Journal of Alloys and Compounds 639 (2015) 106–110

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Journal of Alloys and Compounds

journal homepage: www.elsevier.com/locate/jalcom

Letter

Enhanced thermoelectric performance of PbSe co-doped with Ag and Sb

Haotian Fan a, Taichao Su a,⇑, Hongtao Li b, Baoli Du a, Bingguo Liu a, Hairui Sun c, Yuewen Zhang c,
Liang Li d, Shangsheng Li a, Meihua Hu a, Hongan Ma c, Xiaopeng Jia c
a
Institute of Materials Science and Engineering, Cultivating Base for Key Laboratory of Environment-friendly Inorganic Materials in University of Henan Province, Henan
Polytechnic University, Jiaozuo 454000, China
b
Shanghai Entry-Exit Inspection & Quarantine Bureau, Shanghai 200135, China
c
National Lab of Superhard Materials, Jilin University, Changchun 130012, China
d
Department of Materials Science and Engineering, Muroran Institute of Technology, Muroran 050-8585, Japan

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

Article history: Nanostructured thermoelectric materials PbSe co-doped with Ag and Sb (with the composition of
Received 12 January 2015 (AgSb)xPb1 2xSe) were prepared by high pressure method. It was found that appropriate doping with
Received in revised form 10 March 2015 Ag and Sb could reduce both the electrical resistivity and the phonon thermal conductivity simultane-
Accepted 14 March 2015
ously, consequently greatly enhancing the thermoelectric performance. An enhanced figure-of-merit of
Available online 20 March 2015
1.03 has been achieved at 600 K for the sample with x = 0.03, which is about five times higher than that
of undoped PbSe. The improved thermoelectric performance in this study may be due to the effect of high
Keywords:
pressure and the low phonon thermal conductivity resulting from Ag and Sb as source of dopants.
High pressure
PbSe
Ó 2015 Elsevier B.V. All rights reserved.
Thermoelectric

1. Introduction and conduction type of PbSe could be tuned effectively by chang-

Thermoelectric (TE) materials have drawn vast attention
because TE effects enable direct conversion between thermal and
electrical energy, providing possibilities to replace traditional
power generation and refrigeration [1]. The property of TE material
is characterized by the dimensionless figure of merit ZT. ZT is
defined as ZT = S2r/jT, where S is the Seebeck coefficient, r is the
electrical conductivity, j is the thermal conductivity and T is the
absolute temperature [2,3]. S2r is named as power factor which
determines the electrical properties of TE materials. The total ther-
mal conductivity j is the sum of electron thermal conductivity je
and phonon thermal conductivity jph which could be written as
j = jph + je. Because most TE materials are semiconductors whose
phonon thermal conductivity jph is much higher than their elec-
tron thermal conductivity je, so the high performance thermoelec-
tric materials need low phonon thermal conductivity besides the
high power factor.
PbTe is one of the TE materials applied in spacecraft for more
than 50 years [4–6]. However, Te is rare and expensive. In recent
years, as an alternative for PbTe [7], PbSe is focused on by research-
ers [7–15]. In previous work, undoped PbSe has been prepared by
high pressure method [8]. It was found that transport properties
⇑ Corresponding author. Tel.: +86 391 3987482.
E-mail addresses: taichao80@hotmail.com, stc@hpu.edu.cn (T. Su).
ing the synthetic pressure due to local strains. Besides the pres-
sure-tuning, the internal compressive residual stress could also
be induced by alloying. This internal stress occurs due to lattice
distortion, which results from the substitution of impurity-atom
at the crystal lattice.
Up to date, doping modification is a main research direction for
improving the TE performance of PbSe [9–15]. So far the maximum
ZT of PbSe-based TE materials was 1.6 (923 K) for PbSe doped with
CdS nanostructures which was reported by Zhao et al. [9].
Antimony (Sb) doped PbSe was reported by Yeseul Lee et al. [10]
obtaining the maximum ZT of 1.45 (830 K). Additionally, Zhang
et al. reported the thermoelectric properties of PbSe doped with
aluminium (Al) whose maximum ZT was 1.3 (850 K) [11].
Nevertheless, in 2004, Hsu et al. first reported AgPbmSbTem+2
(m = 10, 18) alloys whose maximum value of ZT was 2.2 at
800 K [13]. Shortly afterwards Bilc et al. studied the role of
Ag–Sb microstructures for AgPbmSbTem+2 [14]. Bilc et al. discovered
that Ag and Sb in AgPbmSbTem+2 exited in pairs. Li and his cowork-
ers studied AgPb18SbTe20 system by combining mechanical alloy-
ing (MA) and spark plasma sintering (SPS) [16]. They found that
a similar high figure of merit (1.5 @ 700 K) could be obtained when
the composition was rich in Pb. It was a very good signal to find a
new method improving the thermoelectric properties of PbSe. Cai
et al. synthesized AgPbmSbSem+2 by hydrothermal successfully
[15,17]. They found its maximum power factor was 6  10 4

http://dx.doi.org/10.1016/j.jallcom.2015.03.117
0925-8388/Ó 2015 Elsevier B.V. All rights reserved.
 H. Fan et al. / Journal of Alloys and Compounds 639 (2015) 106–110 107

W/mK2. Zhang et al. reported the thermoelectric properties of
Cl doped P-type AgPb18SbSe20 whose maximum ZT was 1.3
(873 K).
In this paper, P-type PbSe co-doped with Ag–Sb samples are
successfully prepared by high pressure method. The results indi-
cated that PbSe samples co-doped with Ag and Sb exhibited high
power factor and low lattice thermal conductivity, which results
in enhancing thermoelectric performance.
3. Results and discussion
The X-ray diffraction patterns of (AgSb)xPb1 2xSe (x = 0, 0.01,
0.03, 0.05) prepared by high pressure method are shown in
Fig. 1a. It can be seen that the main diffraction peaks match very
well with the standard diffraction data of PbSe (JCPDS card No.
06-0354) indicating that they are NaCl-type structures. All the
peaks (here, we take peaks (2 0 0) for examples in Fig. 1b) move

2. Experimental

(AgSb)xPb1 2xSe (x = 0, 0.01, 0.03, 0.05) samples were prepared with the ele-
ments of lead (99.9%), selenium (99.95%), silver (99.9%) and antimony (99.999%)
as sources which were weighed according to the stoichiometry. After being uni-
formly mixed in an agate mortar, the mixtures were shaped with the size of
£10.5 mm  3 mm. The pole shaped samples were assembled in pyrophyllite for
high-pressure synthesis. (AgSb)xPb1 2xSe compounds were prepared in a cubic anvil
high pressure apparatus (SPD 6  1200) for 30 min at 2.0 GPa and 900 K. The pres-
sure was estimated by the oil press load which was calibrated by the pressure
induced phase transitions of bismuth, thallium and barium metals. The tempera-
ture was estimated by the relationship of input heater power and temperature,
which was measured by the platinum–rhodium thermocouple.
X-ray diffraction (XRD) measurements with Cu Ka radiation were performed on
an X-ray diffractometer (D/MAX-RA). The Seebeck coefficient and electrical resistiv-
ity were measured from 300 K to 600 K by LRS-3. The thermal conductivity was cal-
culated by using j = DqCp, where D was the thermal diffusivity measured by a laser
flash method (Netzsch LFA457), q was the density which was measured by
Archimedes principle. The microstructures of the products were observed by a high
resolution transmission electron microscope (HRTEM, JEOL JEM-2100).

Fig. 2. Temperature dependence of electrical properties of (AgSb)xPb1 2xSe (a)

Fig. 1. The XRD patterns of (AgSb)xPb1 2xSe (a) and details of peak (2 0 0) (b). electrical conductivity, (b) Seebeck coefficient and (c) power factor.
108 H. Fan et al. / Journal of Alloys and Compounds 639 (2015) 106–110

Fig. 3. Temperature dependence of thermal conductivity of (AgSb)xPb1 2xSe.

to high angle with an increase of x indicating that Pb atoms have

been replaced by Ag and Sb whose atom radius are smaller than
that of Pb. These results indicate that (AgSb)xPb1 2xSe samples
could be synthesized by high pressure successfully.
The electrical properties of (AgSb)xPb1 2xSe samples are shown
in Fig. 2. The temperature dependence of electrical conductivities
for (AgSb)xPb1 2xSe samples are shown in Fig. 2a. It can be seen
that the conductivities of the samples doped with Ag and Sb are
much higher than that of undoped PbSe. And it increases with an
increase of x except the sample with x = 0.05. That the electrical
conductivity for sample x = 0.05 decreases can be attributed to
the decrease of carrier mobility. The maximum value is about
6.59  104 S m 1 for (AgSb)0.03Pb0.94Se at 350 K, which is about
ten times higher than that of undoped PbSe. This value matches
to that of AgPbmSbSem+2 heavily doped with Cl reported by
Zhang [18] and it is much higher than that of AgPbmSbSem+2 pre-
pared at normal pressure [18]. It indicates that PbSe doped with
Ag and Sb under high pressure is helpful to increase the electrical
conductivity without further doping. In general, the charge trans-
port properties of narrow gap semiconductors are sensitive to
extremely small changes in effective mass, mobility, and concen-
tration of carriers around the Fermi level, which are affected by
the changes in the dopants composition. The band gap of PbSe
becomes smaller under high pressure. So, the effect of the pressure
and doping makes the electrical conductivity increase largely.
The composition dependence of conductivity for
(AgSb)xPb1 2xSe (x = 0, 0.01, 0.03) is similar to the effect of high
pressure for PbSe [8]. According to our previous report, the electri-
cal transport properties of PbSe can be varied effectively by chang-
ing the pressure due to the residual stress after high pressure
quenching. The replacement of Ag and Sb for Pb can result in the
dislocation due to the large ionic radius difference between Pb
and Ag–Sb, which is tested by the TEM pattern. The chemical inter-
nal stress resulted from the substitution of Pb by Ag and Sb should
increase with an increase of doping content. The residual stress
and internal stress could modify the band structure so that it
changes the electrical transport properties [8]. This result is in
satisfactory agreement with those results measured in-situ under Fig. 4. The typical HRTEM image of (AgSb)0.01Pb0.98Se, showing grain boundaries (a)
pressure [19] and our previous result of PbSe prepared by HPHT and dislocations (b) and (c) is the detail view of dislocations in b.
[8]. The higher the pressure is, the higher electrical conductivity
obtained. positive. It indicates that all PbSe samples are P-type semiconduc-
The temperature dependence of Seebeck coefficients for tors because mobility of holes in the Se valance band is greater
(AgSb)xPb1 2xSe samples are shown in Fig. 2b. It can be seen that than that of electron in the Pb conduction band which is similar
all the values of Seebeck coefficients for (AgSb)xPb1 2xSe are to that of PbTe [20,21]. The Seebeck coefficients of
 H. Fan et al. / Journal of Alloys and Compounds 639 (2015) 106–110
Fig. 5. Temperature dependence of ZT for (AgSb)xPb1 2xSe.
(AgSb)xPb1 2xSe decrease with an increase of x. That may be caused
by the increasing carrier concentration which increases with an
increase of the doping amount [22].
Base on the above values of electrical conductivity and Seebeck
coefficient, power factors were calculated for all the samples
shown in Fig. 2c. It can be seen that the power factors of
(AgSb)xPb1 2xSe increase first and then decrease with an increase
of x above 350 K. The maximum power factor reaches 23.02
lW/cm K2 at x = 0.03 (450 K), which is much higher than that of
undoped PbSe. In addition, this value matches to that of well-
known AgPbmSbTem+2 reported by Li [16]. Base on these results,
high thermoelectric performance will be expected if a low thermal
conductivity is obtained.
The temperature dependent thermal properties of
(AgSb)xPb1 2xSe (x = 0, 0.01, 0.03, 0.05) are shown in Fig. 3. The
thermal conductivity of PbSe at room temperature is about
1.6 W/mK. The value increases after doping with Ag and Sb in
the measured temperature range. As is mentioned above, the ther-
mal conductivity is composed of the electrical thermal conductiv-
ity je and the phonon thermal conductivity jph. Here je is directly
related to the electrical conductivity through the Wiedemann–
Franz law, je = LrT, where L is the Lorenz number
(L = 2.45  10 8 WX/K2) and T is the absolute temperature. At
600 K, jph for doped sample is about 0.64 W/mK, which is lower
than that of the undoped PbSe, whose jph is about 0.75 W/mK.
To investigate the mechanism of the low phonon thermal conduc-
tivity obtained in the study, HRTEM is investigated.
A HRTEM investigation of (AgSb)xPb1 2xSe reveals striking
structural nanoscopic, coherent inhomogeneities. As seen from
Fig. 4a, the typical HRTEM image of the Ag–Sb co-doped PbSe sam-
ple reveals the existence of nanoscale features. It can be seen that
there are a certain amount of well crystallized nano-regions and
wavy pattern with several nanometers inside of the crystal grains.
They should be related to compositional fluctuations between Ag,
Sb and Pb base on the above charge-balance theory [13]. These
nanostructures of PbSe doped with Ag and Sb would effectively
scatter phonons to lower the lattice thermal conductivity. In addi-
tion, lots of dislocations exist within micrograins (Fig. 4b and c).
The lattices are heavily distorted and twisted because of these
defects which would strongly scatter phonons. These defects
should come from elemental fluctuations at nanoscale.
According to the measured electrical conductivity, Seebeck
coefficient, and thermal conductivity, ZT values for all the samples
were calculated shown in Fig. 5. As can be seen, the ZT of the
109
undoped PbSe sample increases slightly first and then decreases
with the increase of temperature. The figure of merit is improved
after doping, especially at the high temperature. The maximum
ZT value of 1.03 is obtained at 600 K for the sample with x = 0.03,
mainly due to its highest electrical conductivity and lower phonon
thermal conductivity. The value is much higher than that of
undoped PbSe. It indicates that Ag–Sb co-doping under high pres-
sure could enhance the thermoelectric performance of PbSe
effectively.
4. Conclusions
P-type PbSe compounds co-doped with Ag and Sb have been
fast prepared by high pressure method. A large number of nanos-
tructure phases distribute in the doped sample. An enhanced
ZT  1.03 is obtained for x = 0.03 (600 K), which is about five times
higher than that of undoped PbSe. The improved thermoelectric
performance of PbSe in this study due to the large power factor
induced by high pressure and the low phonon thermal conductiv-
ity resulted from nanostructure of Ag–Sb doping.
Acknowledgments
This work was supported by the National Science Foundation of
China (11204067 and 51206060), the Scientific and Technological
Projects under Shanghai Entry-Exit Inspection and Quarantine
Bureau (HK009-2013), Program of Key Young Teacher of Henan
Polytechnic University Program for Innovative Research Team (in
Science and Technology) in the University of Henan Province
(2012IRTSTHN007).
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