ISSN 1063-7826, Semiconductors, 2017, Vol. 51, No. 7, pp. 854–857. © Pleiades Publishing, Ltd., 2017.

Original Russian Text © L.P. Bulat, V.B. Osvenskii, A.A. Ivanov, A.I. Sorokin, D.A. Pshenay-Severin, V.T. Bublik, N.Yu. Tabachkova, V.P. Panchenko, M.G. Lavrentev, 2017,
published in Fizika i Tekhnika Poluprovodnikov, 2017, Vol. 51, No. 7, pp. 892–895.

XV INTERNATIONAL CONFERENCE “THERMOELECTRICS AND THEIR

APPLICATIONS—2016”, ST. PETERSBURG, NOVEMBER 15–16, 2016

Experimental and Theoretical Study of the Thermoelectric

Properties of Copper Selenide
L. P. Bulata†, V. B. Osvenskiib, A. A. Ivanovb, c*, A. I. Sorokinb, D. A. Pshenay-Severind, e, V. T. Bublikf,
N. Yu. Tabachkovaf, V. P. Panchenkob, f, and M. G. Lavrentevb
a ITMOUniversity, St. Petersburg, 191002 Russia
b
Joint Stock Company “Giredmet”, Moscow, 119017 Russia
c
Moscow Technological University (MIREA), Moscow, 119454 Russia
d
Ioffe Institute, Russian Academy of Sciences, St. Petersburg, 194021 Russia
e
Peter the Great St. Petersburg Polytechnic University, St. Petersburg, 195251 Russia
f
National University of Science and Technology (MISiS), Moscow, 119991 Russia
*e-mail: girlab22@mail.ru
Submitted December 27, 2016; accepted for publication January 19, 2017

Abstract—The temperature dependences of the specific heat, thermal conductivity, coefficient of thermal
expansion (CTE), and transport coefficients (electrical conductivity and thermoelectric power) of copper
selenide are experimentally and theoretically investigated in the temperature range of 300–873 K. The calcu-
lation results correlate with the experimental data up to a temperature of ~773 K. The maximum thermoelec-
tric figure of merit of nanostructured copper selenide is ZT ~ 1.8. The correlation dependence between ZT
and the thermal conductivity within the entire temperature range under consideration is shown.

DOI: 10.1134/S1063782617070041

INTRODUCTION The synthesized material was compacted by spark

Copper selenide is a promising thermoelectric
material for thermoelectric generators (TEGs) with
extremely high thermoelectric figure of merit. The
fabrication of a Cu2Se sample with a Q factor ZT of
1.2–1.6 at temperatures of 800–1000 K has been
reported [1, 2]. It is believed that such high values are
primarily due to the anomalously low thermal con-
ductivity of copper selenide at high temperatures,
which is explained by the high mobility of copper ions.
In this paper, we report the results of theoretical and
experimental investigation of the specific heat, ther-
mal conductivity, coefficient of thermal expansion
(CTE), and transport coefficients (electrical conduc-
tivity and thermoelectric power coefficient) of copper
selenide.
EXPERIMENTAL
The experimental samples were prepared by a tech-
nology that has been successfully used by us to fabri-
cate Bi2Te3-based nanostructured materials [3, 4].
Copper-selenide nanopowder was prepared by mech-
anochemical synthesis (MCS) in a high-energy ball
mill at 300 rpm for 2–10 h. Cu powder (99.9%) and Se
grains (99.999%) were used as the initial materials.
† Deceased.
plasma sintering (SPS) at a temperature of 550° C, a
pressure of 50 MPa, and an exposure time of 10 min.
RESULTS AND DISCUSSION
The decrease in the specific heat with increasing
temperature is believed to be one of the possible rea-
sons for an increase in ZT [4]. A theory of the specific
heat of the Cu2Se cubic β phase has been proposed
based on theoretical calculation of its phonon spec-
trum. Here, we take into account the decrease in the
specific heat, which may occur due to the high mobil-
ity of copper ions. With an increase in temperature,
the selenium sublattice in Cu2Se retains properties
inherent in solids, while the sublattice of more mobile
copper ions becomes disordered and liquid-like in its
properties. Since the specific heat of liquids is lower
than that of solids, one can suggest a decrease in the
specific heat of copper selenide with an increase in
temperature. The Trachenko theory [5], which is
based on the Frenkel theory of liquids [6], was used to
explain the decrease in the specific heat. Within this
approach, a solid is used as a starting point to describe
the properties of a liquid. Since the probability of
atomic jumps increases with increasing temperature,
some transverse modes disappear in the liquid to
reduce the specific heat. Since only the copper sublat-

854
 EXPERIMENTAL AND THEORETICAL STUDY
2.0
1.8 1 1.5 × 10–8 (W Ω)/K2 is the Lorenz number, σ is the
1'
1.6 2 ture.
1.4 2'
κ, W/(m K)
1.2
1.0
0.8
0.6
0.4
0.2
0
400 500 600 700 800 900 1000
T, K
Fig. 1. Temperature dependence of the thermal conductiv-
ity κ. Curves 1 and 1' correspond, respectively, to the total
thermal conductivity and its lattice component for the
nanostructured samples obtained in this study and
curves 2 and 2 ' correspond, respectively, to the values of
the total thermal conductivity and its lattice component
taken from [1].
tice in Cu2Se is believed to pass to the liquid-like state,
we selected not only the longitudinal and transverse
vibrational components but also the contributions of
copper and selenium atoms to the specific heat.
The results on measuring the specific heat Cp in the
temperature range below 973 K show that Cp barely
changes (the decrease is on the level of 5%), which is
in agreement with the calculated temperature depen-
dence of the specific heat with allowance for the jump
rate, determined from the copper self-diffusion coeffi-
cient. The specific heat of copper selenide was dis-
cussed in more detail in our previous study [7].
In order to determine the mechanism of the
decrease in the thermal conductivity of copper sele-
nide, the temperature dependence of the thermal con-
ductivity was theoretically calculated using the
method of equilibrium molecular dynamics and the
classical interatomic potential.
According to the calculation, the lattice thermal
conductivity amounts to ~0.6 W/(m K) and weakly
changes with temperature. The simulation results con-
firmed the high mobility of copper ions. This fact sug-
gests that the very low lattice thermal conductivity in
Cu2Se is due to strong phonon scattering from mobile
Cu atoms.
The temperature dependences of the total (κ) and
lattice (κlat) thermal conductivities were also experi-
mentally investigated. The lattice thermal conductiv-
ity κlat was calculated from the formulas
κ lat = κ − κ e,
κ e = Lσ T ,
SEMICONDUCTORS Vol. 51 No. 7 2017
855
where κе is the electron thermal conductivity, L =
electrical conductivity, and T is the absolute tempera-
Figure 1 shows the temperature dependences of the
total (κ) and lattice (κlat) thermal conductivities for a
bulk nanostructured Cu2Se sample obtained by the
SPS method. The data of [1] are also presented for
comparison. The experimentally obtained total ther-
mal conductivity decreases with an increase in tem-
perature (the decrease is most pronounced at T >
800 K) and equals ~0.62 W/(m K) at T = 900 K. The
lattice thermal conductivity is much lower than κ
(especially at temperatures below 700 K). At T =
900 K, κlat is ~0.25 W/(m K) for the SPS samples. The
κlat value barely changes in the temperature range up to
~750 K.
When calculating the temperature dependences of
the thermoelectric power α and electrical conduc-
tivity σ, the energy and temperature dependences of
the relaxation time corresponding to the strongest and
most dominant mechanism of scattering from acous-
tic phonons were taken into account.
Figure 2 shows the calculated dependences of (a) σ
and (b) α for p-type β-Cu2Se. Our experimental data
are also presented. On the whole, there is satisfactory
agreement between the calculation and experiment in
the range of 450–773 K. At higher temperatures, the
experimental thermoelectric power sharply increases,
while the electrical conductivity drops. On the
assumption that the hole concentration remains con-
stant, this fact indicates an increase in the effective
mass of charge carriers with an increase in tempera-
ture.
Possible reasons for the increase in the effective
mass are the complex band structure, spectrum non-
parabolicity, and crystal thermal expansion. The cal-
culation used in this study takes into account the spec-
trum nonparabolicity and the presence of deeper
valence bands. The electronic spectrum of Cu2Se was
calculated with the experimental values of the lattice
constant in the range of 700–1000 K (according to the
data of [8]) in order to illustrate the influence of ther-
mal expansion. The calculation showed that the
change in the energy spectrum, taking into account
crystal thermal expansion, increases the effective mass
of charge carriers and the thermoelectric power. How-
ever, its value is insufficiently high to explain the
experimental dependences. The additional contribu-
tion is likely related to a change in the spectrum caused
by enhancement of the disorder of lattice atoms at
higher temperatures.
The behavior of point defects in copper selenide
upon heating can be analyzed by measuring the ther-
(1) mal expansion and the temperature dependence of the
lattice constant. The results of investigating the ther-
(2) mal expansion of thermoelectric material Cu2Se are
856 BULAT et al.

1800
180 αL 25
1600 (a) ΔL
150
1400

αL × 10−6, K1
20
120

ΔL, μm
1200
15
α, S/cm

1000 90
800 60 10
600
1 30 5
400 2
0
200 3 0
0 100 200 300 400 500 600
0 T, K
400 500 600 700 800 900
T, K
Fig. 3. Temperature dependences of CTE αL and the rela-
(b) tive elongation ΔL of copper selenide.
1
200 2
3 Cu and Se atoms. The rms displacement of Cu atoms
exceeded that for Se by a factor of about 4. This fact
150
indicates that the copper diffusion coefficient is
α, μV/K

higher, while the vacancy-formation enthalpy is lower

100 than the corresponding values for selenium.
The temperature dependence of the lattice con-
stant was found from the positions of the Bragg peak in
50
the diffraction pattern at different temperatures in the
range from 473 to 673 K. With a change in temperature
400 500 600 700 800 900
T, K above 673 K, the increase in the lattice constant is
somewhat slowed down.
Fig. 2. (a) Experimental (1) and calculated (2, 3) tempera- The presence of inflections at ~773 K in the tem-
ture dependences of the electrical conductivity σ for hole perature dependences of Cp, CTE, κ, σ, and α is
concentrations of (2) 4 × 1020 and (3) 6 × 1020 cm–3 in explained in [4] by the fact that this temperature is the
p-Cu2Se. (b) Experimental (1) and calculated (2, 3) tem-
perature dependences of the thermoelectric power α for lower temperature boundary of the disorder of Cu+
hole concentrations of (2) 4 × 1020 and (3) 6 × 1020 cm–3 ions (by analogy with glass) without the first-order
in p-Cu2Se. phase transition. We note that the Cu ion state also
changes (from Cu–Se to (Cu–Cu)°).

shown in Fig. 3. The upper and lower curves therein
are the temperature dependences of the CTE and rel-
ative elongation, respectively. It can be seen in Fig.3
that after the end of the first-order phase transition
(beginning at about 473 K), the thermal expansion
corresponds to the high-temperature cubic phase. It is
noteworthy that CTE increases at temperatures below
673 K, which is generally observed for solids at tem-
peratures above the Debye temperature. However, at
temperatures above 673 K (up to ~773 K), CTE some-
what decreases rather than increases. This behavior of
CTE may be related to a change in the state of point
defects (in particular, the formation of selenium
vacancies due to Cu2Se sublimation upon heating).
Measurement of the peaks in diffraction patterns
recorded at different temperatures allowed us to esti-
mate the Debye–Waller factors and determine sepa-
rately the rms (root-mean-square) displacements of
Figure 4 shows the experimental temperature
dependence of ZT obtained in this study for a Cu2Se
samples fabricated by SPS. At a temperature of 870 K,
ZT reaches a value of 1.8, which is much higher than
the thermoelectric figure of merit of the Cu2Se sam-
ples obtained by other methods [1, 2, 9]. As was indi-
cated above, a distinctive feature of the SPS material is
its nanocrystalline structure. The temperature depen-
dence of ZT for a nanostructured material fabricated
by a similar technology [10] is also shown in Fig. 4
(ZT reaches a value of 2.0 at 950 K). This fact indicates
that the thermoelectric figure of merit of nanostruc-
tured Cu2Se is higher. The data in Fig. 4 confirm the
correlation dependence of ZT on the thermal conduc-
tivity. This fact indicates that the low lattice thermal
conductivity, which is related to the high mobility of
copper ions, is the main reason for the large ZT values;
this conclusion is confirmed by the calculation results.

SEMICONDUCTORS Vol. 51 No. 7 2017

 EXPERIMENTAL AND THEORETICAL STUDY
2.5
2.0
1.5
ZT
1.0
0.4 1 11, 422 (2012).
0.5 2
0.2 3 2. B. Yu, W. Liu, S. Chen, H. Wang, H. Wang, G. Chen,
0 0
200 300 400 500 600 700 800 900 1000
T, K
Fig. 4. Temperature dependences of (1) ZT and (2) κ
obtained in this study and (3) the temperature dependence
of ZT from [9].
CONCLUSIONS
The temperature dependences of the specific heat,
thermal conductivity, and kinetic coefficients (electri-
cal conductivity and thermoelectric power), as well as
their contributions to the thermoelectric figure of
merit of copper selenide, were experimentally and
theoretically investigated. Satisfactory agreement
between the experimental data and calculation results
was observed at temperatures below ~773 K, after
which the experimental temperature dependences
exhibit an inflection. The nonmonotonic change in
the CTE at temperatures in the range from 400 to
800 K may be due to a change in the state of point
defects. The ZT value for nanostructured SPS Cu2Se
samples at temperatures from 850 to 950 K may reach
1.8 and even 2.0 (according to the data of [10]). The
correlation dependence of ZT on the thermal conduc-
tivity was observed, which is in agreement with the
results of theoretical calculation.
SEMICONDUCTORS Vol. 51 No. 7 2017
857
1.8 ACKNOWLEDGMENTS
1.6 This study was supported by the Ministry of Edu-
1.4 cation and Science of the Russian Federation (grant
κ, W m1 K1
no. RFMEFI57914X0039-14.579.21.0039).
1.2
1.0
0.8
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Translated by Yu. Sin’kov