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High-Ranged ZT Value Promotes Thermoelectric Cooling

and Power Generation in n-Type PbTe
Yu Xiao,* Haijun Wu, Haonan Shi, Liqing Xu, Yuke Zhu, Yongxin Qin, Guyang Peng,
Yang Zhang, Zhen-Hua Ge, Xiangdong Ding, and Li-Dong Zhao*

1. Introduction
Excellent thermoelectric cooling and power generation are simultaneously
realized in an n-type PbTe-based thermoelectric material. The cooling tem- Thermoelectric technology is capable of
realizing direct conversion between heat
perature difference (ΔT) of ≈15.6 K, maximum power density of ≈0.4 W cm−2
and electricity, which is regarded as an
and conversion efficiency of ≈1.5% with TC = 295 K and TH = 765 K can be alternative route to deal with energy and
obtained in a single-leg device composed of PbTe-30%SnSe-1.5%Cu. This environment issues.[1] However, the rela-
advanced thermoelectric performance in n-type PbTe-30%SnSe-1.5%Cu tively low conversion efficiency of thermo-
mainly originates from its high-ranged ZT value achieved through opti- electric technology largely limits its wide
applications. The thermoelectric conver-
mizing its bandgap, carrier density, and microstructure. The bandgap in
sion is closely related to the performance
PbTe is first reduced by SnSe alloying to facilitate the carrier transport of thermoelectric material, characterized
properties at low temperature range (300–573 K). With further tuned car- by dimensionless Figure of merit (ZT),
rier density, the average power factor increases from ≈10.2 µW cm−1 K−2 in ZT = S2σT/κ, where S, σ, T, and κ denote
Pb0.985Sb0.015Te-30%SnSe to ≈16.2 µW cm−1 K−2 in PbTe-30%SnSe-1.5%Cu the Seebeck coefficient, electrical conduc-
at 300–773 K. Moreover, microstructure observation reveals high-density tivity, temperature in Kelvin, and thermal
conductivity, respectively. To realize
dislocations in PbTe-30% SnSe-1.5% Cu, which can dramatically suppress
advanced thermoelectric technology, the
the room-temperature lattice thermal conductivity from ≈2.21 Wm−1 K−1 in priority is to develop efficient thermoelec-
Pb0.985Sb0.015Te to ≈0.53 Wm−1 K−1 in PbTe-30%SnSe-1.5%Cu. As a result, tric material with high ZT value by bal-
a room-temperature ZT value of ≈0.7 and high average ZT value (ZTave) of ancing these thermoelectric parameters
≈0.98 can be obtained in PbTe-30%SnSe-1.5%Cu at 300–573 K, which makes above.[2]
To date, many effective strategies have
its performance comparable to the commercial n-type Bi2Te3-based thermo-
been explored to pursue high-perfor-
electric material. mance thermoelectric materials, such as
band structure manipulation,[3] dynamic
doping,[4] hierarchical structure design,[5]
etc. Based on these methods, a lot of promising thermoelec-
tric materials have been successfully developed. According
Y. Xiao, H. Wu, L. Xu, G. Peng, X. Ding
State Key Laboratory for Mechanical Behavior of Materials
to their optimal working temperature ranges, thermoelectric
Xi’an Jiaotong University materials can be divided into three categories. In low tem-
Xi’an 710049, China perature range (300–500 K), the representative thermoelec-
E-mail: xiao_yu@xjtu.edu.cn tric materials are Bi2Te3-based compounds,[6] Mg3(Bi, Sb)2,[7]
H. Shi, Y. Qin, L.-D. Zhao MgAgSb,[8] etc.; In middle temperature range (500–900 K),
School of Materials Science and Engineering there are many good thermoelectric materials, including lead
Beihang University
Beijing 100191, China chalcogenides,[9] BiCuSeO,[10] Sn(Se, S),[11] skutterudites,[12]
E-mail: zhaolidong@buaa.edu.cn clathrates,[13] etc.; In high temperature range (>900 K), rep-
Y. Zhu, Z.-H. Ge resentative thermoelectric materials are Si–Ge alloys,[14] half-
Faculty of Materials Science and Engineering Heusler alloys,[15] (Pr, La)3Te4,[16] etc. Obviously, less low-tem-
Kunming University of Science and Technology perature thermoelectric materials have been found compared
Kunming 650093, China
with diverse middle-temperature compounds. Among these
Y. Zhang
Instrumental Analysis Center of Xi’an Jiaotong University
low-temperature materials, Bi2Te3-based compound is still the
Xi’an Jiaotong University main commercial thermoelectric material, but its comparably
Xi’an 710049, China low performance in n-type Bi2Te3 restricts its device efficiency.
Therefore, it is meaningful to develop more high-performance
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/aenm.202200204.
near-room-temperature thermoelectric materials, which can
work as a candidate of n-type Bi2Te3 materials applied near
DOI: 10.1002/aenm.202200204 room temperature.

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PbTe, a typical lead chalcogenide, has always been considered

as a middle-temperature thermoelectric material used for power
generation.[3b,17] But recent results prove that PbTe can also show
potential low-temperature thermoelectric performance due to its
high electrical transport properties at room temperature.[4a,d,18]
Herein, this work attempts to extend its high thermoelectric
property in n-type PbTe to low temperature range (300–573 K).
It is known to all that the optimal working temperature for
thermoelectric material is mainly determined by its bandgap
and low bandgap can benefits low-temperature thermoelectric
performance, vice versa.[19] Therefore, the room-temperature
bandgap in n-type PbTe is first narrowed from ≈0.28 eV in
Pb0.985Sb0.015Te to ≈0.12 eV in Pb0.985Sb0.015Te-35%SnSe, which
make its peak ZT shift from 773 K in Pb0.985Sb0.015Te to 473 K
in Pb0.985Sb0.015Te-35%SnSe. To further enhance the carrier
transport properties, Cu interstitial doping is introduced into
PbTe-30%SnSe-x%Cu (x = 0–2.0) to reoptimize the carrier den-
sity. Then, the electrical transport properties undergo remark-
able improvement in the entire working temperature range,
and the average power factor increases from ≈10.2 µW cm−1 K−2
in Pb0.985Sb0.015Te-30%SnSe to ≈16.2 µW cm−1 K−2 in PbTe-
30%SnSe-1.5%Cu at 300–773 K. What’s more, high-density
dislocations form in PbTe-30%SnSe-x%Cu (x = 0–2.0) due to
large mismatch atom size between SnSe and PbTe, which can
strongly intensify phonon scattering. Accordingly, the lattice
thermal conductivity is largely suppressed from ≈2.21 W m−1 K−1 Figure 1. Thermoelectric performance of PbTe-30%SnSe-1.5%Cu sample:
in Pb0.985Sb0.015Te to ≈0.53 W m−1 K−1 in PbTe-30%SnSe-1.5%Cu a) comparison of ZT values between PbTe-30%SnSe-1.5%Cu, high-perfor-
mance n-type PbTe-based materials and Bi2Te3-based materials; b) com-
at 300 K. Finally, the ZT values in PbTe-30%SnSe-x%Cu (x =
parison of ZTave (300–573 K) values between PbTe-30%SnSe-1.5%Cu and
0–2.0) are obviously enhanced especially at low tempera- other high-performance PbTe-based thermoelectric materials; c) com-
ture range (300–573 K), and the room-temperature ZT value parison of thermoelectric cooling performance between PbTe-30%SnSe-
increases from ≈0.1 in Pb0.985Sb0.015Te to ≈0.7 in PbTe-30%SnSe- 1.5%Cu and commercial n-type Bi2Te3, the inset shows the home-made
1.5%Cu, which favorably contributes to a high average ZT value device test of thermoelectric cooling property; d) power density, the inset
of ≈0.98 at 300–573 K. shows the mini-PEM test; e) thermoelectric conversion efficiency; f) com-
parison of maximum thermoelectric conversion efficiency and output
power between PbTe-30%SnSe-1.5%Cu and Bi2Te3-based thermoelectric
materials.
2. Results and Discussion
2.1. ZT Value and Single-Leg Device Performance Both the thermoelectric cooling test and power generation
test are implemented with a single-leg device based on PbTe-
To enhance the near-room-temperature thermoelectric prop- 30%SnSe-1.5%Cu. The thermoelectric cooling test is conducted
erties in n-type PbTe-based material, this work conducts two using a home-made setup,[24] and the single-leg thermoelec-
successive methods, including SnSe alloying to manipulate tric device is shown in the inset of Figure 1c. With increasing
bandgap and Cu interstitial doping to reoptimize carrier density, applied current, the temperature difference (ΔT) presents a
which can synergistically optimize its carrier and phonon trans- linear increase between two sides of single leg, and a maximum
port properties. As a result, a maximum room-temperature ZT ΔT of ≈15.6 K can be produced with current of ≈2 A in Figure 1c.
value of ≈0.7 can be achieved in n-type PbTe-30%SnSe-1.5%Cu. This produced maximum ΔT in n-type PbTe-30%SnSe-1.5%Cu
This highly enhanced ZT value in PbTe-30%SnSe-1.5%Cu out- is much higher than the maximum ΔT of ≈6.0 K in commercial
performs other high-performance n-type PbTe samples, such as n-type Bi2Te3. The low ΔT in n-type Bi2Te3 could be due to its
PbTe-Ga,[4a] PbTe-In,[4d] PbTe-Cu,[20] PbTe-CuSbSe2,[18a] shown in relatively high thermal conductivity,[21] and the thermal conduc-
Figure 1a. Thus, PbTe-30%SnSe-1.5%Cu presents a favorable tivity in PbTe-30%SnSe-1.5%Cu will be discussed in following
low-temperature thermoelectric performance and its average part. The detail data of thermoelectric cooling performance can
ZT value can reach ≈0.98 at 300–573 K, shown in Figure 1b. be found in Tables S1 and S2 (Supporting Information). The
More importantly, this high thermoelectric performance in power generation test is conducted with mini-PEM instrument,
PbTe-30%SnSe-1.5%Cu is comparable with the property in as shown in the inset of Figure 1d. The single leg owns potential
some n-type Bi2Te3-based materials, including commercial output power density at different temperature, and produces a
n-type Bi2Te3 (Bi2Te2.5Se0.5),[21] Bi2Te2.7Se0.3-1wt%Bi2S3,[22] and maximum power density of ≈0.40 W cm−2 at TC = 295 K and
Bi2Te3-1wt%Ru,[23] indicating that PbTe-30%SnSe-1.5%Cu could TH = 765 K. And finally, the maximum thermoelectric conver-
own potential thermoelectric cooling and power generation sion efficiency of ≈1.5% can be achieved in Figure 1e. Compared
near room temperature. with the thermoelectric power generation in commercial n-type

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Bi2Te3, the PbTe-30%SnSe-1.5%Cu presents higher output Figure 2b,c shows the temperature-dependent electrical
power and can extend its working condition to higher tempera- conductivity and Seebeck coefficient in Pb0.985Sb0.015Te-
ture range, as shown in Figure 1f. The relatively lower conver- x%SnSe (x = 0–35). The electrical conductivity undergoes
sion efficiency in PbTe-30%SnSe-1.5%Cu-based single leg could large decrease after SnSe alloying, which might arise from
be caused by its mismatched electrode contact material, and reduced carrier density and intensified carrier scattering. Cor-
higher thermoelectric performance is to be expected in PbTe- respondingly, the absolute Seebeck coefficient largely increases
30%SnSe-1.5%Cu-based device if the electrode interface can be from ≈62.1 µV K−1 in Pb0.985Sb0.015Te to ≈162.5 µV K−1 in
further optimized. Pb0.985Sb0.015Te-35%SnSe, proving the reduced carrier density
in SnSe-alloyed PbTe in Figure 2d. Consequently, the power
factor in Pb0.985Sb0.015Te-x%SnSe (x = 0–35) maintains at high
2.2. Thermoelectric Performance in Pb0.985Sb0.015Te-x%SnSe value (≈10 µW cm−1 K−2) near room temperature, but dra-
(x = 0–35) matically decreases at high temperature range, as shown in
Figure S3 (Supporting Information). Although the carrier
Because small bandgap can facilitate electrical transport prop- density decreases from ≈4.77 × 1019 cm−3 in Pb0.985Sb0.015Te to
erties at low temperature, SnSe alloying in Pb0.985Sb0.015Te ≈4.58 × 1018 cm−3 in Pb0.985Sb0.015Te-35%SnSe, the carrier mobility
is conducted to narrow its bandgap. In Figure 2a, the room- in Pb0.985Sb0.015Te-x%SnSe (x = 0–35) can be obviously boosted,
temperature bandgap in Pb0.985Sb0.015Te-x%SnSe (x = 0–35) and the maximum carrier mobility achieves at ≈547 cm2 V−1 s−1
continuously decreases with increasing SnSe alloying content, at 300 K, as shown in Figure 2d. From the Pisarenko relation-
from ≈0.28 eV in Pb0.985Sb0.015Te to ≈0.12 eV in Pb0.985Sb0.015Te- ship in Figure 2e, SnSe alloying in PbTe reduces the carrier
35%SnSe, see the fitted bandgap value in Figure S1 (Sup- effective mass, and the room-temperature carrier effective
porting Information). The continuously decreasing bandgap in mass decreases from ≈0.29 me in Pb0.985Sb0.015Te to ≈0.19 me in
Pb0.985Sb0.015Te-x%SnSe (x = 0–35) also signifies a large solu- Pb0.985Sb0.015Te-35%SnSe. The reduced carrier effective mass in
bility of SnSe in PbTe matrix. As proved by X-ray diffraction Pb0.985Sb0.015Te-x%SnSe (x = 0–35) originates from conduction
(XRD) patterns in Figure S2 (Supporting Information), all the band sharpening caused by Sn element, and the carrier effective
samples in Pb0.985Sb0.015Te-x%SnSe (x = 0–35) present cubic mass presents a proportional relationship with its bandgap value
phase and the lattice parameter linearly decrease from ≈6.46 Å in Figure 2f, which has been observed in lead chalcogenides.[25]
in Pb0.985Sb0.015Te to ≈6.28 Å in Pb0.985Sb0.015Te-35%SnSe. Figure 3a presents the total thermal conductivity in
Pb0.985Sb0.015Te-x%SnSe (x = 0–35). It is shown that the
total thermal conductivity in Pb0.985Sb0.015Te-x%SnSe (x =
0–35) is obviously suppressed after SnSe alloying, from
≈3.84 Wm−1 K−1 in Pb0.985Sb0.015Te to ≈0.95 Wm−1 K−1 in
Pb0.985Sb0.015Te-35%SnSe at 300 K. This largely suppressed
total thermal conductivity arises from both reduced elec-
tronic thermal conductivity and lattice thermal conductivity
shown in Figure S4a (Supporting Information) and Figure 3b,

Figure 2. Electrical transport properties in Pb0.985Sb0.015Te-x%SnSe Figure 3. Thermal transport properties and ZT values in
(x = 0–35): (a) optical bandgap (Eg); b) electrical conductivity; c) See- Pb0.985Sb0.015Te-x%SnSe (x = 0–35): a) total thermal conductivity; b) lat-
beck coefficient; d) room-temperature carrier density and carrier mobility; tice thermal conductivity; c) the ratio of weighted carrier mobility to lattice
e) Pisarenko relationships with different effective mass m* = 0.4, 0.3, and thermal conductivity; d) ZT values, the inset shows relationship between
0.2 (me); f) relationship between m* and Eg. temperature of maximum ZT and SnSe content.

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respectively. Notably, the room-temperature lattice thermal

conductivity in Pb0.985Sb0.015Te-x%SnSe (x = 0–35) decreases
from ≈2.20 Wm−1 K−1 in Pb0.985Sb0.015Te to ≈0.67 Wm−1 K−1 in
Pb0.985Sb0.015Te-30%SnSe, as shown in Figure S4b (Supporting
Information), due to the increased phonon scattering by
imported defects, which will be discussed in microstructure
observation part. More details about thermal transport proper-
ties, such as sample density, thermal diffusivity, heat capacity,
and Lorenz number, can be found in Figure S5 (Supporting
Information).
To evaluate the synergistic effect of SnSe alloying in
Pb0.985Sb0.015Te-x%SnSe (x = 0–35), the ratio of weighted carrier
mobility (µW) to lattice thermal conductivity (κl) is calculated.
The weighted carrier mobility can be calculated with measured
electrical conductivity (σ) and Seebeck coefficient (S), and fol-
lows the relationships below[26]

3/2
3σ  h2 
µW = (1)
8π eF0 (η )  2m ekBT 

∞ xn
Fn (η ) = ∫ dx (2)
0 1 + e x −η

kB  (r + 5/2) Fr +2/3 (η ) 
S=± − η (3) Figure 4. Electrical transport properties in PbTe-30%SnSe-x%Cu (x =
e  (r + 3/2) Fr +1/2 (η )  0–2): a) electrical conductivity; b) Seebeck coefficient; c) power factor;
d) room-temperature carrier density and carrier mobility; temperature-
where e, h, me, and kB denote the unit charge, Planck con- dependent e) carrier density and f) carrier mobility.
stant, electron mass, and the Boltzmann constant, respec-
tively. Fn(η) is the Fermi integral, η is reduced Ferimi level,
r is the scattering factor and equals −1/2 when acoustic PbTe-30%SnSe-x%Cu (x = 0–2) shows a similar temperature-
scattering mechanism dominates.[27] The calculated values dependent tendency with electrical conductivity in Figure 4b.
of µW/κl in Pb0.985Sb0.015Te-x%SnSe (x = 0–35) at 300, Compared with Sb doping in Pb0.985Sb0.015Te-30%SnSe
373, and 473 K are shown in Figure 3c with increasing sample, Cu interstitial doping in PbTe-30%SnSe-x%Cu (x =
SnSe alloying content. Results show that SnSe alloying 0–2) cause exceptional electrical transport properties. And
in Pb0.985Sb0.015Te-x%SnSe (x = 0–35) can boosts µW/κl at the power factor in PbTe-30%SnSe-x%Cu (x = 0–2) under-
low temperature, thus contributing to obviously enhanced goes large increase in Figure 4c. The maximum power
ZT value especially at low temperature range, as shown in factor and average power factor increase from ≈12.5 and
Figure 3d. And the inset in Figure 3d shows the peak ZT ≈10.2 µW cm−1 K−2 in Pb0.985Sb0.015Te-30%SnSe to ≈19.3 and
values in Pb0.985Sb0.015Te-x%SnSe (x = 0–35) continuously ≈16.2 µW cm−1 K−2 in PbTe-30%SnSe-1.5%Cu at 300–773 K,
shift to low temperature with increasing SnSe content, and the average power factor can be found in Figure S7 (Sup-
proving that narrowing bandgap is effective to optimize ther- porting Information).
moelectric performance near room temperature. Hall measurement reveals that the boosted electrical trans-
port properties in PbTe-30%SnSe-x%Cu (x = 0–2) originate
from the reoptimized carrier density and carrier mobility.
2.3. Electrical Transport Properties in PbTe-30%SnSe-x%Cu Figure 4d presents the room-temperature hall results, and the
(x = 0–2) Cu interstitial doping in PbTe-30%SnSe-x%Cu (x = 0-2) leads
to lower carrier density than that in Pb0.985Sb0.015Te-30%SnSe,
To further enhance the electrical transport properties in thereby benefiting high carrier mobility at room temperature.
SnSe-alloyed PbTe, Cu doping is conducted to reoptimize Additionally, high-temperature hall measurement uncloses
carrier density in PbTe-30%SnSe-x%Cu (x = 0–2). The that Cu interstitial doping in PbTe-30%SnSe-1.5%Cu shows a
XRD patterns in Figure S6 (Supporting Information) show dynamic doping behavior in Figure 4e, as observed in previous
that all PbTe-30%SnSe-x%Cu (x = 0–2) samples own cubic works.[20] This Cu dynamic doping in PbTe-30%SnSe-1.5%Cu
crystal structure and the calculated lattice parameter slightly facilitates much higher carrier mobility in the whole tem-
increases after Cu interstitial doping. With Cu intersti- perature range when compared with Pb0.985Sb0.015Te and
tial doping, the temperature-dependent electrical conduc- Pb0.985Sb0.015Te-30%SnSe, shown in Figure 4f. A maximum
tivity in PbTe-30%SnSe-x%Cu (x = 0–2) first decreases at carrier mobility of ≈2400 cm2 V−1 s−1 can be obtained in
300–573 K and then goes up at 573–773 K, shown in Figure 4a. PbTe-30%SnSe-1.5%Cu at 300 K and it still maintains at
Besides, the absolute value of Seebeck coefficient in ≈110 cm2 V−1 s−1 at 773 K.

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Figure 5. Structural defects in PbTe-30%SnSe-1.5%Cu. a) Low-magnification TEM image, with the respective electron diffraction pattern along [110]
inset, b) Low-magnification STEM ABF image, with the respective STEM HAADF image inset, and c) STEM ABF image, showing high density of dislo-
cations arrays. d,e) Selected area electron diffraction pattern along [111] with a short and long exposure time. f) high-magnification STEM ABF image
focusing on one dislocation intersection. g) Atomically-resolved STEM ABF image and its FFT h). i1–i4) IFFT image of the region marked in g) from
the reflections of -11-1, 11-1, 200, and 02–2.

2.4. Microstructure Observation in PbTe-30%SnSe-1.5%Cu when the exposure time of electron diffraction pattern was
enhanced largely. These diffused superlattices suggests the
To reveal the structural origin of the lowered thermal trans- existence of high-density dislocations with certain ordered
port of PbTe with the introduction of SnSe and Cu, the patterns. Here, the dislocation array is actually composed with
microstructure of PbTe-30%SnSe-1.5%Cu was studied by several dislocations in an array, whose strain fields interact
means of (scanning) transmission electron microscopy (TEM/ with each other. When the density of dislocation increases,
STEM) techniques. First of all, there are almost no precipi- dislocation arrays further interact with each other to form
tates although a large fraction of SnSe is introduced into various types of dislocation intersection patterns, as shown
PbTe, which suggests that SnSe has been well dissolved in in Figure 5c, which form a larger scale of structural defects.
the PbTe matrix. The low-magnification TEM, scanning TEM The high-magnification STEM ABF in Figure 5f,g presents
(STEM) images in Figure 5a–c present the major structural two representative interacted dislocation arrays. To visualize
feature: a high density of dislocations, in the form of disloca- the dislocation clearly, Figure 5i1–i4 are the IFFT (inverse fast
tion arrays.[28] The contrast of these line defects is strongest Fourier transformation) images transformed from the reflec-
in the TEM mode (Figure 5a), and still obvious in STEM ABF tions of -11-1, 11-1, 200, and 02-2 shown in Figure 5h. They
(annular bright field) mode (Figure 5b,c), while weakest in the show that the dislocation core could be found along different
STEM-HAADF (high angle annular dark field) mode (inset in planes, except one plane, e.g., (-11-1) plane, which is actu-
Figure 5b), revealing strong strain contrast without composi- ally parallel with the extra atom plane of the dislocation. It is
tion segregation. The electron diffraction was also employed readily seen that the high density of dislocations with various
to reveal the structural feature. As shown in Figure 5d,e, the scales of patterns can contribute much to phonon scatterings
weak and diffused superlattice reflections could be found with different wavelengths.

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3. Conclusions
In summary, a high average ZT value of ≈0.98 has been
obtained in n-type PbTe-30%SnSe-1.5%Cu at 300–573 K,
making it as a potential near-room-temperature thermoelec-
tric material. This high-ranged thermoelectric performance in
n-type PbTe-based material is mainly attributed to its narrowed
bandgap with SnSe alloying and reoptimized carrier density
with Cu interstitial doping. Narrowed bandgap in PbTe can
benefit electrical transport properties near room temperature,
and the reoptimized carrier density can well match its lowered
carrier effective mass, which effectively enhances the carrier
transport properties in n-type PbTe-30%SnSe-1.5%Cu. Fur-
thermore, large amount of SnSe alloying in PbTe cause high-
density dislocations in matrix, thus the phonon transport can
be strongly blocked. With these optimized carrier and phonon
transport properties, high thermoelectric performance in n-type
PbTe can be successfully extended to room temperature range.
Figure 6. Thermal transport properties and ZT values in PbTe-30%SnSe- This work provides a very useful strategy to optimize low-
x%Cu (x = 0–2): a) total thermal conductivity; b) lattice thermal conduc- temperature thermoelectric performance, which could be also
tivity; c) comparison of lattice thermal conductivity between PbTe-30% applied in other systems.
SnSe-1.5% Cu and some other n-type PbTe-based thermoelectric mate-
rials; d) ZT values.

4. Experimental Section
All the n-type PbTe-based samples in this work were prepared by melting
reaction and then spark plasma sintering (SPS-211Lx). The room-
2.5. Thermal Conductivity and ZT Value in PbTe-30%SnSe-x%Cu
temperature optical bandgap was measured using Infrared Diffuse
(x = 0–2) Reflection method with a Fourier Transform Infrared Spectrometer
(IRAffinity-1S). The Room-temperature and high-temperature Hall
Figure 6a shows the temperature-dependent total thermal measurements were conducted in Lake Shore 8400 instrument using
conductivity in PbTe-30%SnSe-x%Cu (x = 0–2), and all the Van der Pauw method. Scanning transmission electron microscopy
Cu-doped samples present a very low total thermal con- (STEM) studies were conducted using aberration-corrected electron
ductivity (<0.9 W m−1 K−1) in the whole temperature range. microscopies, JEOL JEM-ARM300F2 and JEM-ARM200F NEOARM.
Thermal diffusivity (D) was acquired with Netzsch LFA457. The
The low total thermal conductivity in PbTe-30%SnSe-x%Cu electrical conductivity and Seebeck coefficient were measured using CTA
(x = 0–2) arises from both suppressed electronic thermal instrument. More experimental details can be found in the Supporting
conductivity in Figure S8d (Supporting Information) and Information.
largely reduced lattice thermal conductivity in Figure 6b.
As unclosed microstructures in TEM results, these high-
density dislocations in PbTe-30%SnSe-x%Cu (x = 0–2) can
strengthen phonon scattering. Therefore, the lattice thermal Supporting Information
conductivity is dramatically reduced from ≈2.2 Wm−1 K−1 Supporting Information is available from the Wiley Online Library or
in Pb0.985Sb0.015Te to ≈0.53 Wm−1 K−1 in PbTe-30%SnSe- from the author.
1.5%Cu at room temperature, and continuously decreases to
≈0.4 Wm−1 K−1 at 773 K. More details about thermal transport
properties can be found in Figure S8 (Supporting Informa-
tion). Compared with other high-performance n-type PbTe- Acknowledgements
based materials, such as PbTe-CuSbSe2,[18a] PbTe-Cd,[29] Y.X. and H.W. contributed equally to this work. The authors acknowledge
PbTe-Cu2Te,[18b] PbTe-Cu,[20] PbTe-InSb,[30] PbTe-S-Cu,[31] and the financial support from the Fundamental Research Funds for the
PbTe-Se-Cu,[32] PbTe-30%SnSe-1.5%Cu presents a relatively Central Universities (No. xtr042021007), Top Young Talents Programme
low lattice thermal conductivity especially at 300–573 K, of Xi’an Jiaotong University, National Natural Science Foundation
of China (Nos. 52172236 and 52172128), National Key Research and
shown in Figure 6c. Combining the largely reduced thermal Development Program of China (No. 2021YFB3201100), and National
conductivity and boosted power factor, the room-temper- Science Fund for Distinguished Young Scholars (No. 51925101). The
ature ZT value obtains sevenfold increase, from ≈0.1 in authors would like to acknowledge the strong support from Instrumental
Pb0.985Sb0.015Te to ≈0.7 in PbTe-30%SnSe-1.5%Cu, shown in Analysis Center of Xi’an Jiaotong University.
Figure 6d. More importantly, the ZT value in PbTe-30%SnSe-
x%Cu (x = 0–2) can continuously increase at 300–773 K,
which contributes to a high-ranged ZT value and makes its
performance comparable to some n-type Bi2Te3-based ther- Conflict of Interest
moelectric materials.[21,23] The authors declare no conflict of interest.

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