Materials Science in Semiconductor Processing 48 (2016) 85–94

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Materials Science in Semiconductor Processing

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Thermoelectric studies of IV–VI semiconductors for renewable energy

resources
Amir Abdullah Khan, Imad Khan n, Iftikhar Ahmad, Zahid Ali
Center for Computational Materials Science, Department of Physics, University of Malakand, Chakdara, Dir (Lower), Pakistan

art ic l e i nf o a b s t r a c t

In the present study we explore the structural, electronic and thermoelectric properties of IV-VI semi-
Keywords: conductors using first principle calculations based on the density functional theory. Generalized gradient
Heat transfer approximation (GGA-PBEsol) is used as an exchange-correlation functional for the structural properties
Renewable energy resources of the different crystal phases of these semiconductors. The compounds SnS, SnSe, GeS and GeSe favor
Seebeck effect orthorhombic structure, lead chalcogenides (PbS, PbSe and PbTe) are stable in the cubic rocksalt struc-
Semiconductors ture, while SnS2 and SnSe2 exist in hexagonal structure. For band structures additional to GGA, modified
Ab-initio Becke and Johnson (mBJ) exchange potential is used. These compounds are narrow band gap semi-
conductors in the energy range 0.2–2.8 eV. These binary IV-VI chalcogenides have direct band gap nature
in cubic crystals while indirect in the orthorhombic phases. The post-DFT (BoltzTraP) calculations are
performed to estimate Seebeck coefficient, electric and thermal conductivities, power factor and figure of
merit of these compounds to check their applicability in thermoelectric devices. Spin orbit coupling
effect influences the electronic and thermoelectric properties of these compounds due to the large size of
the constituent elements. Further, the total thermal conductivity is computed using ad-hoc calculation
with the experimental results. The calculated values of figure of merit for PbS, PbSe, PbTe and SnTe are in
the range 0.68–0.77 at room temperature.
& 2016 Elsevier Ltd. All rights reserved.

1. Introduction
The energy crises make the world eager for energy resources,
causing social and economical problems. The globe will become
energy desert if new abundant and environmental friendly re-
sources are not identified. One of the solutions to the problem is
the recovery of waste heat for useful purposes. Therefore, re-
searchers across the world are searching for efficient thermo-
electric materials.
Thermoelectric conversion technology has received increasing
attention in the recent years because of the worldwide energy
needs and environmental problems. In this regard great progress
has been observed in the development of high-performance
thermoelectric materials. Thermoelectric generator is a device that
converts waste heat into useful energy. Thermoelectric generator
is based on Seebeck effect while cooler is based on Peltier effect,
containing no moving parts unlike traditional heat engines, re-
frigerators and air conditioners. These devices could be used re-
liably for 25–30 years without any repairing operations. Thermo-
electric devices have lower efficiency than common used
n
Corresponding author.
E-mail address: imadkhan723@gmail.com (I. Khan).
generators but for small applications these devices are very useful
for energy harvesting. These devices are useful to harvest waste
heat in automobiles, industries and even from human body for
wristwatch design by Seiko and Citizen. For high efficiency of
thermoelectric devices, recently new approaches are developed in
nanowires, thin films and bulk nano-structured materials.
The efficiency of thermoelectric materials is determined by the
dimensionless figure of merit ( ZT = S2σT /κ ), which depends on
Seebeck coefficient (S), electrical conductivity (s), thermal con-
ductivity (κ) and absolute temperature. The relationship between
thermopower (seebeck coefficient), electrical conductivity and
thermal conductivity is quite complex, but it is possible to fluc-
tuate one of the parameters while keeping the others constant
with band gap engineering. High ZT means increase in power
factor ( S2σ ) and decrease in thermal conductivity without de-
pressing the electric conductivity of a material. An average ZT, in
the operating temperature range must be higher than 1 to make a
thermoelectric device competitive [1]. There have been persistent
efforts to improve ZT values during the past two decade, in
(i) superlattices [2], and (ii) bulk materials, [3]. Although high ZT
values are reported in superlattice structures, but it has been
proven that these materials are difficult to use in large-scale en-
ergy-conversion applications because of their limitations of heat
transfer and cost. Bulk materials with improved ZT, such as lead

http://dx.doi.org/10.1016/j.mssp.2016.03.012
1369-8001/& 2016 Elsevier Ltd. All rights reserved.
86 A.A. Khan et al. / Materials Science in Semiconductor Processing 48 (2016) 85–94
antimony silver telluride (LAST) and IV-VI monochalcogenide
semiconductors are ideal for high-temperature operations [4].
The IV-VI chalcogenides family such as SnSe, SnS, SnTe, PbSe,
PbS, PbTe, GeSe, GeS, GeTe, SnSe2, SnS2 and their alloys are pro-
mising materials for thermoelectric generators, optoelectronic
devices, temperature sensors, telecommunications, holographic
recording systems, memory switching devices, etc. [5–8]. Different
physical properties of these semiconductors such as structural,
electronic and optical properties are extensively investigated ex-
perimentally, however most of the theoretical studies are limited
to the understanding of their basic physics and chemistry of the
structural phase transitions, electronic band gaps and ferroelectric
like behavior at low temperatures [9]. These IV-VI compounds
crystallize in different crystal structures. The lead chalcogenides
PbS, PbSe, PbTe, GeTe and SnTe adopt the NaCl structure with each
atom in an octahedral coordination of six atoms of the other type
[10]. The compounds SnS, SnSe, GeS and GeSe have orthorhombic
crystal structure with the space group Pnma (#62) [11], except
SnSe which occurs in space group Cmcm (#63) [12]. Whereas,
SnSe2 and SnS2 exist in hexagonal crystallographic structure with
space group P-3ml (#164) and P3ml (#156) respectively [13,14].
Ettema et al. [10] theoretically reported the structural phase
transition of SnS between α (low temperature phase) and β (high
temperature phase), having space group Pnma and Cmcm re-
spectively, but α-phase has larger band gap than β. Loa et al. [15]
found orthorhombic structural phase transition of SnSe from low
pressure phase α (Pnma #62) to high pressure phase (10.5 GPa) β
(Cmcm#63) using angle-dispersive synchrotron x-ray powder
diffraction method. Below 100 K, the cubic structure of SnTe is
changed to rhombohedral structure which is the equilibrium
structure of SnTe [14].
Lead chalcogenides have been extensively studied theoretically
and experimentally due to their potential applications in ther-
moelectric energy converters and electronic devices. The experi-
ments as well as first principle calculations confirm direct band
gap nature of these materials [9,16]. PbX (X¼ Se, S, Te) crystallize
in NaCl-type structure at lower pressure, where adopt orthor-
hombic structure in the pressure range 2.5–6 GPa, however on
further increase in pressure (13–25 GPa) they transform to CsCl-
type structure, metallic and superconductors [16]. Wiedemeier
et al. [17] investigated the structure of GeS and GeSe by using
X-ray diffraction technique. They predict that GeSe transfers from
orthorhombic to cubic phase with increasing temperature while
GeS (space group Pnma, #62) melts before transformation to other
structure, but Durandurdu [18] theoretically predicts NaCl type
structure as high pressure phase of GeS (space group Cmcm, No.
63). Edwards et al. [19] studied the electronic structure of GeTe
both for low temperature rhombohedral phase and high tem-
perature cubic phase by using SEQQUEST and ABINIT plane-wave
pseudo-potentials method in DFT.
Thermoelectric properties of pure and doped IV-VI semi-
conductors are extensively studied experimentally and there are
also available some theoretical results on these compounds in
different crystal structures. Tan et al. [20] investigated the ther-
moelectric properties of SnS both in pure and doped form. Cheng
et al. [21] investigated thermoelectric properties of SnSe doped
with Ag and measured ZT ¼0.6. The thermoelectric power factor of
SnS, SnSe, GeS, and GeSe are theoretically calculated as 21.25,
20.07, 30.25 and 35.03 mW cm  1 K  2 for n-type concentration and
14.70, 23.48, 15.03 and 15.02 mW cm  1 K  2 respectively for p-type
concentration at 300 K [22]. Seebeck coefficient, electric and
thermal property of lead chalcogenides are calculated both in pure
and doped form [23–27].
The above extensive literature confirms the versatility of these
compounds in different device applications. In the present theo-
retical studies structural, electronic and thermoelectric properties
of IV-VI binary compounds in different crystal structures are
investigated.
2. Method of calculations
We make use of the density functional calculations in the frame
work of full potential linearized augmented plane-wave (FPLAPW)
method as implemented in the Wien2k package [28]. For the
calculation of structural and electronic properties exchange and
correlation interactions are described using the generalized gra-
dient approximation (GGA-PBEsol) [29] and modified Becke-
Johnson (mBJ) exchange potential [30]. Both local density ap-
proximation (LDA) and generalized gradient approximation (GGA)
are somewhat successful in calculating the structural properties
but fails to reproduce experimental band gaps of semiconductors
and insulators. Recently Tran and Blaha develop modified Becke
and Johnson (mBJ) approximation for the exchange potential for
the calculation of the band structures, whereas the correlation
potential comes from the original LDA or GGA [30]. The mBJ ex-
change potential is an empirical relation of the form:
υx, σ mBJ (r ) = cυx, σ BR (r ) + (3c − 2)
1 5 2tσ (r )
π 12 ρσ (r ) (1)
where ρs(r) is the spin dependent density of states, ts(r) is the
kinetic energy density and Vx,sBR (r) is the Becke-Roussel potential,
and c is density dependent parameter given by:
1
⎛ 1 ∇ρ(r′) 3 ⎞ 2
c = α + β⎜
⎝ Vcell
∫cell ρ(r′)
d r′⎟
⎠ (2)
In this equation, α ¼ 0.012 and β ¼1.023 bohr1/2 are two free
parameters. The values of these parameters are generally fixed by
experiments for compounds. The mBJ calculations are computa-
tionally as cheaper as ordinary LDA or GGA calculations. As a
general result, this potential causes a rigid displacement of the
conduction bands toward higher energies with respect to the top
of the valence band, with small differences in the dispersion at
some regions of the Brillouin zone but reproducing, in general, the
characteristic behavior of the bands for each semiconductor ac-
cording to experiment [31]. mBJ offer high-precision and accurate
calculations of electronic band structures which is required to
quantify accurately thermoelectric coefficients. Spin-orbit cou-
pling (SOC) is a relativistic effect and is an interaction of particles
that depends on the values and mutual orientations of the parti-
cles, orbital and spin angular momenta and that leads to the fine-
structure splitting of the system's energy levels. We include the
spin-orbit coupling in our calculations by using the second varia-
tional method [32] programmed in the WIEN2K code. The second
variational method, which makes use of the scalar-relativistic ba-
sis, is based on the reduction of the original basis. In the first step
of this approach, the scalar-relativistic part of the Hamiltonian is
diagonalized in the scalar-relativistic basis. In the second step, the
full Hamiltonian matrix including SOC is constructed using the
eigen functions of the first step Hamiltonian [33].
In full potential scheme, the wave functions inside the non-
overlapping spheres are expanded as spherical harmonics up to
angular momentum l¼10. Plane wave expansion is used in the
remaining space of the unit cell (interstitial region) fixing the
parameter RMT/Kmax ¼7. The atomic spheres are used in such a way
that no charge leakage occurred. The Brillouin zone integration is
performed with a 200 k-point for the self-consistency cycle which
is taken to be converged when the forces on the atoms fell below
1.0 mRy/a.u. Whereas to calculate the thermoelectric parameters a
dense k mesh of 50,000 k points is used in this work as the
 A.A. Khan et al. / Materials Science in Semiconductor Processing 48 (2016) 85–94 87

method proposed by Madsen and Singh [34]. The electrical based on Boltzmann semi-classical theory and Fourier interpola-
transport properties, like electrical conductivity and Seebeck tion of the calculated bands. All of the calculations are im-
coefficient, are computed using the BoltzTraP code [34], which is plemented by solving the Boltzmann transport equation with the

Table 1
Comparison of experimental and theoretical lattice constants and other structural parameters of IV-VI semiconductors.

Comp. Phase Lattice constant (Å) Bulk modulus (GPa) E0(Ry)

Exp. present Other Exp. present Other

SnS Fm-3m a 5.7a 5.70 5.75b, 6.31c 182.54  13149.994

Pnma a 4.30 4.30 4.35, 4.24 58.3u 63.35  52600.007
b 11.20 11.19 11.39, 11.12
c 3.99d 3.99 4.04y, 3.97a,e
Cmcm a 4.14 4.40 4.1 86.0w 68.54  26300.001
b 11.48 11.31 11.76
c 4.17d,f 4.03 4.10c
SnSe Fm-3m a 5.99o 5.94 6.05v 180.95  17210.019
Pnma a 4.44 4.40 4.44 47.04  68840.076
b 11.50 11.53 11.75
c 4.15g 4.17 4.20y
Cmcm a 4.31 4.18 57.90  34420.044
b 11.70 11.58
c 4.31f 4.21
SnTe Fm-3m a 6.31h 6.29 6.40i 57.48  25940.852
PbS Fm-3m a 5.93j 5.87 6k, 5.99l 62.8u 73.82 55.7l  42643.313
Pnma a 11.28 11.45 11.19 62.2u 73.82  170572.895
b 3.98 4.24 4.06
c 4.21o 4.38 4.17s
PbSe Fm-3m a 6.12j 6.12 6.20l,k 28.8u 97.32 49.2l  46703.331
Pnma a 11.61 12.00 73u 56.51  18813.20
b 4.00 4.36
c 4.39o 4.28
PbTe Fm-3m a 6.46j 6.44 6.56l,k 33.9u 64.31 40.4l  55434.165
Pnma a 11.71 12.42 36u 42.1  221736.47
b 4.36 4.53
c 4.42o 4.59
GeS Pnma a 4.30 4.15 4.73, 4.18 50.3u 57.22 58.3  19969.222
b 10.52 10.62 10.64, 10.12
c 3.65p,m 3.70 3.69y, 3.55m
Cmcm a 4.24 3.27 68.55  9984.606
b 10.45 9.57
c 3.69 3.66q
GeSe Fm-3m a 5.73n 5.58 88.01  9052.347
Pnma a 4.38 4.31 4.49 47.5u 36.71  36209.352
b 10.79 10.85 10.95
c 3.82p,n 3.90 3.82y
GeTe Fm-3m a 6.01r 5.91 6.01i 138.92  17783.186
SnS2 P-3ml a 3.64 3.64 3.66 37.13  13149.976
c 5.89z 6.02 6.06b
SnSe2 P3ml a 3.81 3.81 65.34  22067.083
c 6.14t 6.35

a
[67].
b
[38].
c
[40].
d
[10].
e
[11].
f
[41].
g
[5].
h
[14].
i
[42].
j
[43].
k
[16].
l
[9].
m
[44].
n
[17].
o
[45].
p
[46].
q
[18].
r
[47].
s
[48].
t
[49].
u
[50].
v
[51].
w
[52].
y
[22].
z
[68].
88 A.A. Khan et al. / Materials Science in Semiconductor Processing 48 (2016) 85–94
constant relaxation time approximation. The time is assumed to be
a constant, based on the consideration that the electrons con-
tributing to transport are in a narrow energy range due to the
delta-function like Fermi broadening. The relaxation time is nearly
the same for the electrons in such a narrow energy range. The
validity of this method is tested earlier, and the method actually
turns out to be a good approximation even for anisotropic systems
[34–36].
Seebeck coefficient tensors, electrical conductivity tensors and
electronic thermal conductivity tensors at non-zero electric cur-
rent are obtained by the following equations [34]:
⎡ agreement with the experimental [53,65] measured values,
1 ∂fo (T , ε, μ) ⎤
Sαβ(T , μ) =
eTσαβ(T , μ)
∫ σ¯αβ(ε)(ε − μ)⎢⎣ − ∂ε
⎥dε
⎦
1 ⎡ ⎤
σαβ(T , μ) =
Ω
∫ σαβ(ε)⎢⎣ − ∂∂fε ⎥⎦dε
And
1 ⎡ ⎤ mental values. These results confirm the suitability of our theo-
o
καβ (T , μ) =
e2TΩ
∫ σαβ(ε)(ε − μ)2⎢⎣ − ∂∂εf ⎥⎦dε
Where e is electron charge, Ω is reciprocal space volume,
carrier energy and f is Fermi distribution function.
3. Result and discussions
3.1. Structural properties
The IV-VI compounds exist in different crystal structures,
therefore, we calculate the lattice parameters a, b and c through
optimization process in which each unit cell is optimized i.e. the
total energy is minimized with respect to the unit cell volume
using Murnaghan's [37] equation of state. The calculations confirm
that SnS and SnSe are found more stable in α-phase than the β-
phase and cubic, whereas SnTe is crystallized in cubic structure
only. In PbS, PbSe and PbTe the most stable phase is cubic. Simi-
larly GeS and GeSe stabilized in Pnma. SnS2 and SnSe2 are found in
hexagonal crystal structure with space group P-3m1. The calcu-
lated lattice constants, bulk moduli and ground state energies are
listed in Table 1. The table shows that our calculate lattice con-
stants for SnS in cubic phase (5.70 Å) and α-phase (Pnma)
(a ¼4.30 Å, b¼ 11.19 Å, c¼ 3.99 Å) are in good agreement with ex-
perimental and theoretical results [10,38–43,67]. While in β-phase
(Cmcm) the calculated lattice constants a ¼4.40 Å, b ¼11.31 Å,
c¼ 4.03 Å are somewhat underestimated from accessible experi-
mental and theoretical data [10,40]. The underestimation or
overestimation in lattice constants of all these IV-VI compounds is
less than 0.5%. Bulk modulus is an another important parameter,
which estimate the hardness or softness of material. The calcu-
lated bulk modulus for the compounds under study are compared
with the available experimental and theoretical results in Table 1.
From the calculated ground state energy values it is clear that SnS
and SnSe is most stable in orthorhombic α-phase (Pmna). Similarly
GeS and GeSe are stabilized in orthorhombic crystal structure. The
stable phase of lead chalcogenides, tin and germanium telluride
(SnTe, GeTe) is cubic rocksalt crystal structure and orthorhombic
structure is their high pressure phase.
3.2. Electronic properties
The study of band structure and calculation of energy band
gaps are very important for any material to determine their useful
applications in optoelectronic and thermoelectric properties. Ev-
ery solid state material has unique electrical and optical properties
due to the difference in the band structure. In the present work
GGA and mBJ þ GGA are used as an exchange-correlation potentials
for the calculation of the electronic band structure of the IV-VI
binary compounds. The calculated band structures are plotted in
Fig. 1 and the calculated values are listed in Table 2. From the
figure it is clear that all these IV-VI chalcogenides are direct band
gap semiconductors in cubic phase while indirect in orthorhombic
(both in α- and β-phase) structure. Whereas the hexagonal
structured SnS2 and SnSe2 are indirect band gap materials. The
calculated band gap energy values for tin chalcogenides are 0.25,
0.23 and 0.182 eV in cubic structure using mBJ which are in
whereas GGA results are underestimated. Similarly in orthor-
(3) hombic phases the mBJ results are in agreement with the ex-
perimental and other theoretical available data. The value of our
(4)
calculated band gaps for lead chalcogenides are 0.369, 0.254,
0.40 eV for cubic phases and 1.925, 0.885, 0.994 eV for orthor-
hombic phases, similarly the band gap energies of germanium
chalcogenides (GeS, GeSe, GeTe) also coincide with the experi-
(5) retical model used for the calculation of the band gaps which is
mBJ. These results of electronic structures are further used for the
ε is calculations of thermoelectric properties.
Electronic band structures clarify directly or indirectly most of
the physical properties of a material, for example, analysis of di-
electric functions, transport properties, photoemission spectra of
materials etc. Density of states (DOS) describes the electronic band
structure of a material and also explains the contribution of dif-
ferent electronic states in the valence or conduction band. Total
and partial densities of state with the effect of spin orbit coupling
(SOC) and without SOC of binary IV-VI compound are presented in
Fig. 2(a-c). It is clear from the Fig. 2(a and b) that the maxima of
valence band and minima of the conduction band do not cross the
Fermi-energy level for any compound which is evidence for their
narrow band semiconducting behavior. The top of the valence
band is mostly composed of the VI-p state, whereas the bottom of
the valence band is mainly contributed by IV-s state. The con-
duction band in both cubic and orthorhombic phase are con-
tributed by mixed VI-s and VI-p orbitals.
As these system involve heavy elements such as Pb and Te,
therefore spin orbit coupling (GGA þSOC) calculations are per-
formed in order to calculate the electronic properties of these
semiconductors in cubic phase and are plotted in Fig. 2(c). The
figure clearly indicates that the band gaps for all of these com-
pounds in the cubic phase are decreased by the spin orbit effect as
compared to mBJ results. In GeS, except reduction in the band gap
there is negligible SOC effect however strong SOC effects are ob-
served in PbS, PbSe, PbTe and SnTe compounds. This effect prin-
cipally splits the peaks in the valence and conduction band and it
has been observed that SOC effect increases as the element size is
increased i.e. from Ge to Pb (left to right in figure). In PbS not only
the peaks split but also the band is pushed towards the Fermi level
in conduction band, results reduction in the band gap energy. This
reduction in the band gap shows that there is strong effect of SOC
in PbS due to heavier element lead (Pb). The maximum splitting of
peaks are observed in PbTe which can be related to the heavier
elements that constituent the compound. As we go from up to
down in this plot, from lighter to heavier element, the SOC effect
increases. The splitting in the peaks are also increased from top to
bottom. So it is concluded that SOC effect increases from left to
right and from top to bottom (Fig. 2. (c)) which affects the band
gaps of these compounds directly.
3.3. Thermoelectric properties
Thermoelectric properties can be quantified using different
 A.A. Khan et al. / Materials Science in Semiconductor Processing 48 (2016) 85–94
Fig. 1. Band structures of IV-VI semiconductors in cubic crystal structure.
parameters, such as power factor and figure of merit (ZT) and
these parameters are strongly dependent on Seebeck coefficient
(S), electric conductivity (s), thermal conductivity (κ) and absolute
temperature. In the present work these coefficients are calculated
for binary IV-VI semiconductors in the temperature range 200–
900 K and discussed in detail below.
3.3.1. Seebeck coefficient
Seebeck coefficient or thermopower plays an important role in
the characterization and quantifying efficiency of thermoelectric
materials. Materials having large Seebeck coefficient have large
figure of merit which means higher efficiency to convert heat into
electrical energy and vice versa. Semiconductors are low carrier
concentration materials and show large Seebeck coefficients.
Seebeck coefficient is quantified in microVolt per Kelvin (mV/K)
and is sensitive to carrier concentration, effective mass of the
carrier and band shape. The calculated Seebeck coefficients of IV-
VI binary chalcogenides are plotted against temperature in Fig. 3
(a). The figure shows that the value of the Seebeck coefficient for
SnS at room temperature (300 K) is 200 mV/K, this value is de-
creased with increases in temperature. Seebeck coefficient for
89
SnSe, SnTe, SnS2 and SnSe2 at room temperature are 135, 209, 204
and 210 mV/K respectively, the plot remain flatten with the in-
crease in temperature but quite increase in the range 200–350 K
for these compounds. An increase in Seebeck coefficients is ob-
served for PbS and GeTe in the temperature range 200–500 K with
room temperature value 218 mV/K and then decrease with further
increase in temperature. Our calculated Seebeck coefficient for
PbSe at 300 K is 202 mV/K which is in good agreement with ex-
perimental value 212 mV/K [60]. There are exponentially increase
in the Seebeck with temperature of PbSe which follow the ex-
perimental trend [60]. Our calculated plot of Seebeck coefficient
for PbTe follow the experimental trend [61] and room temperature
value is 304 mV/K which is overestimated than the experimental
value 287 mV/K [62]. Seebeck coefficient for PbTe is larger as
compare to other IV-VI semiconductors which is the evidence for
its better thermoelectric performance. The Seebeck coefficient of
GeSe is decreasing with temperature up to 350 K and then remain
constant with small increase with temperature, while the room
temperature value is 306 mV/K. The Seebeck coefficient for SnSe is
less than the Seebeck coefficient of SnSe2, because SnSe is exist in
cubic while SnSe2 is crystallized in hexagonal structure; i.e. the
90 A.A. Khan et al. / Materials Science in Semiconductor Processing 48 (2016) 85–94

Table 2
Comparison of the direct and indirect band gap energies (eV) of IV-VI semiconductors.

Comp. Phase Experimental Theoretical

Present GGA Present mBJ Other

Direct Indirect Direct Indirect Direct Indirect Direct Indirect

a b
SnS Fm-3m 0.2 0.05 0.25 0.20
Pnma 1.16c,1.07d 0.951 1.27 0.52r, 0.91t, 1.20b
Cmcm 0.28 0.904 0.32b,0.57b
SnSe Fm-3m 0.04 0.23
Pnma 0.86c,e,0.95f 0.81 1.17 0.69t, 0.41r, 0.61e
Cmcm 0.37 0.832 0.39e
SnTe Fm-3m 0.20v 0.04 0.182 0.06g
PbS Fm-3m 0.29i, 0.41j 0.25 0.369 0.44h
Pnma 1.46 1.25 0.27k
PbSe Fm-3m 0.17i, 0.27k 0.30 0.254 0.31h, 0.28m
Pnma 0.4k 0.743 0.885 0.12k
PbTe Fm-3m 0.19i 0.41 0.40 0.8h, 0.36m
Pnma 0.734 0.994 0.17k
GeS Pnma 1.58n 1.27 1.56 1.25 t
Cmcm 0.32 0.63
GeSe Fm-3m 0.303 0.631
Pnma 1.2n 0.53 0.731 0.99 1.09 0.87 t
GeTe Fm-3m 0.20u 0.461 0.29 0.34g,0.14o
SnS2 P-3ml 2.88q 2.07q 2.05 2.00 2.85 2.24 3.15p 2.9b, 2.19p
SnSe2 P3ml 1.62q,1.33f 0.97q,1.03f 0.521 0.793 1.75p 0.91p

a
[53].
b
[40].
c
[54].
d
[63].
e
[23].
f
[49].
g
[42].
h
[9].
i
[64].
j
[56].
k
[47].
m
[57].
n
[46].
o
[19].
p
[55].
q
[58].
r
[59].
t
[22].
u
[66].
v
[65].

number of atom per unit cell of SnSe is small as compare to SnSe2.
The large Seebeck coefficient of SnSe2 as compare to SnSe can be
related to the extremely populated electronic band structure of
SnSe2 near the fermi-level. Similarly the figure show that some
compounds show high Seebeck coefficients than other, this is
because of different carrier concentration, effective mass, band
shape and electronic band nature of the material.
The comparison of calculated band gaps with the spin-orbit
interaction with the experimental data show significant im-
provement over the results based on mBJ, which may lead to es-
timate the Seebeck coefficient accurately. The effect of SOC on
Seebeck coefficient is calculated for some selected compounds and
are shown in Fig. 3(b). Significant improvement in the Seebeck
coefficients of GeTe, SnTe and PbSe is observed, whereas a notable
decrease in the Seebeck coefficients of PbS and PbTe is compre-
hended. The alteration of Seebeck coefficient with spin orbit cal-
culations for these selected compounds confirm the strong influ-
ence of SOC on lead base compounds.
3.3.2. Electric conductivity
Efficient thermoelectric devices needs high enough electrical
conductivity to attain large figure of merit. In semiconductors both
electrons and holes are responsible for electric conduction.
The calculated electric conductivity for IV-VI semiconductors
are plotted in Fig. 4(a). In these compounds electrical conductivity
almost linearly increases with temperature, due to the increase in
the number of carriers. The electrical conductivities of SnSe, SnTe,
SnSe2 and GeTe are higher than the other IV-VI chalcogenides
which lead them to paramount thermoelectric compounds. The
room temperature electrical conductivities with relaxation time
factor of these four compounds are 5.6, 0.65, 2.26 and
0.75  1019 (Ωms)  1 respectively. The conductivity of SnS2 also
increase with temperature but less value than the above discussed
compounds while the conductivity plot of SnS, PbS, PbSe, PbTe and
GeSe are almost remain flatten as temperature increases. We do
not compare our calculated electrical conductivity with experi-
mental results because BoltzTraP code cannot estimate the elec-
trical conductivity due to involving of relaxation time for the
compounds [34]. In Fig. 4(b) the SOC effect on electrical con-
ductivities for selected compounds are presented. The figure
shows that there is a significant improvement in the electric
conductivities of these compounds except SnTe and GeTe with the
inclusion of spin orbit interaction.
3.3.3. Thermal conductivity
Thermal conductivity is the ability of a material to conduct
 A.A. Khan et al. / Materials Science in Semiconductor Processing 48 (2016) 85–94 91

Fig. 2. (a): Total density of state (without SOC) of IV-VI compounds in different crystal phases. (b): Partial density state (without SOC) of IV-VI semiconductors in cubic crystal
structure. (c): Total density of state (with SOC) of IV-VI compounds in cubic crystal phase.

Fig. 3. (a) Seebeck coefficient verses temperature (without SOC) of IV-VI semiconductors. (b): Seebeck coefficient verses temperature (with SOC) of IV-VI semiconductors.

heat. Thermal conductivity ( κ ) for a material is due to two reasons,
(i) electron and hole motion that is electronic thermal
conductivity.
( κe ) and (ii) lattice vibration (phonons) that is lattice thermal
conductivity ( κl ). The measurement of κe is important, while κl is
usually computed as the difference between κ and κe using the
experimental data of electrical conductivity. The determination of the
total thermal conductivity is of great interest because it contributes
to the performance of thermoelectric materials. However BoltzTraP
can estimate the electronic part of thermal conductivity and do not
calculate the lattice thermal conductivity due to which the thermal
conductivities are underestimated [34]. Presently calculated
92 A.A. Khan et al. / Materials Science in Semiconductor Processing 48 (2016) 85–94

Fig. 4. (a) Electric conductivity (without SOC) with respect to scattering time s/t verses. temperature of IV-VI semiconductors (b) Electric conductivity (with SOC) with
respect to scattering time s/t verses. temperature of IV-VI semiconductors.

Fig. 5. (a) Thermal conductivity with respect to scattering time к/t verses temperature (without. SOC) of IV-VI semiconductors (b) Thermal conductivity with respect to
scattering time к/t verses temperature (with. SOC) of IV-VI semiconductors.

electronic thermal conductivities of IV-VI semiconductors are plotted
in Fig. 5(a). The electronic thermal conductivities of SnSe, SnTe, GeTe
and SnSe2 are increases as temperature increase. At room tempera-
ture their conductivities are 0.62, 0. 20, 0.159 and 0.22  1015 W/Kms
respectively. The remaining compounds have low thermal con-
ductivities as compared to the above discuss compounds and remain
constant up to 700 K temperature. Hence, the electronic thermal
conductivity for tin chalcogenides is higher as compared to lead
chalcogenides and all compounds have nearly the same electronic
thermal conductivities at lower temperatures. We do not compare
our calculated thermal conductivity with experimental results be-
cause BoltzTraP code cannot estimate the lattice thermal con-
ductivity and also the involvement of relaxation time factor.
The total thermal conductivities of SnTe, PbS, PbSe and PbTe are
calculated with SOC. Ad-hoc calculations of the total thermal
conductivity are performed by adding the electronic part from
present (BoltzTraP) results and lattice part from the experimental
data [69,70] and the results are presented in Fig. 5(b). The figure
shows that the lattice thermal conductivities are significant in
these compounds in the temperature range 300–700 K.
3.3.4. Power factor (P.F)
The effectiveness of thermoelectric materials are estimated by
power factor (P.F˭S2s), calculated from the Seebeck coefficient and
electric conductivity of the same material under a given tem-
perature difference. Materials having large P.F are more efficient to
generate or extract heat but not necessarily efficient in generating
useful energy. The calculated values of power factor with relaxa-
tion time factor (P.F˭S2s/t) for these binary IV-VI chalcogenides are
presented in the Fig. 6(a). At room temperature the P.F of tin mono
chalcogenides SnS, SnSe and SnTe are 1.34838  1011,
1.02546  1012 and 2.8582  1011 W/mK2s respectively. The figure
shows that the P.F of the SnS and SnSe is decreasing and increasing
respectively as temperature increase from room temperature
while the P.F for SnTe is increase exponentially with temperature
and have high value 1.686  1012 W/mK2s at 900 K. the P.F of the
lead chalcogenides PbS, PbSe and PbTe at room temperature are
3.4870  1010, 5.09748  1010 and 5.79009  1010 W/mK2s respec-
tively. There are no considerable increases in P.F of PbS with
temperature while in case of PbSe and PbTe, the P.F are increase
with increase in temperature. The P.F for GeSe and GeTe are
3.60087  1010 and 3.56778  1011 W/mK2s at room temperature
and increase with increase in temperature. Power factor of GeSe
remain constant with increase in temperature till 650 K and in-
crease with temperature as temperature increase above 650 K.
Similarly P.F for GeTe increase with temperature and have high
 A.A. Khan et al. / Materials Science in Semiconductor Processing 48 (2016) 85–94
Fig. 6. (a): Power factor of IV-VI semiconductors with respect to scattering time S2s/t verses. temperature (without SOC) (b): Power factor of IV-VI semiconductors with
respect to scattering time S2s/t verses. temperature (with SOC).
Fig. 7. Figure of merit of IV-VI semiconductors verses temperature (with SOC).
value 1.65094  1012 W/mK2s at 900 K. From Fig. 6(a), it is clear
the P.F of SnSe and SnSe2 are high from the other IV-VI semi-
conductor at room temperature as well as at high temperature.
The power factors of these compounds with the inclusion of
SOC effect are also calculated and presented in Fig. 6(b). The re-
duction in electric conductivities and enhancement in the Seebeck
coefficients with SOC; the power factor of GeTe, SnTe and PbSe are
significantly enhanced.
3.3.5. Figure of merit (ZT)
Dimensional less figure of merit ZT compared to seebeck,
electrical conductivity is the comprehensive parameter to in-
vestigate the thermoelectric performance of a material. With the
help of SOC and ad-hoc calculations we have computed figure of
merit for some selected compounds to obtain rational results. Our
calculated ZT for SnTe, PbS, PbSe and PbTe are plotted in the Fig. 7.
The figure show that the figure of merit value for SnTe and PbSe is
large then PbS and PbTe. The Seebeck coefficient and electric
conductivity of SnTe and PbSe is higher and total thermal con-
ductivity is lower as compared to the rest of the compounds, put
together these two compounds to high figure of merit. PbS have
ZT ¼0.7 at room temperature which decrease as the temperature
increases. This is due to the increase in the thermal conductivity
with raising the temperature. Similarly PbSe and PbTe have nearly
93
0.76 value of ZT, decreasing with temperature for PbTe due to large
increscent in thermal conductivity with temperature as compared
to its Seebeck coefficient and electric conductivity. The higher
values of ZT suggests that these compounds have great potential
for thermoelectric applications.
4. Conclusions
In the present manuscript DFT and post-DFT methods are used
to investigate the structural, electronic and thermoelectric prop-
erties of IV-VI semiconductors. The compounds such as SnS, SnSe,
GeS, GeSe are stable in orthorhombic phase, SnTe, PbS, PbSe, PbTe
are exist in cubic and SnS2 and SnSe2 are in hexagonal phase.
Electronic band gap calculations reveal that these compounds are
narrow band gap semiconductors in the energy range 0.1–2.8 eV.
Tin, lead and germanium chalcogenides show direct band gap
nature in cubic phase while indirect in orthorhombic phases.
BoltzTraP calculations are performed to investigate seebeck coef-
ficient, power factor, electronic and thermal conductivity for these
compounds. The Seebeck coefficient of PbTe is higher at room
temperature than the other compounds under study. The electrical
conductivity of SnSe is larger which is also an important feature of
a good thermoelectric material. The power factor is larger for
SnSe2 and SnSe at room temperature. Spin orbit coupling effect
greatly influence the electronic and thermoelectric properties of
these compounds.
Acknowledgement
We acknowledge the financial support from the Higher Edu-
cation Commission of Pakistan (HEC), project no. 20-3959/NRPU/
R&D/HEC2014/119.
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