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A Promising Mid-Temperature Thermoelectric Material
Candidate: Pb/Sn-Codoped In4PbxSnySe3
Zhi-Sheng Lin, Ling Chen, Li-Min Wang, Jing-Tai Zhao, and Li-Ming Wu*
Thermoelectric (TE) materials that directly convert waste heat
into electricity has attracted renewed intense attention since
1990s because of the increasing understanding of global energy
and environmental issues.[1–3] The high efficiency of TE conver-
sion technique requires not only a large working temperature
gradient but also key TE materials with a high figure-of-merit
(ZT = S2σT/κ, where S is the Seebeck coefficient, σ is the elec-
trical conductivity, T is the absolute temperature, and κ includes
lattice thermal conductivity, κlatt, and electronic conductivity,
κe.). The state-of-the-art TE materials can be divided into three
classes according to the working temperature: i) Low-temper-
ature materials, i.e., Bi2Te3 based alloys for applications from
near room temperature up to 473 K with peak ZT values in the
range of 1.2 to 1.5;[4] ii) Mid-range temperature (500–900 K)
materials, typically tellurides, such as PbTe showing the max-
imum ZT of about 1.3 in optimized n-type material[5] or 2.2 in
p-type.[2] But only the p-type alloy (GeTe)0.85(AgSbTe2)0.15 with
a maximum ZT greater than 1.2 has been successfully used
in long-life TE generators;[2,3] 3) High-temperature (>900 K)
materials, typically SiGe alloy with ZT up to 1 for p-type and
1.5 for n-type.[6,7] Enhancement in ZT can be achieved by either
increasing power factor (S2σ) or reducing thermal conductivity
κ via many strategies, such as band engineering,[8,9] energy
barrier filtering,[10–12] additional carrier pocket,[13] resonant
states,[14] and nanostructuring.[15–19] However, it remains a great
challenge because S, σ and κ are strongly interdependent and
vary inversely.
The crystal structure of In4Se3 features anionic layers of
[In3Se3]− that are interconnected by In1+ cations (In4 shown in
Figure 1a) via ionic bonding interactions, and such a layer is
built by trinuclear [(In3)5+(Se3)6−] clusters (In 1–3) through cova-
lent In–Se bonds.[20,27] This compound has a reasonable band
gap of 0.42 eV, suggesting a maximum ZT at high temperature
according to the 10kBT rule.[21] Recently, single crystals with
Dr. Z.-S. Lin, Prof. L. Chen, Prof. L.-M. Wu
State Key Laboratory of Structural Chemistry
Fujian Institute of Research on the Structure of Matter
Chinese Academy of Sciences
Fuzhou, Fujian, 350002, People’s Republic of China
E-mail: liming_wu@fjirsm.ac.cn.
Prof. L.-M. Wang
State Key Lab of Metastable Materials Science and Technology
Yanshan University
Hebei, 066004, People’s Republic of China
Prof. J.-T. Zhao
Key Laboratory of Transparent Opto-Functional Inorganic Materials
Shanghai Institute of Ceramics
Chinese Academy of Sciences
Shanghai, 200050, People’s Republic of China
DOI: 10.1002/adma.201302038
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Se deficiency, In4Se2.35[21] and In4Se2.67Cl0.03,[22] show strongly
anisotropic TE properties, i.e., a high ZT value of 1.5 at 713
K in the bc plane, but a much lower ZT about 0.5 in the ab
plane (because the high S and low κ are only achieved in the
charge density wave plane). Such an anisotropic feature will
be a big issue of the application together with the consider-
able high cost and difficult manufacturing of large size single
crystals. It is therefore desirable to achieve a high performance
polycrystalline form of such a material. Unfortunately, many
efforts in this trend have only shown trivial effects on the ZT
enhancement.[23–27] For example, the polycrystalline In4Se2.2
featuring both a high Se deficiency and a considerably low κ of
0.41 W·m−1·K−1 only peaks ZT = 0.93 at 703 K, which is about
half of the maximum value of the single crystal.[26]
In this work, we report a new promising mid-temperature
thermoelectric material cadidate, polycrystalline In4PbxSnySe3,
with an enhanced ZT = 1.4 at 733 K via not only utilizing effec-
tive electron donor codopants that substitute at the energetically
favorite lattice sites, but also simultaneously including nano
particles in the bulk matrix as scattering centers.
Compared with indium, lead carries one more electron
and serves as an effective electron donor if the Pb2+ substitu-
tion at the In3+ sites in the In4Se3 lattice can be realized. Pre-
vious studies on polycrystalline n-type In4Se3 only achieve ZT
values in the range of 0.6–0.93 with carrier densities about 1017
cm−3. Note that, such carrier concentrations are significantly
lower than the optimal concentration (1019 cm−3) of a conven-
tional TE material.[23–25] In this work, firstly, series of Pb-doped
In4-xPbxSe3 (x = 0.01–0.06) samples have been prepared as
homogenous phases that are well indexed as Pnnm In4Se3 (PDF
−83–0039) without any other detectable impurity. (Figure 1b)
Meanwhile, undoped In4Se3 sample has also been prepared to
approve the reliability of our experiment. The as-synthesized
udoped In4Se3 sample exhibits agreeable TE properties with
the previous works.[23,25,26] (Figure 1, Supporting Information,
Table S1) The Pb-doped samples show carrier concentra-
tions on the order of 1018 cm−3 at room temperature, which
are one order of magnitude higher than the reported value of
1017 cm−3.[22–25] The carrier concentration increases as the Pb
amount (x) increases from 0.01 to 0.05, but drops at x = 0.06,
which may indicate a solubility limit of Pb in the In4Se3 lat-
tice. (Supporting Information, Table S1) The electrical resis-
tivity (ρ) varies from 1.0–2.4 × 10−4 Ω·m at room temperature
to 1.0–0.8 × 10−4 Ω·m at 703 K. These are lower than the cor-
responding values of the undoped polycrystalline In4Se3, i.e.,
17.7 × 10−4 Ω·m at room temperature,[23,25,26] and 2.7 × 10−4
Ω·m at 703 K.[23] (Figure 2a) The resistance does not show a
systematic dependence on the Pb concentration, but exhibits
a slope turning around 475 K. Such a slope turning has also
been observed previously in In4Se3 or other systems.[21,23,30–32]
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Figure 1. a): Crystal structure of as-synthesized In4Se3 viewed along the
c axis with selected bond lengths marked. b): Powder X-ray diffraction
patterns of the Pb-doped In4-xPbxSe3 samples (x = 0.01–0.06). c): Powder
X-Ray diffraction patterns of the Pb/Sn-codoped In4Pb0.01SnySe3 samples
(y = 0.02–0.05). All XRD patterns in b and c are well indexed as Pnnm
In4Se3 (PDF-83-0039) that is shown at the bottom of each panel. The
main diffraction peaks are indicated.
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As expected, these results clearly indicate that the Pb dopant is
an effective electron donor, and enhances the carrier density.
According to the VASP calculations on the Pb substitution on
each of the In sites in the In4Se3 lattice, the Pb substitution on
the In4 (i.e., In+) site has the lowest formation energy.[27] There-
fore, Pb should substitutes at the energetically most favorable
In4 site in our samples.
Both Seebeck coefficient (S) (Figure 2b) and Hall measure-
ment result (Supporting Information, Table S1) reveal that the
Pb-doped sample is an n-type semiconductor dominated by
electrons. S falls in the range of −190 to −275 μV/K, which is
lower than that of the undoped In4Se3 (varying from −314 to
−422 μV/K). This may originate from the increase of the car-
rier density. Figure 2b also shows the absolute S value firstly
increases with the temperature increase and reaches a max-
imum of −275 μV/K at 550 K, then decreases to −240 μV/K at
713 K. Similar slope change is observed in many other cases,
e.g., lead chalcogenides[27,28] and Se-deficient In4Se2.35[21] or
chlorine doped In4Se2.67Cl0.03,[30] which is supposed to relate to
the melting of the inclusive element that is embedded within
the bulk material. We substantiate this with the DSC observa-
tion of the melting of the inclusive element In nano particles
discussed below.
Figure 2c reveals that the power factor (S2σ) has been
improved considerably. For example, at 703 K, In3.95Pb0.05Se3
and In3.96Pb0.04Se3 realize 8.0× and 7.9 × 10−4 W·m−1·K−2,
respectively, both are higher than those of the undoped In4Se3
reported by different groups: i.e., 5.2× (this work), 6.5×,[23]
or 4.2 × 10−4 W·m−1·K−2.[25,26] The thermal conductivity (κ)
decreases linearly from 300 to 703 K indicating a typical crystal-
line heat transport behavior. (Figure 2d) When x = 0.01–0.05, κ
roughly decreases from 1.05–1.25 to 0.75 W·m−1·K−1, which
fall in the range of the reported values, i.e., 0.61 W·m−1·K−1,[26]
0.5–0.6 W·m−1·K−1.[23,25] When x = 0.06, κ systematically shifts
to higher values that decrease from 1.6 to 0.97 W·m−1·K−1 in
the temperature range of 300–703 K. (Figure 2d) Neverthe-
less, κ of the Pb-doped In4-xPbxSe3 is higher than that of the
undoped sample.[23,25] According to the Wiedemann-Franz (WF)
relation, κe = L0T/ρ, the Pb-doped sample shows a very small κe
(about 0.04–0.12 W·Ω·K−2) suggesting that κ is dominated by
κlatt, which falls in the range of 1.01–1.55 W·m−1·K−1 (Table S1)
that is close to that of the undoped In4Se3 (1.04 W·m−1·K−1).[23]
These effects generate a ZT = 0.8 at 703 K (that is ∼30% higher
than that of the undoped polycrystalline In4Se3) suggesting that
by increasing the electrical conductivity, the appropriate Pb
concentration significantly enhance the ZT performance. But,
further increasing x to 0.06 can not increase the carrier con-
centration any more that may be limited by the solubility of Pb
in the In4Se3 lattice, instead, it consequently decreases S2σ and
increases κ, and inevitably results in a reduction of ZT to 0.3 at
703 K (that is roughly half of that of the undoped sample).
Hereto, we realize that when x = 0.01–0.05, Pb-doping at
the energetically favorable In4 site (In+) can improve the ZT of
In4-xPbxSe3 samples via increasing the carrier density. However,
as listed in Table S1, For these samples, the maximum carrier
density (3.46 × 1018 cm−3) is still one order of magnitude lower
than the normal value (1019 cm−3) of a heavily doped semicon-
ductor. In order to further increase the carrier density in the
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proposed to substitute the In2 and In3 sites

Figure 2. Thermoelectric properties of as-synthesized samples. a–d): Pb-doped In4-xPbxSe3 work)). Such an enhancement resulted from
(x = 0, 0.01, 0.03–0.06). e–h): Pb/Sn-codoped In4Pb0.01SnySe3 (y = 0.03–0.05). Temperature-
dependent electrical resistivity (ρ), (a, e), Seebeck coefficient (S), (b, f); power factor (σS2), (c,
g), and thermal conductivity (κ), (d, h). The same symbol notation for the samples is used in other systems, for example, K/Na-codoped
a–d and e–h, respectively. The temperature-dependent transport data for the undoped In4Se3 PbTe,
sample are shown for comparison.
In4-xPbxSe3 sample, we consider it is possible to carry out the
simultaneously substitution on the other In sites (i.e., In1, In2,
+
In3 sites) while keep the Pb-substitution on the In sites. As we
know, the Sn belongs to the same 14 group as Pb does (thus
it shows similar chemical and physical properties), Sn is also
in the In4Se3 lattice according to the VASP
formation energy calculations.[27] These
imply that Pb/Sn codoping in the In4Se3 lat-
tice is highly possible, consequently, we have
explored the synthesis of Pb/Sn-codoped
sample.
Homogeneous In4Pb0.01SnySe3 (y =
0.02–0.05) have been prepared that are
well indexed as orthorhombic In4Se3 phase
(Pnnm, PDF−83–0039) without any detect-
able impurity. (Figure 1c) The ρ-temperature
dependence of In4Pb0.01SnySe3 (y = 0.03–
0.05) sample is presented in Figure 2e. The
ρ decreases from 2.39–6.78 × 10−4 Ω·m at
room temperature to 0.56–0.69 × 10−4 Ω·m
at 733 K. The room temperature ρ value is
one order of magnitude lower than that of the
undoped In4Se3 sample (17.7 × 10−4 Ω·m),[23]
and similar to that of the Pb-doped sample.
Although the dispersion below 500K, the Pb/
Sn-codoped samples tend to have similar ρ
values at higher temperature. The ρ of the
Pb/Sn-codoped sample at 733 K is lower than
those of the undoped (2.7 × 10−4 Ω·m)[23–25]
and the Pb-doped (0.8 × 10−4 Ω·m) samples.
Clearly, Sn dopant is also an effective elec-
tron donor for In4Se3 that increases the elec-
trical conductivity.
Compared to the Pb-doped In4-xPbxSe3
sample, the Pb/Sn-codoped In4Pb0.01SnySe3 (y
= 0.03–0.05) is also an n-type semiconductor
with similar S-temperature curve turning at a
higher point. S values of the Pb/Sn-codoped
In4Pb0.01SnySe3 samples vary from −220 to
−310 μV/K, which are slightly higher than
those of the Pb-doped In4-xPbxSe3 samples
(216–249 vs 190 μV/K) at room temperature,
but comparable at high temperature. These
indicate that Sn is a much weaker n-type
dopant with respect to Pb.[27] The power factor
(S2σ) values of In4Pb0.01SnySe3 samples with
y = 0.03, 0.04 are about 1.0 × 10−4 W·m−1·K−2
at 733 K, (Figure 2g) nearly 80% higher than
that of the undoped In4Se3 sample (4.5×,[23]
6.5×,[24,26] and 5.2 × 10−5 W·m−1·K−2 (this
the double doping has also been observed in
[28] Ag/Sb-codoped PbTe,[34] and V/
Sb-codoped Hf0.75Zr0.25NiSn,[35] in which
the enhancement of the power factor is
dominated by the considerable increase
of S owning to the resonance of density of states around the
Fermi level.[28,34,35] Differently, S value of the Pb/Sn-codoped
In4Pb0.01SnySe3 sample has not been enhanced significantly,
instead, the power factor is improved by the substantial enhanc-
ment of the electrical conductivity without decreasing S value.

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Figure 3. The temperature dependent ZT values for. a): Pb-doped
In4-xPbxSe3 (x = 0, 0.01, 0.03–0.06). b): Pb/Sn-codoped In4Pb0.01SnySe3 (y
= 0.03–0.05).
According to the standard charge transport theory, the intrinsic
reason is related to the increase in relaxation time and carrier
mobility. Similar phenomenon was found in the Pb/Sb-codoped
PbTe system.[5,36–38]
The inversely temperature dependent κ is presented in
Figure 2h. The nearly linear κ reduction in the whole tempera-
ture range suggests a typical crystalline heat transport behavior.
The Pb/Sn-copoded In4Pb0.01SnySe3 samples with y = 0.03,
0.04, 0.05 exhibit κ values varying from ∼1.0 W·m−1·K−1 at
293 K to ∼0.56 W·m−1·K−1 at 733 K. Note that the κ value at
733K is lower than those of the undoped In4Se3 and the Pb-
doped In4-xPbxSe3 samples (0.65 or 0.75 W·m−1·K−1).[23–25] The
inversely temperature dependence of κ indicates the predomi-
nant phonon contribution to the thermal conductivity. Note
that such a Pb/Sn-codoped sample exhibits a desirable low κ
value as the well established materials, such as Ag(Pb1-ySny)m
SbTe2+m(0.7 W·m−1·K−1),[40] optimized Bi2Te3 (0.6 W·m−
1
·K−1),[5] Ag2Te dispersed PbTe (0.65 W·m−1·K−1),[40] or Na-
doped PbTe-SrTe (0.52 W·m−1·K−1).[2]
As shown in Figure 3, a maximum ZT = 1.4 is achieved at
733 K for In4Pb0.01SnySe3 (y = 0.03, 0.04), which is higher than
those of the undoped In4Se3 (0.6), or the Pb-doped In4-xPbxSe3
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(0.8) (this work). Such a value is comparable with those
achieved at the same temperature by the best mid-temperature
thermoelectric materials, PbTe (∼1.7 at 733 K) and filled skut-
terudite (∼1.4 at 733 K). Besides, the very low concentration of
the toxic Pb component in comparison with the PbTe-based
materials makes the Pb/Sn-codoped In4Pb0.01SnySe3 (y = 0.03,
0.04) material a new promising candidate for the mid-tempera-
ture waste-heat recovery application.
Now a question remains to be answered why the transport
properties of both the Pb-doped and the Pb/Sn-codoped sam-
ples exhibit slope-turning behaviors? To probe this, we have
carried out scanning transmission electron microscopy (STEM)
investigations on the argon-ion-milled Pb-doped In3.96Pb0.04Se3
and Pb/Sn-codoped In4Pb0.01Sn0.03Se3 samples. The low mag-
nification TEM images in Figure 4a, b show the widespread
presence of nano particles with coherent or semi-coherent
interfaces with the host matrix. The major morphologies in
both samples are spherical or ellipsoidal shapes. In the Pb/Sn-
codoped sample, the nano particles have diameters of 5–70 nm;
and in the Pb-doped sample, the nano particles are larger
(30–100 nm). These results give a better explanation on the κ
reduction. Usually, the different mean free paths phonons of
a crystalline solid contribute differently to the heat transport,
and most heat is carried by short and medium mean free paths
phonons. Therefore, the more number of small nano particles
in the sample (that are smaller than the short or medium mean
free paths), the more effective reduction in κ value is achieved.
For example, κ of PbTe reduces 50% by the inclusion of 42 nm-
particles; and κ of Si reduces 90% because of the involvement of
20 nm-particles.[3] Here, our results show that the 30–100 nm-
particles in the Pb-doped In3.96Pb0.04Se3 sample do not affect
κ noticeably, however, smaller 5–70 nm-particles in the Pb/
Sn-codoped In4Pb0.01Sn0.03Se3 sample considerably reduce
κ. These indicate that most of the heat in the as-synthesized
sample should be carried by phonons of mean free paths
about 30 nm or shorter. In addition, the fast Fourier transform
(FFT) of HRTEM images reveal the lattice discontinuity indi-
cating interfacial dislocations due to the excess of the coher-
ency strain. (Figure 4c, d) Therefore further modifications on
size, morphology and dispersion of the inclusive nano species
in the In4Se3 matrix via many approaches, such as optimizing
the Pb/Sn ratio, doping with multiple components, etc., should
improve the ZT value owning to the nano effect and grain
boundary effect.[5,15,36–38]
Although it is difficult to quantitatively determine the com-
position of each individual nano particle owing to the overlap-
ping with the matrix, the energy dispersive X-ray spectroscopy
(EDX) results indicate a remarkable increase of the In signal
from the particles (Supporting Information, Figure S1b–g) in
comparison with the matrix regions (Figure S1a). The differen-
tial scanning calorimetry (DSC) measurements (Figure 5) show
evident heat absorption and desorption peaks at 430 and 427 K
in the Pb/Sn codoped In4Pb0.01Sn0.03Se3 sample, which are
in good agreement with the melting point of In element
(m.p. 430 K).[34] These data substantiate that the inclusion
nano particles are indeed element indium. While a very weak
absorption peak around 427 K (correpsonding to an enthalpy of
melting of 0.18 J/g) is observed in the Pb-doped In3.96Pb0.04Se3
sample owning to the very small amount of element In that
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Figure 4. Nano structures embedded in In4Pb0.01Sn0.03Se3 and In3.96Pb0.04Se3 samples. In4PbxSnySe3 sample exhibits a ZT = 1.4 at
a,b): TEM images revealing presence of spherical or ellipsoidal nano particles. c, d): High- 733K, this materical is a new promising mid-
resolution TEM images showing In nano precipitate embedded within the host matrix with
coherent or semi-coherent interfaces.
is below the detective limit of XRD technique (usually 5%).
Undoubtedly, the Pb/Sn-codoped sample contains more In
nano particles than the Pb-doped sample, which agrees well
with the κ measurement shown in Figure 2. That is, the more
number of nano particles that are embedded inside the sample,
the high density of the interfacical dislocation, the more effec-
tively heat is scattered.[30] Consequently, κ ofthe Pb/Sn-codoped
In4PbxSnySe3 sample is lower than those of the Pb-doped In4-
xPbxSe3 and the undoped In4Se3 samples. Meanwhile, the exist-
ence of the inclusive element In nano particles also explains the
slope change behaviors in κ and ρ as shown in Figure 2, and
the curve turning is substantiated to relate to the melting of the
In element. Although the similar phenomena were repeatedly
observed in other systems,[21,30–32] this is the first direct evi-
dence of the suspected melting of the inclusive nano species.
As summarized in Table S2, Supporting Information, the Pb/
Sn-codoped In4PbxSnySe3 samples are new promising candi-
dates as mid-temperature thermoelectric materials. The micro-
structure analyses reveal that the κ reduction mainly arises
from the scattering of the medium mean−free paths phonons
at the interface of the 5–70 nm element In nano particles. The
Pb/Sn-codoped In4PbxSnySe3 sample exhibits lower κ because
the increase of the scattering centers. The Pb/Sn substitution
at the In sites in the In4Se3 lattice may break the translation
symmetry leading to the enhancement of the Peierls distortion
effect, and therefore reduce the lattice thermal conductivity.[27]
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Additionally, the Pb/Sn doping gives rise to
the fluctuation of atom size, mass, and lattice
force that may enhance the phonon scattering
and consequently result in the low lattice
thermal conductivity.[2] Again, the improve-
ment of the thermoelectric properties of the
as-synthesized sample owns to not only the
intrinsic substitution effect on the electronic
states, but also the nano effect of the inclu-
sion nano particles and the grain boundary
effect.[5,15,36–38] Previous studies suggest that
extremely fine (< 10 nm) nano structures
can scatter more effectively the short mean
free paths phonons and thus reduce the lat-
tice thermal conductivity,[11–15] therefore fur-
ther reduction of the thermal conductivity of
the Pb/Sn-codoped In4PbxSnySe3 sample is
still possible by modifications of size, iden-
tity, and distribution of the inclusive nano
particles.
In summary, polycrystalline Pb-doped
In4-xPbxSe3 (x = 0.01–0.06) and Pb/Sn-
codoped In4Pb0.01SnySe3 (y = 0.03–0.05) sam-
ples were successfully prepared using solid-
state methods and spark plasma sintering
technique. The doping- and nano-effects
on the thermoelectric properties are inves-
tigated. Among them, the Pb/Sn-codoped
temperature TE material. Although it con-
tains considerably less toxic Pb component
with respect to the well established mid-tem-
perature PbTe material, a non Pb-containing environmentally
friendly In4Se3 based material is still highly desired. Further ZT
enhancement of this type of material is ongoing via tuning the
Pb/Sn ratio, controlling the size and distribution of the inclu-
sion nano particles, exploring multiple doping, excluding Pb
dopant, adjusting the Se deficiency, etc.. This work suggests
a new path to fabricate facile, isotropic, polycrystalline In4Se3-
based materials that are desirable as a new mid-temperature
TE materials, and further enhancement of its TE property is
promising.
Experimental Section
Syntheses: In4-xPbxSe3 (x = 0.01–0.06) and In4Pb0.01SnySe3 (y =
0.01–0.05) were synthesized by solid-state reaction. Appropriate amount
of starting materials, In (granular, 5N), Pb (granular, 5N), Sn (granular,
5N) and Se (shot, 3N) were weighed and mixed in a silica crucible in an
Ar-filled glove box. The crucible was transferred into a larger silica jacket,
which was flame sealed under high vacuum. The assembly was slowly
heated to 1223 K over 15 h, and dwell there for 1 day. The assembly was
then cold-water quenched. The obtained product was ground into a fine
powder and pressed into a pellet in an argon-filled glove box. The pellet
was annealed at 753 K for 5 days, then ground into a fine powder and
subsequently sintered by spark plasma sintering (SPS 2040, Sumitomo
Coal Mining Co.) at 700 K for 5 min under uniaxial pressure of 70 MPa
under vacuum (10−3 Pa). The experimental relative densities of sample
pellets were all above 95%. (diameter, ∼10 mm; thickness, ∼2 mm) The
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Figure 5. The differential scanning calorimetry (DSC) curves. a), heating
curve of In3.96Pb0.04Se3 with a very weak absorption peak around 427 K
(corresponding to an enthalpy of melting of 0.18 J/g). b), heating and
cooling curves of In4Pb0.01Sn0.03Se3 with evident heat absorption or des-
orption peaks at 430 and 427 K, respectively, which are in good agreement
with the melting point of In element (430 K). The difference between the
heat absorption shown in a and b is caused by the different amount of
the inclusive In nano particles in the sample.
measured density (d) was calculated by d = m/V, where m was the mass
and V the volume.
The powder X-Ray diffraction (PXRD) data were obtained on a Rigaku
DMAX2500 powder diffractometer with Cu Kα radiation (λ = 1.5418
Å) and operating at 40 kV and 40 mA (2θ range from 4 to 85° with a
step size of 0.02°). The electrical conductivity (σ) and the Seebeck
coefficient (S) were measured simultaneously from room temperature
to 733 K under an argon atmosphere by using the standard four-probe
method with a ULVAC-RIKO ZEM-3 instrument system on rectangular
samples with dimensions of ∼2 × 3 × 8 mm3. Heating and cooling cycles
gave repeatable electrical properties for a given sample. The thermal
diffusivity (α) and the specific heat capacity, Cp, were measured on
a sample disk with 10 mm in diameter and 3 mm in thickness under
an argon atmosphere in the range 300–733 K on a Netzsch LFA-457
MicroFlash instrument. The specific heat capacity, Cp, was derived
using pyroceram as the standard. Cpsam. = Cpstd. × (ΔUstd. × mstd.)/
(ΔUsam. × msam.), where ΔUstd. and ΔUsam. were the detector signal
differences of the standard and sample, respectively. The total thermal
conductivity κtotal was calculated by κtotal = α · Cp · d, where d was the
measured density. The electronic contribution κe was calculated by
the Wiedemann-Franz relation κe = L0T/ρ, where ρ, T, and L0were the
electrical resistivity, absolute temperature and Lorenz number 2.44
× 10−8 W·Ω·K−2, respectively.
The homogeneity and microstructure were examined by the TEM
examinations performed on a JEM-2100F field-emission transmission
electron microscope and a field emission scanning transmission electron
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microscope (STEM) equipped with an energy dispersive spectrometer
(EDS). The specimen with φ = 3 mm for STEM investigations was cut
from the sintered pellet using an ultrasonic cutting machine (Model
601, Gatan, USA). It was then submitted to the multistep grinding and
polishing processes with final polishing using the 0.5 μm diamond
powders to achieve a thickness of ∼50 μm. The polished specimen was
finally argon-ion-milled (Emres 101, Leica, Germany) until perforation.
The Hall effects are measured on square shaped samples measuring 3 ×
3 × 0.2 mm3 in size with the aid of the physical property measurement
system (PPMS, Quantum Design, Inc.) in magnetic flux density up to 5 T.
The carrier concentration (ne) was calculated from the Hall coefficient Re
(assuming a scattering factor of 1.0 in a single-carrier scheme) by ne =
−1/(e·Re), where ne was the carrier concentration and e was the electron
charge. The Hall mobility μe is calculated from the Hall coefficient and
electrical resistivity with μe = Re/ρ.
The calorimetric measurements were performed on a Perkin-
Elmer differential scanning calorimetry (DSC) calibrated by indium
and cyclohexane for the high and low temperature regions. A heating-
cooling-heating cycle was imposed in the temperature range from 145
(125) to 170 (155) °C at a rate of 2.5 K/min.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
This research was supported by the National Natural Science Foundation
of China under Projects (20973175, 21225104, 90922021, 21233009,
51131002, 51271160), the “Knowledge Innovation Program of the
Chinese Academy of Sciences” (KJCX2-YW-H20). We thank Prof. Fang-
Fang Xu at SIC and Dr. Ping Huang at FJIRSM for TEM measurements.
Received: May 6, 2013
Revised: May 21, 2013
Published online: July 12, 2013
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