Journal of Materiomics 7 (2021) 146e155

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Journal of Materiomics
journal homepage: www.journals.elsevier.com/journal-of-materiomics/

Synergistic optimization of electrical and thermal transport in n-type

Bi-doped PbTe by introducing coherent nanophase Cu1.75Te
Chen Zhu a, b, Jian Zhang a, *, Hongwei Ming a, b, Lulu Huang a, b, Yuanyue Li c, Tao Chen a, b,
Di Li a, **, Baoli Zhang a, d, Jingtao Xu e, Xiaoying Qin a, ***
a
Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei, 230031, China
b
University of Science and Technology of China, Hefei, 230026, China
c
College of Microtechnology & Nanotechnology, Qingdao University, Qingdao, 266071, China
d
Anhui University, Hefei, 230601, China
e
Ningbo Ruiling Advanced Energy Materials Institute Co., Ltd, Ningbo, 315500, China

a r t i c l e i n f o a b s t r a c t

Article history: Based on the calculated results of band structures and density of states, Bi doping is used to adjust its
Received 21 May 2020 carrier concentration in order to obtain n-type PbTe materials with high power factor. Then, coherent
Received in revised form nanophase Cu1.75Te is in situ formed in the n-type PbTe matrix, which can simultaneously optimize the
16 July 2020
thermal and electrical properties. As a result, at a relative lower temperature than other reports, the
Accepted 4 August 2020
highest ZT value of 1.4 is obtained at 623 K for the nominal Pb0.995Bi0.005Teþ0.86 wt% Cu1.75Te sample.
Available online 12 August 2020
More importantly, the ZT hold a higher value in the broad temperature; especially, ZT value is about 1.2
e1.4 in the temperature range of 573e773 K, which is beneficial to the significant average ZT value
Keywords:
Thermoelectric
ZTave ~ 0.9 in the temperature range of 300e773 K. These results indicate that it is an effective and
n-type PbTe feasible method to enhance the thermoelectric properties via synergistic modulation of electrical and
Electrical transport thermal transport properties by element doping and in situ coherent nanophase.
Thermal transport © 2020 The Chinese Ceramic Society. Production and hosting by Elsevier B.V. This is an open access
Nanophase article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction
Thermoelectric can directly generate electricity from heat or
vice versa, which shows important promising applications in en-
ergy harvesting, thermoelectric coolers, and thermal detectors [1].
The efficiency of thermoelectric device is determined by the figure
of merit ZT ¼ S2sT/(keþkL), where S, s, T, ke and kL are the Seebeck
coefficient, electrical conductivity, the absolute temperature, and
the electronic and lattice components of the thermal conductivity,
respectively [2e4]. In addition, we usually use the power factor (PF)
to represent the electrical transport properties of thermoelectric
(TE) materials, which is defined as PF ¼ S2s [5].
In order to improve ZT, higher PF and lower keþkL are needed for
good thermoelectric materials. However, it is difficult to achieve
* Corresponding author.
** Corresponding author.
*** Corresponding author.
E-mail addresses: zhangjian@issp.ac.cn (J. Zhang), lidi@issp.ac.cn (D. Li), xyqin@
issp.ac.cn (X. Qin).
Peer review under responsibility of The Chinese Ceramic Society.
higher ZT because all of these parameters are related to each other
through carrier concentration, band structure, primary scattering
mechanism, and so on [6]. Recently, many researchers have focused
on increasing the power factor S2s by studying the influence of
resonant states, band convergence [7e9], and energy filtering ef-
fects [10]. Meanwhile, other people make a great deal of efforts to
decrease the lattice thermal conductivity kL by various methods,
such as introducing of nanoprecipitation, point defects [11e17],
nanoscale phonon scattering centers [18], nanoscale grain bound-
aries [19e21], and so on [22,23].
PbTe is one of the best middle-temperature thermoelectric
materials, which has been applied extensively in recycling waste
heat from factories, engines, etc. [24]. As we know, the ZT values for
p-type PbTe alloys have been considerably improved in recent year.
The maximum value ZT > 2 was obtained by Wu et al. [21,25]. But
the ZT values in n-type PbTe are relatively lower compared with p-
type [26e28]. Notably, it is necessary to maximize the efficiency for
a thermoelectric device through developing the well-matched
performance for both p-type and n-type PbTe [29]. Therefore, the
researches on n-type PbTe materials are urgent. However, it is re-
ported that the power factor of n-type PbTe could not be effectively

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2352-8478/© 2020 The Chinese Ceramic Society. Production and hosting by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://
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C. Zhu, J. Zhang, H. Ming et al.
improved by band convergence because of the large offset between
light (L) and heavy (S) conduction bands [29]. Besides, the thermal
conductivity is higher and bipolar thermal conductivity cannot be
entirely prohibited. At present, optimization of electron concen-
tration, nano-structuring and point defects etc. are used widely in
enhancing the thermoelectric performances for n-type PbTe alloys
[24].
In this work, firstly, element Bi is selected to dope at the Pb site
for improving the electrical properties by adjust electron concen-
tration. Then, CuO nanoparticles are introduced as precursor to in
situ form Cu1.75Te coherent nanophase and then reduce the thermal
conductivity via phonon scattering. Finally, the maximum of ZT ~
1.4 is obtained at 623 K for the Pb0.995Bi0.005Teþ0.86 wt% Cu1.75Te
sample, which is about 366% larger than that of pristine PbTe.
2. Experimental section
2.1. Synthesis
Elemental Pb shots (Alfa Aesar, 99.999%), Bi granules (Alfa Aesar,
99.997%), and Te broken ingots (Alfa Aesar, 99.99%) were used as
raw materials for the synthesis of Pb1-xBixTe (x ¼ 0, 0.0025, 0.005,
0.01, 0.015 and 0.02) compounds. The mixture was sealed in an
evacuated quartz tube, heated to 1323 K in 5.5 h, and maintained at
this temperature for 24 h followed by room-temperature water
quenching. Eventually, the Pb1-xBixTe samples, which were
embedded in ingot by this method, were obtained. Based on the
thermoelectric performance of doped compounds, Pb0.995Bi0.005Te,
which has the best thermoelectric properties, was selected as
matrix to composite with CuO (Aladdin, 99.5%) nanoparticles. And
then, the composites nominal Pb0.995Bi0.005Te þ y wt.% CuO
(y ¼ 0.25, 0.5, 0.75, 1.0) bulk was prepared using graphite die by
spark plasma sintering (SPS) process, in which CuO nanoparticles
would be reduced to copper in the reducing atmosphere, then react
with the PbTe and in situ form CuPb defects and/or Cu1.75Te nano-
phase embedded in the PbTe matrix. And then, the content of bulk
composites should be described as Pb0.995Bi0.005Te þ f wt.% Cu1.75Te
(f ¼ 0.43, 0.86, 1.29, 1.72).
2.2. Structural characterization
The structure analysis was carried out by X-ray diffraction (XRD)
on a Philips X’Pert PRO X-ray diffractometer equipped with graphite
monochromatic Cu Ka radiation (l ¼ 1.54056 Å), for which the
operating voltage and current were kept at 40 kV and 40 mA. XRD
data was collected between the range 10e90 with a step size of
0.033 for 2q at room temperature. Microstructures were charac-
terized by transmission electron microscopy (TEM) performed on a
JEOLF2010 instrument with an acceleration voltage of 200 kV.
2.3. Transport property measurements
The electrical conductivity and Seebeck coefficient were
measured simultaneously between 300 and 773 K by using com-
mercial four-probe equipment (ZEM-3(M10) Ulvac Riko, Inc.). The
Hall coefficient (RH) was measured under a reversible magnetic
field (0.8 T) by the Vander Pauw method via the Hall measurement
system (Lake Shore 8400 Series, Model 8404, USA) across a wide
temperature range from 300 to 773 K. The carrier density (n) was
obtained via n ¼ 1/(eRH), and the carrier mobility (m) was calculated
by m ¼ sRH. The thermal conductivity was calculated from
k ¼ a,Cp,d, where a, Cp, and d are the thermal diffusivity and
specific heat and density, respectively. The thermal diffusivity a
was measured by the laser flash method (Netzsch, LFA-457). Heat
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Journal of Materiomics 7 (2021) 146e155
capacity Cp was estimated according to the Dulong-Petit limit with
a value of ~0.15 J/g,K [30]. The density of bulk samples was
determined by Archimedes’ methods in absolute ethanol, all which
were larger than 97% of the theoretical density (Table A.1).
2.4. Computational details
The first-principles calculation have been carried out by the
Vienna ab initio simulation package (VASP [31]) using the Perdew-
Burke-Ernzerhof generalized gradient approximation and projector
augmented wave pseudopotentials [32]. Supercell models of 64
atoms and 216 atoms were built for PbTe. The plane-wave cutoff
energy of 500 eV was adopted. Monkhorst-Pack k-point mesh and
an energy conversion criterion of 1  104 eV per atom were used in
the calculations.
3. Results and discussion
Fig. 1(a, b) shows the XRD patterns for Pb1-xBixTe (x ¼ 0, 0.0025,
0.005, 0.01, 0.015 and 0.02) and Pb0.995Bi0.005Te þ f wt.% Cu1.75Te
(f ¼ 0.43, 0.86, 1.29, 1.72) samples. One can see that the main
diffraction peaks for Pb1-xBixTe samples are consistent with the
standard card (PDF# 03-065-2953). No impurity diffraction peak is
found in XRD patterns for all samples, which indicates that both
Pb1-xBixTe and Pb0.995Bi0.005Te þ f wt.% Cu1.75Te mainly consist of
single phase structure. To further confirm the existence of second
nano-phase Cu1.75Te, XRD experiments with a slow scan rate were
carried out. One can see from Fig. A1 that there is a peak at ~43 ,
which matches well with the strongest peak of Cu1.75Te, proving the
existence of Cu1.75Te. Note that the peak of Cu1.75Te is only found in
PBTþ1.72 wt% Cu1.75Te sample because the content of Cu1.75Te in
other samples is too slight to be found. The insets of Fig. 1(a)and (b)
show that the (200) peak gradually shifts to higher 2q angle as
increasing the Bi content x or the Cu1.75Te content f, which means
that the unit cell of both Pb1-xBixTe and Pb0.995Bi0.005Te þ f wt.%
Cu1.75Te is gradually shrink after Bi doping or Cu1.75Te addition. In
order to determine the change behavior of the unit cell in detail, the
lattice parameters are calculated using the Rietveld refinement for
the XRD results by GSAS. The results of refined lattice parameters
(a) and the factor of GSAS Rietveld refinement (Rw) are shown in
Table A.1 in detail. The factor of GSAS Rietveld refinement (Rw) is
less than 9%, which proves that the result of the refinement is
sufficiently reliable. As shown in Fig. 1(c), one can see that the
parameter a decreases regularly from 6.462 Å to 6.454 Å, which
should be due to the slightly smaller ionic radius of Bi3þ (1.03 Å)
than that of Pb2þ (1.19 Å). Moreover, the lattice parameter a of
Pb0.995Bi0.005Te þ f wt.% Cu1.75Te also decreases after incorporation
of Cu1.75Te (Fig. 1(d)), which results from that the Cuþ ions with
smaller radius (0.77 Å) would be introduced into the PbTe matrix
with the formation of CuPb in the SPS process as described in the
experimental section.
Fig. 2 shows the temperature dependence of the electrical
conductivity and Seebeck coefficient for Pb1-xBixTe (0  x  0.02)
and Pb0.995Bi0.005Te þ f wt.% Cu1.75Te (0  f  1.72) samples. One can
see from Fig. 2(a) that the electrical conductivity gradually in-
creases from 1.75 to 7.87  104 S m1 with increasing Bi content
from 0 to 0.02 at the room temperature. The Seebeck coefficient of
all Bi-doped samples are negative in the entire investigated tem-
perature range, which indicates that electrons are the major charge
carriers and n-type PbTe based compounds are obtained by Bi
doping. Besides, the absolute values of Seebeck coefficient slightly
but firmly decrease with increasing the Bi content from 0.0025 to
0.02, which can be ascribed to the increased electron concentration,
as shown in Fig. 3(a). Due to the substitution of Bi3þ for Pb2þ, the
C. Zhu, J. Zhang, H. Ming et al. Journal of Materiomics 7 (2021) 146e155

Fig. 1. XRD patterns for (a) Pb1-xBixTe (x ¼ 0, 0.0025, 0.005, 0.01, 0.015 and 0.02) and (b) Pb0.995Bi0.005Te þ f wt.% Cu1.75Te (f ¼ 0.43, 0.86, 1.29, 1.72) samples at room temperature, and
the inset shows the enlarged (200) diffraction peak, (c) and (d) shows the parameters for Pb1-xBixTe and Pb0.995Bi0.005Te þ f wt.% Cu1.75Te samples obtained from GSAS Rietveld
refinement.

Fig. 2. Temperature dependence of (a) (b) electrical conductivity ðs) and (c) (d) Seebeck coefficient (S) for Pb1-xBixTe (x ¼ 0, 0.0025, 0.005, 0.01, 0.015 and 0.02) and
Pb0.995Bi0.005Te þ f wt.% Cu1.75Te (f ¼ 0.43, 0.86, 1.29, 1.72) samples.

electron concentration increases from 0.82 to 1.38, 2.00 and 2.65  temperature range. Moreover, as shown in Fig. 2(b), the electrical
1019 cm3, as the Bi content increases from x ¼ 0.0025, to 0.005, conductivity decreases from 2.57 to 1.48 104 S m1 after intro-
0.01 and 0.015, respectively. In addition, the electron concentration ducing 0.43 wt% Cu1.75Te into the matrix; however, when the
n presents weakly temperature dependence in the whole content of Cu1.75Te increases further, the electrical conductivity

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Fig. 3. Temperature dependence of (a) (b) electron concentration n and (c) (d) mobility m for Pb1-xBixTe (x ¼ 0, 0.0025, 0.005, 0.01, 0.015 and 0.02) and Pb0.995Bi0.005Te þ f wt.%
Cu1.75Te (f ¼ 0.43, 0.86, 1.29, 1.72) samples.

presents gradual enhancements. The change behavior of electrical respectively, as shown in Fig. 4. One can see- that pure PbTe has a
conductivity for the composites with f > 0 is similar to that of light conduction band at the G point of the Brillouin zone, and with
electron concentration, as shown in Fig. 3(b). After the incorpora- Bi doping, the electron concentration increases, the Fermi level was
tion of Cu1.75Te, the electron concentration n first decreases from pushed into the bottom of the conduction band from near the top of
1.38 to 0.21  1019 cm3 and then gradually rises with increasing f the valence band, which means that the p-type semiconductor
from 0.86 to 1.72 wt%. Fig. 2(d) shows that the absolute values of transform to n-type. In addition, Bi doping can cause an obvious
Seebeck coefficient increase after incorporation of Cu1.75Te almost increment in electronic density of states (DOS), which should be a
in the whole temperature range, which should be resulted from the reason for the enhanced electrical properties. These results are
decreased electron concentration. One can see from Fig. 3(c) that consistent to the measurements of Hall and Seebeck coefficient, as
the mobility m decreases with increasing the Bi doping content due shown in Fig. 3(a) and Fig. 2(c).
to the increased point defects caused by Bi doping and increased Generally, S is inversely proportional to carrier concentration n,
carrier concentration. However, from Fig. 3(d), one notice that the as expressed by the Mott equation [36]:
mobility m is obviously increased especially near the room tem-



perature after incorporation of Cu1.75Te, which can be ascribed to p2 k2B T vlnðsðEÞÞ p2 k2B T 1 vnðEÞ 1 vmðEÞ
the significantly suppressed carrier concentration, and also, the S¼ ¼ þ (1)
3e vE E¼EF 3e n vE m vE E¼EF
other reason should be referred, the weak scattering for electronic
transport by the coherent nanophase Cu1.75Te, as discussed in the
where s is the electrical conductivity, e is the electron charge, kB is
later section. This is why the electrical conductivity holds higher
the Boltzmann constant, and EF is the Fermi energy. Like the work
values although the electron concentration declines after the
reported by Heremans et al. [37], and based on the assuming that
incorporation of Cu1.75Te. Furthermore, it can be found from
the energy bands have a parabolic dispersion relation, the relaxa-
Fig. 3(d) that mobility m for the composite samples roughly obeys
tion time t(E), which can be expressed as the form of a power, with
m f Tg and g  1.5 law in the whole temperature range, indicating
energy E, i.e., t(E) ¼ t0El1/2 [38] then, Equation (1) can be
that acoustical scattering dominates their transport properties
expressed as:
[33e35]. The experiment data slightly deviates from the fitting
curve with increasing f, especially for Pb0.995Bi0.005Te þ 1.72 wt% 2 3
Cu1.75Te sample, suggesting other scattering mechanism may be p2 k2B T 61 vnðEÞ l  127
involved. Notably, other scattering mechanisms such as by grain S¼ 4 þ 5 (2)
3e n vE E
boundaries, ionized impurities, and polar-optical phonons predict
E¼EF
g  0.5 implying that these mechanisms do not dominate the
transport properties. from equation (2), one can notes that S can be enhanced by
In order to elucidate the electrical transport properties for Pb1- increasing the scattering parameter l, and an enhanced l means a
xBixTe, we have performed density functional theory (DFT) calcu- stronger energy filtering effect. In order to check that energy
lations to obtain the electronic band structures and density of states filtering effect is responsible for significant enhancement of S, l can
(DOS) for PbTe, Pb107BiTe108, Pb106Bi2Te108 and Pb31BiTe32, be calculated by using a single parabolic band model in which the
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Fig. 4. Band structures for (a) PbTe and (b) Pb31BiTe32 respectively, (ced) density of states (DOS) for PbTe, Pb107BiTe108, Pb106Bi2Te108 and Pb31BiTe32, respectively.

density of state effective mass m*d and S can be expressed as: increasing f from 0 to 0.86, 1.29 and 1.72. This increase in l results in
increases of ~168, 161 and 154 mV K1 in S at room temperature for
!2=3 the samples with f ¼ 0.86, 1.29 and 1.72, respectively, as shown in
h2 n
m*d ¼ (3) Fig. 5(b) (where the solid line is the Pisarenko relationship [36] for
2kB T 4pF1=2 ðxF Þ
Pb0.995Bi0.005Te and shows the dependence of S on n as calculated
according equation (6)). The enhancement of S is in accordance


kB ðl þ 2ÞFlþ1 ðxF Þ with the scattering parameter l results from the Cu1.75Te existence.
S¼  xF (4)
e ðl þ 1ÞFl ðxF Þ Due to the significantly larger electrical conductivity and absolute
Seebeck coefficient, all specimens show higher power factors
with the Fermi integral of order i: across the entire temperature range. It is important to note that the
sample with x ¼ 0.005 shows a larger power factor, reaches 16.5 
ð
∞
104 W m1 K2, as shown in Fig. 5(c). And furtherly, one can see
xi
Fi ðxF Þ ¼ dx (5) from Fig. 5(d) that the power factor value is elevated to about
1 þ eðxxF Þ
0 20 W m1 K2 after introducing Cu1.75Te into Pb0.995Bi0.005Te.
Especially, the power factor of the composite
where h is Planck’s constant and xF is the reduced Fermi level EF/ Pb0.995Bi0.005Teþ0.86 wt% Cu1.75Te is obviously promoted almost in
(kB T). the whole investigated temperature range, and presents higher
For a degenerate semiconductor, the Seebeck coefficient S can be values (>17 W m1 K2) in a broad temperature range (from 300 to
simplified as an inversely proportional to the carrier concentration 687 K), which is beneficial to average ZT values. In our work, the
n obeys following Mott formula [36]: power factor is enhanced by energy filtering effect due to nanosized
potential barriers. Analogous work has been reported by Neo-
8p2 k2B T *  p 2=3 phytou et al. [40] and Yang et al. [41]. Neophytou et al. [40] pre-
S¼ md (6)
3eh2 3n sented analysis and optimization of such barriers for improved
energy filtering, and synergetic scattering of electrons in semi-
where m*d is the density of state effective mass. m*d ¼ 0.34 m0 (here conductors with metal nanoinclusions was reported by Yang et al.
m0 is the free electron mass) can be obtained for the specimen In agreement with Neophytou et al. [40], to maximize energy
Pb0.995Bi0.005Te according equation (6) and S, n values from Fig. 2(d) filtering, in the region prior to the barrier, the Fermi level needs to
and Fig. 3(b). Using the values of Seebeck coefficient S, the electron be pushed down so that carriers have higher velocity and that
concentration n at room temperature, and assuming the density of scattering by ionized dopant impurities will be weaker, which are
state effective mass m*d is constant in the different composite achieved in our work. Thus, the enhanced thermopower can be
samples [39], the scattering parameters l can be calculated ac- ascribed to the energy filtering effect to some extent.
cording equations (2)e(5). The l values of the composite samples Fig. 6(a-b) shows that the temperature dependence of total
are larger than that of the Bi-doped specimen Pb0.995Bi0.005Te, thermal conductivity for the samples Pb1-xBixTe (0  x  0.02) and
which means that the energy filtering effect works in the Pb0.995Bi0.005Te þ f wt.% Cu1.75Te (0  f  1.72). As the temperature
Pb0.995Bi0.005Te þ f wt.% Cu1.75Te (f > 0) composites system. As increases, the thermal conductivity of all samples decreases due to
shown in Fig. 5(a), l increases from zero to 0.32, 0.48 and 0.71 with enhanced Umklapp phononephonon scattering [35]. And one can

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Fig. 5. (a) The scattering parameter l for composites Pb0.995Bi0.005Te þ f wt.% Cu1.75Te (f ¼ 0.43, 0.86, 1.29, 1.72). (b) Shows the room-temperature Seebeck coefficient versus carrier
concentration, and the solid line is the pisarenko relationship. (c) and (d) show the temperature dependence of power factor PF for Pb1-xBixTe (x ¼ 0, 0.0025, 0.005, 0.01, 0.015 and
0.02) and Pb0.995Bi0.005Te þ f wt.% Cu1.75Te (f ¼ 0.43, 0.86, 1.29, 1.72) samples.

Fig. 6. (a) (b) Temperature dependence of thermal conductivity k and (c) (d) lattice thermal conductivity kL for Pb1-xBixTe (x ¼ 0, 0.0025, 0.005, 0.01, 0.015 and 0.02) and
Pb0.995Bi0.005Te þ f wt.% Cu1.75Te (f ¼ 0.43, 0.86, 1.29, 1.72) samples.

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Fig. 7. (a) The low magnification TEM image for Pb0.995Bi0.005Teþ0.86 wt% Cu1.75Te bulk sample; (b) the selected area electron diffraction (SAED) (false colored); (c) (e) show the
high resolution TEM images for the specimen with f ¼ 0.86; (d) (f) are the GPA results for (c) and (e), respectively.
see that the total thermal conductivity mainly come from the lattice
thermal conductivity, as shown in Fig. 6(ced). The lattice thermal
conductivity (kL) for all samples are calculated from total thermal
conductivity by subtracting the carrier contribution (ke). ke is
calculated from electrical conductivity by using the Wiedemann-
Franz relation, ke ¼ LsT. The value of the Lorenz number L can be
calculated by using the following formula [42]:
 2
kB 3F0 ðhÞF2 ðhÞ  4F12 ðhÞ
L¼
e F02 ðhÞ
where e is the electron charge, Fn is Fermi integral with the order n,
and h is reduced Fermi energy that can be determined from the
Seebeck coefficient, as follows [42]:
 
kB F ðhÞ
S¼± 2 1 h
e F0 ðhÞ
One can see from Fig. 6(ced) that the lattice thermal conductivity
presents a similar value almost in the whole temperature range for
all Bi-doped samples, which successive decreases with increasing
the temperature from 300 to 773 K. This should be result from the
similar mass and radius for Bi3þ and Pb2þ and in accordance with
the reported data [24,43]. Fortunately, the lattice thermal conduc-
tivity for the composites Pb0.995Bi0.005Te þ f wt.% Cu1.75Te
(0  f  1.72) significantly decrease after incorporation of Cu1.75Te,
especially, at the room temperature, the lattice thermal
Journal of Materiomics 7 (2021) 146e155
conductivity for the sample with f ¼ 1.72 reaches 1.32 W m1 K1,
which is 45% smaller than that of Pb0.995Bi0.005Te. The large
reduction of lattice thermal conductivity should be ascribed to the
phonon scattering by point defects and second phases.
In order to clarify the mechanism for the reduction of thermal
conductivity and enhancement of power factor, we have performed
transmission electron microscopy (TEM) measurements to study
the microstructures of the composites Pb0.995Bi0.005Te þ f wt.%
Cu1.75Te. Take the specimen Pb0.995Bi0.005Teþ0.86 wt% Cu1.75Te as
(7) the example, the TEM results are presented in Fig. 7. Fig. 7(a) is a
low magnification transmission electron microscopy image of
Pb0.995Bi0.005Teþ0.86 wt% Cu1.75Te, which shows a nano Cu1.75Te
particle embedded in the Pb0.995Bi0.005Te matrix. The Moire fringe
in Fig. 7(a) implies that the Cu1.75Te nanoprecipitates have a crys-
tallographic relation with respect to the matrix PbTe grains. To
verify that the nano particle is Cu1.75Te, firstly, we have studied the
energy dispersive spectroscopy (EDS) mapping uses the area con-
(8)
tained this nano particle in Fig. A2, in which we can see that the
nano particle is only consist of elements Cu and Te. Secondly, the
selected area electron diffraction (SAED) was performed along the
PbTe [1ðdÞ24] zone axis within the area including nano particles,
as shown in Fig. 7(b), which is false colored. The main spots in the
experimental SAED pattern nicely matches the simulated values of
PbTe not only in the sense of reciprocal distance but also the angles.
For example, as indicated in Fig. 7(b), the measured angle of PbTe
(420) and PbTe (042ðdÞ) is 66.4 , which is nicely close to the ideal
value of 66.42 . In addition, a faint spot appears among the main
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Fig. 8. Temperature dependence of (a) (b) ZT values for Pb1-xBixTe (x ¼ 0, 0.0025, 0.005, 0.01, 0.015 and 0.02) and Pb0.995Bi0.005Te þ f wt.% Cu1.75Te (f ¼ 0.43, 0.86, 1.29, 1.72) samples,
(c) shows average ZT and maximum of ZT values for Pb0.995Bi0.005Te þ f wt.% Cu1.75Te (f ¼ 0, 0.86, 1.72) samples compared with reported data [30,43,44].

spots, which exactly matches the simulated values of Cu1.75Te, the
measured angle of Cu1.75Te (013) and Cu1.75Te (11ðdÞ4) is 96.4 ,
which is nearly consist with the ideal value of 97.1. And the
measured reciprocal distance between the (000) and Cu1.75Te (013)
is about 3.18 nm1, which is also closed to the theoretical value
3.10 nm1. These results can be considered as the proof for the
existence of Cu1.75Te. It is worth noting that the spots PbTe (420)
and (42ðdÞ2) are overlapped with Cu1.75Te (2ðdÞ28ðdÞ) and
(1ðdÞ32), respectively. Furthermore, the angles and the reciprocal
distance for almost all spots belong to PbTe is consist with Cu1.75Te,
which means that not only Cu1.75Te (2ðdÞ28ðdÞ) is aligned parallel
to PbTe (420), but also Cu1.75Te is coherent with the matrix PbTe in
the certain direction of the crystal structure. All TEM results indi-
cate that the coherent nano phase Cu1.75Te is in situ formed and
embedded in the matrix, which can be considered as the important
factor for reduced lattice thermal conductivity and enhanced po-
wer factor. As mentioned above, the coherent interfaces can
strongly scatter the heat carrying phonons and slightly affect the
electronic transport, which can significantly suppress the lattice
thermal conductivity and keep the power factor at a higher level
due to the higher electrical conductivity and Seebeck coefficient.
Generally, in the area contained the second phases, the spatial
element fluctuation should bring about the spatial strain field. In
order to reveal this strain field, we conducted geometric phase
analysis (GPA) strain analysis of the HRTEM images, as shown in
Fig. 7(d)(f). The strain maps obtained by GPA unambiguously show
regions with tensile strain (yellow, red, green, and blue colors) and
those without strain (dark color). The distribution of the area with
bigger tensile strain (yellow color) should mean that the coherent
nano phases Cu1.75Te were formed within this area. The existence of
these coherent nano phases must cause strong scattering of heat
carrying phonons and are mainly responsible for the large reduc-
tion of lattice thermal conductivity of Pb0.995Bi0.005Te þ f wt.%
153
Cu1.75Te samples.
Bi doping in the PbTe matrix can adopt the electron concen-
tration and then adjust the electronic transport properties, as a
result, the ZT value can be enhanced especially in the temperature
range of 500e773 K, and then reaches 1.16 @ 773 K by using only
bismuth doping, as shown in Fig. 8(a). More importantly, the
obviously suppressed lattice thermal conductivity and significantly
enhanced power factor are achieved simultaneously by introducing
the coherent Cu1.75Te nano particles into the Pb0.995Bi0.005Te matrix.
Benefit from the enhanced power factor and reduced thermal
conductivity, the composite Pb0.995Bi0.005Teþ0.86 wt% Cu1.75Te
present a higher ZT value about 1.4 at 623 K and average ZT about
0.9, as shown in Fig. 8(b, c), which is higher values comparing with
other reported results related PbTe based materials [24,43e48].
4. Conclusions
In summary, the n-type Bi-doped PbTe compounds and
Pb0.995Bi0.005Te þ f wt.% Cu1.75Te composites were successfully
synthesized by fusion method and solid state reaction, and their
thermoelectric properties were investigated in the temperature
range of 300e773 K. The results indicated that Bi doping are useful
to adjust the carrier concentration and electronic transport prop-
erties for n-type PbTe materials, reaching a ZT value about ~1.16 at
723 K. In order to furtherly optimize the thermoelectric perfor-
mance of n-type PbTe based materials, the compound
Pb0.995Bi0.005Te was selected as the matrix to prepare composites,
and coherent nanophase Cu1.75Te is in situ formed in the
Pb0.995Bi0.005Te matrix by the reaction in SPS process, which can
simultaneously optimize the thermal and electrical properties. As a
result, the highest ZT value of 1.4 was obtained at 623 K for the
nominal Pb0.995Bi0.005Teþ0.86 wt% Cu1.75Te sample and the ZT hold
a higher value in the broad temperature; especially, ZT value is
C. Zhu, J. Zhang, H. Ming et al.
about 1.2e1.4 in the temperature range of 573e773 K, which is
beneficial to the significant average ZT value ZTave ~ 0.9 in the
temperature range of 300e773 K. These results indicate that it is an
effective and feasible method to enhance the thermoelectric
properties via synergistic modulation of electrical and thermal
transport properties by element doping and in situ coherent
nanophase.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgements
This work is supported by funding from the National Natural
Science Foundation of China [grant numbers 51972307, 51672278
and 11674322]. The authors acknowledge X.G. Zhu and Z.M. Wang
from the Key Laboratory of Materials Physics, Institute of Solid State
Physics, Chinese Academy of Sciences for their help in the analysis
of TEM and SEM.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jmat.2020.08.001.
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Chen Zhu is a Ph.D. candidate in Institute of Solid State

Physics (ISSP), Chinese Academy of Sciences (CAS), China.

155