupying its own
space in the structure encouraging a wide range of Sn–Se bond
lengths is behind a case of strong bond anharmonicity that
causes ultra strong phonon scattering.
Although all bonding in real materials is anharmonic,
the degree of anharmonicity varies strongly from material to
material. In general, materials with substantial anharmonic
bonding have low thermal conductivities.35–38 Ideal perfectly
harmonic bonds in one-dimension are schematically illustrated
in Fig. 9. The potential energy to which an atom is subjected is
proportional to its displacement from the equilibrium position,
and the proportionality constant is called the spring constant
or stiffness. In the anharmonic case, the spring stiffness varies
with increasing atom displacement, which has pronounced
consequences when two phonons run into each other, as shown
in Fig. 9. The presence of the first phonon then changes the
spring constant values for the second phonon, which thus runs
into a medium with modified elastic properties.36,38,112 High
anharmonicity therefore results in enhanced phonon–phonon
scattering, which reduces the lattice thermal conductivity.
The Grüneisen parameter is used to measure the strength of
anharmonicity. The larger the Grüneisen parameter, the stronger
the anharmonicity, and thus phonon scattering. The PbTe system
has extraordinary physical and chemical properties favorable
for high thermoelectric performance, one of which is a large
Grüneisen parameter of B1.45.113 The large Grüneisen parameter
in PbTe can be ascribed to the recent discovery that the Pb atoms
are in fact somewhat displaced off the octahedron center in the
rock-salt structure and the displacement increases with rising
temperature (a phenomenon dubbed emphanisis).113,114
What is the atomic level basis for anharmonic bonding in
SnSe? In our view, the broad range of bond lengths between Sn
and Se atoms in the layered accordion-like structure, which is a
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Fig. 10 Schematic indicating resonant bonding in SnSe.
consequence of the tendency of the 5s2 lone pair of electrons
in Sn2+ to stereochemically express itself, is at the root of this
property. This situation creates expanded coordination poly-
hedra around the Sn2+ centers with a mix of weak, medium and
strong Sn–Se interactions which can in principle participate in
resonance bonding states that can be dynamic, especially at
high temperatures. The resonant type bonding is schematically
shown in Fig. 10. This can give rise to a soft malleable coor-
dination environment and crystal structure and high anharmonicity.
The strength of the lattice anharmonicity can be estimated
from the Grüneisen parameters, which characterize the relation-
ship between phonon frequency and crystal volume change.36,38
Therefore, to clarify the origin of the low thermal conductivity
of SnSe, the phonon and Grüneisen dispersions were calculated
using first-principles density-functional theory (DFT) phonon
calculations within the quasi-harmonic approximation.
Fig. 11(a) shows that the acoustic modes along the G–X Bril-
louin zone direction (a axis) are significantly softer (lower
Debye temperatures and smaller phonon velocities) than those
along both G–Y (b axis) and G–Z Brillouin zone directions
(c axis). These soft modes along the a axis suggest weak
interatomic bonding and possible strong anharmonicity.
To quantitatively assess the anharmonicity along the three
directions, the Grüneisen parameter dispersions of SnSe were
plotted (Fig. 11(b)), which shows that the Grüneisen parameters
are all very large, with that along the a axis being larger than
those along both b and c axes. The average Grüneisen parameters
along a, b, and c axes are 4.1, 2.1 and 2.3, respectively. Along the
a axis, the maximum longitudinal acoustic (LA) Grüneisen para-
meter around the G point is extraordinarily high, i.e. B7.2.35
In contrast, the Grüneisen parameter is 2.05 for AgSbTe2,
3.5 for AgSbSe2, and 1.45 for PbTe corresponding to a lattice
thermal conductivity of 0.68 W m 1 K 1, 0.48 W m 1 K 1 and
2.3 W m 1 K 1, respectively, measured at room temperature.34,46
The anomalously high Grüneisen parameter of SnSe is a
reflection of its crystal structure which contains very distorted
SnSe7 polyhedra and the zig-zag accordion-like geometry of
slabs in the b–c plane. This implies a soft lattice that would not
directly change the Sn–Se bond length if mechanically stressed
along the b and c directions, but instead the zig-zag geometry
would allow it to be deformed like a retractable spring. In
addition, along the a direction the weaker bonding between
SnSe slabs makes them a good stress buffer or a ‘‘cushion’’,115
thus dissipating phonon transport laterally.36,38 The anoma-
lously high Grüneisen parameter is therefore a consequence of
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Fig. 11 Theoretically calculated (a) phonon dispersions and (b) Grüneisen dispersion;35 (c) inelastic neutron scattering (INS) measurements reveal the
strong dispersion anisotropy and softening of the low-energy optic phonons with temperature.37 The top two panels show the first-principles calculation
at 100 K, which shows a good agreement with INS data obtained at 100 K (intermediate two panels) and the bottom two panels also reveals drastic
softening of phonon dispersions and strong anisotropy at 648 K.37 (a and b) Reproduced with permission from ref. 35. Copyright 2014 Nature Publishing
Group. (c) Reproduced with permission from ref. 37. Copyright 2015 Nature Publishing Group.

‘‘soft’’ bonding (i.e., a broad distribution of Sn–Se bond lengths) in
SnSe, which leads to a very low lattice thermal conductivity.
Recently, the strong anharmonicity in single crystal SnSe
was experimentally confirmed by inelastic neutron scattering
studies.37 As shown in Fig. 11(c), both transverse acoustic (TA)
and transverse optic (TO) phonons propagate along the G–X
and G–Y (T = 100 K) directions, respectively. Both TA and TO
phonons polarize along the c-axis, the TA modes not surpris-
ingly are considerably softer along the G–X direction than along
G–Y. This is consistent with lattice thermal conductivity being
much lower along the a-axis, perpendicular to the layers, than
within the plane of the layers (b–c plane). Both TA and TO
branches along G–Y are much stiffer than those along G–X,
accounting for anisotropic thermal transport. More importantly,
Fig. 11(c) reveals a drastic softening of phonon dispersions along
G–X at higher temperature (T = 648 K) compared to a much more
modest softening of TA modes along G–Y. Thus, the anharmonicity
of phonons exhibits not just strong dispersion but also strong
anisotropy.36,38
8. Thermoelectric performance
of single crystal and polycrystalline
SnSe samples
To date, most reports on SnSe have been focused on polycrystal-
line samples because of their ease of preparation compared to
the slow process of growing and cutting single crystals. It has so
far proved difficult to translate high ZTs in single-crystal SnSe
to polycrystalline samples because it is a challenge to obtain
comparable electrical transport properties. The polycrystalline
sample preparation can lead to inhomogeneous specimens
where the segregation of Sn is frequently observed, and the
defects introduced by the lack of homogeneity have a strong
impact on the number of carriers, and hence the Seebeck
coefficient and electronic conductivity. It can also lead to
oxidation as we discussed above. Given the strong 2D character
of the SnSe structure, specimen preparation can also lead to
varying degrees of spatially averaged plate orientations and
preferential orientation. The extent of preferential orientation
in samples can vary not only from laboratory to laboratory, but
also from preparation to preparation in the same laboratory.
This can lead to a distribution of results, as is evident in the
reported data. For these reasons, future work on this system
will require a careful characterization of the preferential orien-
tation in such samples using X-ray diffraction, electron micro-
scopy and other techniques.
Single crystals of SnSe show a ZT value of approximately
2.6  0.52 (if the 20% uncertainty criterion is considered) at
923 K along a particular crystallographic direction, the b axis.35
A very high ZT value of about 2.3  0.46 was also observed along
the c axis, whereas a moderate ZT value of approximately
0.8 was measured along the a axis, the axes directions are
shown in Fig. 12(a). Polycrystalline SnSe shows ZT peaks of
1.2 and of 0.7 at 973 K along the radial and axial directions,
respectively. As shown in Fig. 12(a), in a polycrystalline pellet,

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the radial direction is perpendicular to the applied pressure
direction, and the axial direction is parallel to the pressure
direction.
If we describe ZT = a2/L(1 + klat/kele), where L is the Lorenz
number, klat is the lattice thermal conductivity, and kele is the
electronic thermal conductivity, we can see that ZT values will
be enhanced by reducing the ratio of klat/kele.116 Generally,
grain boundary scattering in polycrystalline samples is an
effective way to lower the thermal conductivity in materials
such as half-Heusler,85,86,117 bismuth tellurides,84 skutterudite,87–90
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etc. The grain boundary scattering approach, however, does not
work well for thermoelectrics with low thermal conduc-
tivity,26,31,32,45,46 such as SnSe, since there is little room left
for further reduction through this scattering mechanism.118
The absence of defects associated with grain boundaries can
give single crystals a high carrier mobility, which can also be
anisotropic,39,84 depending on the type of crystallographic
structure.
To enhance the electrical transport properties (power factor),
single crystals are preferred especially for strongly anisotropic
compounds. As shown in Fig. 12(b), the carrier mobility of SnSe
single crystals along the b axis is 10 times higher than the carrier
mobility along the a axis.35 This strong anisotropy character
causes the average carrier mobility in polycrystalline compactions
of SnSe to diminish. For example, at room temperature, the hole
mobility of polycrystalline SnSe is B50 cm2 V 1 s 1 with a carrier
density of 3  1017 cm 3,64 while, the hole mobility of the single
crystals is B250 cm2 V 1 s 1 along the b axis (at a similar carrier
density of 3  1017 cm 3).35 At 750 K, at a carrier density of
4  1018 cm 3, the hole mobility of polycrystalline SnSe is about
10 cm2 V 1 s 1,64 which is only one fifth of the hole mobility of
Fig. 12 Comparison of thermoelectric transport properties of undoped SnSe single crystal35 and polycrystalline pellet samples: (a) schematic diagrams
show how samples were cut for measurements; (b) carrier mobilities, (c) power factor, and (d) ZT.
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B50 cm2 V 1 s 1 for the single crystals. 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
much lower power factors (Fig. 12(c)) and lower ZT values
(Fig. 12(d)).
Zhang et al. reported an ultra low thermal conductivity of
0.25 W m 1 K 1 in polycrystalline SnSe, similar to that of the
SnSe single crystals. However, because the maximum power
factor in polycrystalline SnSe is only about 4 mW cm 1 K 2
at 773 K, a ZT of 1.0 was obtained.55 Correspondingly, the
maximum power factor in undoped SnSe single crystals is
about 6 mW cm 1 K 2 at 773 K, resulting in a ZT of 1.5 at
773 K.35 It should be noted that both reports are on samples
with a similar carrier concentration (B1017 cm 3) and Seebeck
coefficient, and therefore, the difference in the power factor
indeed comes from the carrier mobility difference, which
comes from the strongly anisotropic character of the SnSe
single crystals and also possibly from the oxidation of poly-
crystalline SnSe samples.
9. The maximum and device ZT
Because of the exceptional thermoelectric properties of single
crystal SnSe, it is important to discuss the issues of repeat-
ability and the degree to which the properties vary across a
large number of samples. The available measurements are
limited so far, given the challenges in growing samples and
preparing good orientation specimens, but they can be used to
obtain some statistics for each thermoelectric parameter. The
range of the thermal conductivities is about 20%, Fig. 13(a).
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Fig. 13 (a) A series of total thermal conductivity measurements for hole-doped SnSe crystals along the b axis. BU represents the results measured at
Beihang University of China. Caltech represents the results measured at California Institute of Technology. The solid line represents the average value; the
measurement uncertainty is about 20%;39 (b) the range of ZT values obtained from a series of samples of hole-doped SnSe crystals along the b axis. The
solid line represents the average value, the ZT measurement uncertainty is about 20%;39 (c) ZT values of hole-doped SnSe and undoped SnSe crystals
along different axial directions; the ZT measurement uncertainty is about 20%; (d) the calculated efficiency (based on ZTave values) as a function of the
hot side temperature (cold side temperature is 300 K) of hole-doped SnSe (b axis),39 undoped SnSe (b axis),35 PbTe–4SrTe–2Na,18 and PbTe–30PbS–
2.5K.120 Reproduced with permission from ref. 39. Copyright 2016 The American Association for the Advancement of Science.

As we discussed above, the range of the reported thermal
conductivity values may result from many factors, such as
artificial cracks, variations in carrier concentration, errors in
mass density determination, possible oxidation (unlikely in
single crystals) and variations in stoichiometry. Fig. 13(b)
shows that the room temperature ZTmax for hole doped samples
ranges from 0.6 to 0.9, while the ZTmax at 773 K ranges from
1.6 to 2.4 and the average ZTmax ranges from 0.7 to 2.0,
consistent with the 20% uncertainty of ZTs.39
Doping SnSe with donor and acceptor atoms is not as
straightforward as it is in the case of PbTe, PbSe or PbS. It
seems that many conventional dopants are rejected from the
structure or are accommodated to a very limited degree. We
believe this is because of the layered anisotropic structure
where each SnSe layer is only two-atom thin and the locally
distorted highly covalent bonding around the Sn and Se atoms
may destabilize guest atoms with large differences in chemical
character. We found that sodium is one of the effective acceptor
dopants in SnSe, which causes a two order of magnitude
increase in the hole concentration,39 and a vast increase in
ZT from 0.1 to 0.7 along the b axis at 300 K while obtaining a
ZTmax of 2.0 at 773 K, Fig. 13(c). The ZTmax is large over the
entire working temperature range of 300–773 K and likely also
below 300 K. The material also projects a large so-called average
or device ZTdev, which actually determines the overall thermo-
electric conversion efficiency (Z) of a device.119 In fact, SnSe has
the highest device ZT of B1.34 (ZTdev) from 300–773 K known
among thermoelectric materials. The projected theoretical
conversion efficiency of hole-doped SnSe at Tc = 300 K and
Th = 773 K is B16.7%, higher than that of other high perfor-
mance thermoelectrics,18,120 Fig. 13(d).
10. Summary and outlook
The physics of thermal and charge transport in SnSe is unusual
and fascinating. The high thermoelectric performance of SnSe
crystals suggests that single phase materials with strongly anhar-
monic bonding and ultralow thermal conductivity are promising
candidates for achieving high thermoelectric performance. It is
remarkable that such an ultralow thermal conductivity can be
realized in a simple compound such as SnSe as it does not have a
high molecular weight, a complex crystal structure or a large unit
cell. It is also remarkable that such an ultra-high power factor
can be achieved in a not-so-narrow bandgap semiconductor with
only orthorhombic crystal symmetry. The multiple valence band
extrema lying close in energy are the key to this performance,
which persists over a wide temperature plateau from 300–773 K
and perhaps even wider. Hole doping quickly pushes the Fermi
level deep into the valence band structure, activating several
Fermi pockets to produce enhanced Seebeck coefficients and
high power factors. The resulting high figure of merit improves

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the prospects for realizing very efficient thermoelectric devices
using hole-doped SnSe crystals as a p-type leg.
The discovery of exceptional physical properties in SnSe
clearly points to new directions in thermoelectric science in
terms of what materials systems we might pursue as superior
thermoelectrics. In this context, many more materials are yet to
be investigated, especially those that share electronic and
structural features with SnSe. Although the issue with the exact
thermal conductivity of polycrystalline samples vis-á-vis single
crystal SnSe samples will take a bit longer to be settled, what is
Published on 05 September 2016. Downloaded by Tufts University on 24/03/2018 11:33:13.
not controversial is the outstanding thermoelectric perfor-
mance of single crystal SnSe and, according to recent reports,
even of polycrystalline samples.55,99,121
Acknowledgements
This work was supported in part by a grant DOE-EERE/NSF
(CBET-1048728), 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
(G. J. T. and M. G. K.). This work was also supported by the
‘‘Zhuoyue’’ program of Beihang University, the Recruitment
Program for Young Professionals, and the NSFC under Grant
No. 51571007, and the Fundamental Research Funds for the
Central Universities (C. C. and L. D. Z.). We thank Professors
H. B. Xu, S. K. Gong, Y. L. Pei, G. J. Snyder, C. Uher,
C. Wolverton, V. P. Dravid, J. P. Heremans, S. Q. Hao and
Y. S. Zhang for plentiful discussions and fruitful collaborations.
Of course most of all, we are grateful to the numerous dedi-
cated 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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