International Journal of Thermophysics (2020) 41:58

https://doi.org/10.1007/s10765-020-02630-x

First‑Principles Investigation on Thermoelectric Properties

of VSb2 Material

Siham Malki1 · Larbi El Farh1

Received: 29 October 2019 / Accepted: 19 February 2020

© Springer Science+Business Media, LLC, part of Springer Nature 2020

Abstract
Recently, we have computed the structural and electronic properties of VSb2 using
the first-principles calculations based on the full potential linearized augmented
plane wave (FP-LAPW) method implemented in WIEN2k code. These studies have
shown that this material has a metallic character. In this work, we are interested
in the study of thermoelectric properties of VSb2 material using the semi-classical
Boltzmann transport theory. The Generalized Gradient Approximation (GGA) is
used in the scheme of Perdew–Burke–Ernzerhof (PBE) to treat the exchange corre-
lation effect. Thus, we discuss in detail the temperature effect on the thermoelectric
properties such as: the Seebeck coefficient, the thermal conductivity, the electrical
conductivity, the electronic specific heat, the figure of merit, the power factor and
the Pauli magnetic susceptibility.

Keywords Density functional theory · GGA calculation · Thermoelectric

properties · VSb2

1 Introduction

In recent studies on the VSb2 material, we have explored the structural and elec-
tronic properties using the Generalized Gradient Approximation (GGA) and the
Tran–Blaha modified Becke–Johnson exchange (TB-mBJ) potential to calculate the
density of states and the band structure [1] where the metallic character is observed.
In fact, metals are distinguished from semiconductors [2–4], in that their free elec-
trons provide not only the current conduction, but also the transport of heat. In
metals, the contribution of the charge carriers has an important role in the thermal

* Siham Malki
malkisiham59@gmail.com
Larbi El Farh
elfarhlarbi@yahoo.fr
1
Laboratory of Mechanics and Energetic, Department of Physics Faculty of Sciences,
Mohammed 1st University, Oujda, Morocco

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conductivity called the electronic thermal conductivity 𝜅e, which means that the
electron flow is extremely greater than the contribution of phonons. The electronic
term is therefore assertive and can be used properly to evaluate the heat conduction
potential of metallic materials [5].
According to our investigations, no theoretical results have been reported on
thermoelectric properties of VSb2 compound, which has motivated us to calculate
and discuss these properties over a temperature range 300–800 K. Furthermore,
the inter-metallic compounds have received considerable attention of the materials
researchers due to their vital role in designing new material used in several technolo-
gies such as refractory, spintronics and structural applications [6]. In addition, we
have been particularly interested in studying this binary di-antimonide, because this
type of materials is used a lot as diffusion barriers or electrodes for thermoelectronic
devices based on skutterdites [7]. These studies can contribute to current research on
new materials that can be the basis for new energy sources.

2 Computational Details

In this present study, the calculations are performed using the package BoltzTraP
[8], which contains the Boltzmann Transport Properties program for calculating the
semi-classic transport coefficients. This program is interfaced to the WIEN2k code
[9] which is based on the density functional theory (DFT) within the Full Poten-
tial Linearized Augmented Plane Wave (FP-LAPW) method [10, 11]. For evaluating
the exchange correlation potential, we use the Generalized Gradient Approximation
(GGA) developed by Perdew–Burk–Ernzerhof (GGA-PBE) [12]. The muffin-tin
radii are fixed to 2.5 atomic units for V and Sb atoms. To achieve energy and charge
convergence, the maximum value for partial waves inside muffin-tin spheres are
expanded in spherical-harmonics up to lmax=10. The cut-off parameter RMT ∗ Kmax
is set to 8.5, where RMT is the smallest atomic sphere radii in the unit cell and Kmax is
the plane wave cut-off. The stable structure is obtained when the self-consistency is
assumed to converge at a total energy of 0.0001 Ry.

3 Results and Discussion

3.1 Seebeck Coefficient

The Seebeck coefficient S is calculated to illustrate the thermoelectric response

of materials. Indeed, the Seebeck effect is based on the thermocouple principle of
applying a temperature gradient to cause a reverse electric field and potential differ-
ence called Seebeck voltage [13]:

8𝜋k𝛽2 m∗ T ( 𝜋 )3∕2
S= , (1)
3eh2 3n

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where k𝛽 , m∗, T, n, h, and e are, respectively, the Boltzmann constant, the effective
mass, absolute temperature, carrier concentration, Planck constant and electronic
charge. This coefficient is stated in Volt per Kelvin (V·K−1).
Figure 1 shows the variation of Seebeck coefficient S (in μV⋅K−1) depending
on temperature T (in K) for VSb2 material. We observe that the Seebeck coef-
ficient S takes negatives values, which means that the electrons are the majority
charge carriers in this temperature range, and therefore, VSb2 compound is a good
transport material acting as an n-type material in the temperature range (300–800
K). Additionally, this coefficient varies linearly with temperature T. This confirms
the metallic character of VSb2 compound.
The Seebeck coefficient takes a very low value of − 24 μV⋅K−1 at 800 K, which
means that compound has a dispersive nature at this temperature. It is worth not-
ing that, for this material the Seebeck coefficient at the room temperature 300 K,
is − 6.27 μV⋅K−1.

3.2 Thermal Conductivity

The ability of material to conduct heat and, consequently determine the heat flux
per area of the homogenous material for a given temperature difference is called
the thermal conductivity [14].
The total thermal conductivity 𝜅 includes two contributions, one of the lattice
𝜅l and the other of electronic 𝜅e:
𝜅 = 𝜅l + 𝜅e . (2)
Since VSb2 compound is a metallic character, we assume that the phononic thermal
conductivity is negligible.

Fig. 1 Variation of Seebeck coefficient with temperature using GGA

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The calculated electronic thermal conductivity (𝜅e ∕𝜏) vs. temperature shown
in Fig. 2, where 𝜏 is the relaxation time according to BoltzTrap program that is
used in this calculation, has a constant but unknown value in the constant relaxa-
tion time approximation (CRTA) [8]. The Wiedemann–Franz law represents the
dependence of the electronic thermal conductivity 𝜅e and the electrical conductiv-
ity 𝜎 according to the following equation:
𝜅e = L𝜎T. (3)
For free electrons, L (called Lorentz number) is a constant taking, in the free elec-
trons model, the value: L = 2.45 × 10−8 V⋅K−2. Figure 2 shows that thermal con-
ductivity increases linearly with increasing temperature along the considered range.
This is due to the fact that the electrons are thermally excited when temperature
rises, leading to more heat.

3.3 Electrical Conductivity

The electrical conductivity is considered one of the most important charge trans-
port properties. It can be calculated from the Boltzmann transport equations [8]
as following:
𝜕f𝜇 (T, 𝜖)
[ ]

𝛺∫
1
𝜎𝛼𝛽 (T, 𝜇) = 𝜎𝛼𝛽 (𝜖) − d𝜖, (4)
𝜕𝜖

where, respectively, 𝛼 and 𝛽 represent the tensor indices, 𝜇 is the chemical potential,
𝛺 is the volume of the unit cell, f𝜇 and T stand for the Fermi distribution function
and the absolute temperature. The essential ingredient, the energy projected conduc-
tivity tensors (transport distributions) are:

Fig. 2 Electronic thermal conductivity of VSb2 as a function of temperature

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1∑ 𝛿(𝜖 − 𝜖i,k )
𝜎𝛼𝛽 (𝜖) = 𝜎𝛼𝛽 (i, k) (5)
N i,k d𝜖

and can be obtained using k-dependent conductivity tensor:

𝜎𝛼𝛽 (i, k) = e2 𝜏i,k 𝜐𝛼 (i, k)𝜐𝛽 (i, k), (6)

where N represents the number of k points sampled in the Brillouin zone, 𝜐𝛼 (i, k) is
the component of band velocity, and 𝜏i,k is scattering time. Figure 3 represents the
curve of the conductivity as a function of the temperature for VSb2. It shows a signif-
icant decrease of 𝜎∕𝜏 in the whole temperature region studied, which indicates the
metallic behavior of VSb2 compound. This curve also indicates that the conductivity
decreases slowly in the range 300–800 K.
The electrical conductivity at 800 K is 2.084 × 1020 (Ωms)−1 while the one at the
ambient temperature is 2.112 × 1020 (Ωms)−1.

3.4 Electronic Specific Heat c

The electronic specific heat c can be described as the ratio of the thermal energy
used by the charge carriers to the rise in temperature of the material [15]. This
property is plotted as a function of temperature for VSb2 compound in Fig. 4. It is
related to the temperature and the Sommerfeld constant 𝛾 [16, 17] by the following
expression:
c = 𝛾.T (7)

The increase in the value of the electronic specific heat c of VSb2 compound indi-
cates improvement of density of states at the Fermi level and the itinerant character
of the V-3d electrons, which is clear in density of states of VSb2 compound [1].

Fig. 3 The temperature dependence of the calculated electrical conductivity of the VSb2

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Fig. 4 The electronic specific heat as a function of temperature for VSb2 compound

3.5 The Pauli Magnetic Susceptibility

We have calculated the Pauli magnetic susceptibility 𝜒 as a function of temperature

in order to approve the magnetic order of this material. 𝜒 is given by the following
expression [16]:
𝜕f𝜇 (T, 𝜖)
[ ]

∫
2
𝜒(T, 𝜇) = 𝜇0 𝜇𝛽 n(𝜖) − d𝜖, (8)
𝜕𝜖

where n(𝜖), 𝜇𝛽 , 𝜇0 are, respectively, the electronic density of states, the Bohr mag-
neton and the magnetic permittivity of vacuum. The susceptibility curve decreases
and then continues to decline almost in a linear fashion as shown in Fig. 5. So, the

Fig. 5 Temperature dependence of the Pauli magnetic susceptibility for VSb2 compound

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Curie law [18] is valid, i.e., 𝜒 ∝ 1∕T is obeyed for VSb2 compound. According to
this result, it is well known that Pauli susceptibility magnetic is positive; this indi-
cates that VSb2 is paramagnetic. The value of the Pauli magnetic susceptibility (𝜒) at
ambient temperature (300 K) is 2.4 × 10−9 m3 ⋅mol−1.

3.6 Power Factor

From the Seebeck coefficient (S) and the electrical conductivity (𝜎∕𝜏), we have eval-
uated the evolution of the power factor (PF = S2 𝜎∕𝜏) as a function of temperature.
This parameter is considered one of the important parameters to define the effi-
ciency of the thermoelectric material. The variation of the power factor with tem-
perature from 300 K to 800 K is depicted in Fig. 6. We observe that the PF increases
monotonously from 330 K, until reaching the value 12.05× 1010 W⋅m−1 ⋅s−1 ⋅K−2 at
800 K.

3.7 Figure of Merit

The dimensionless figure of merit was calculated by inserting the desired quantities
such as the electrical and the thermal conductivity. It is expressed as follows [14,
15]:

S2 𝜎T
ZT = , (9)
𝜅l + 𝜅e

where, respectively, T is the temperature, S is the Seebeck coefficient, 𝜎 is the elec-

trical conductivity, 𝜅l and 𝜅e are the thermal conductivities due to lattice and elec-
trons contributions [19]. The figure of merit (ZT) value exceeds the unit essential
for practical use as a Peltier cooler or thermoelectric generator. For metal systems,

Fig. 6 Calculated power factor as a function of temperature for VSb2 compound

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Fig. 7 Figure of merit versus temperature of VSb2

Table 1 Calculated and experimental Seebeck coefficient and figure of merit respectively for VSb2 and
V0.97 Sb2 at ambient temperature
ZT (10−3 )
( )
S μV⋅K−1

VSb2 (calculated) − 6.27 1.63

V0.97 Sb2 (experimental)[7] − 10.5 4.5

they assume that the phononic thermal conductivity is negligible. Then, the figure
of merit becomes: ZT = S2 ∕L [20]. However, a particular effort is needed to ensure
that the contribution from 𝜅l can be neglected. Beyond 330 K, the figure of merit of
VSb2 compound (Fig. 7) increases with temperature until reaching the value of 0.024
at 800 K.
In Table 1, we present a comparison of our values of Seebeck coefficient S and
figure of merit ZT for VSb2 obtained by GGA with those experimental for V0.97 Sb2
[7], at room temperature.
The remarkable difference between the experimental results and the calculated
results can be attributed to the existence of the vacancies in the V0.97 Sb2 compound.

4 Conclusion

In this paper, we have applied the Generalized Gradient Approximation using full
potential linearized augmented plane wave (FP-LAPW) method to obtain an analyti-
cal representation and calculate the transports coefficients.
The thermoelectric properties were investigated by solving the semi-classical
Boltzmann transport equations as implemented in BoltzTrap code. It should be
pointed out that the significant decrease of the electrical conductivity (𝜎∕𝜏) confirms
the metallic character of VSb2 compound.

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Furthermore, the negative values of the Seebeck coefficient mean that electronic
type carriers are dominant in the thermoelectric transport for this material.
The calculated magnetic susceptibility (𝜒) does follow the Curie law. Addition-
ally, the positive values of this coefficient indicate that VSb2 is paramagnetic.
The electronic heat (c) varies according to a linear relationship with temperature.
From 330 K, the calculated power factor (PF) increases rapidly with increasing
temperature.
The results obtained in this work are expected to be a trigger for future experi-
mental interest in this material.

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