International Journal of Thermophysics (2021) 42:5

https://doi.org/10.1007/s10765-020-02755-z

Thermoelectric and Piezoelectric Properties in Half‑Heusler

Compounds TaXSn (X = Co, Rh and Ir) Based on Ab Initio
Calculations

Z. A. A. R. Almaghbash1 · O. Arbouche2,6   · A. Dahani3,6 · A. Cherifi1,6 ·

M. Belabbas1 · A. Zenati2 · H. Mebarki4 · A. Hussain5

Received: 5 September 2020 / Accepted: 10 October 2020

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

Abstract
In this paper, we report a theoretical study of the structural, electronic, thermoelec-
tric and piezoelectric properties of TaXSn (X = Co, Rh and Ir) half-Heusler com-
pounds crystallizing with cubic MgAgAs-type structure. We have made a quanti-
tative evaluation of thermoelectric figure of merit (ZT) and the electromechanical
coupling coefficient (k14) of these compounds. Accordingly, we intend to combine
the first-principles band structure calculations using (DFT)-based FP-LAPW
approach and the semi-classical Boltzmann transport theory within constant scatter-
ing time approximation (CSTA) to interpret and predict the thermoelectric perfor-
mance (ZTe) without the lattice thermal conductivity as a function of the chemical
potential at various temperatures. Further, to obtain a reasonable estimate for (ZT)
with the intrinsic lattice thermal conductivity, we have calculated the relaxation time
(τ) at various temperatures using Bardeen–Shockley theory. Finally, for predicting
piezoelectric coefficients, we have employed the modern theory of polarization as
provided by density-functional perturbation theory (DFPT) based on plane waves
and pseudo-potentials (PP-PW). Our key result is that these half-Heusler semicon-
ductors are attractive for practical applications in energy-harvesting technology,
which has a high (ZT) and (k14) of 0.89 and 0.25, respectively, at room temperature.

Keywords  CSTA · Deformation potential DP · DFT · DFPT · FP-LAPW · Half-

Heusler · Piezoelectric properties · PP-PW

* O. Arbouche
arbouche_omar@yahoo.fr; omar.arbouche@univ‑saida.dz
Extended author information available on the last page of the article

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1 Introduction

Energy harvesting has become a topic increasingly discussed by scientists and

environmentalists. A thermoelectric device that effectively recycles wasted
energy would be desirable because it would not only open the way to the crea-
tion of sustainable systems, but would also support the principle of green energy.
An attractive family of intermetallic ternary compounds is very relevant, given
their different properties that make them potential candidates for a number of
applications. The motivation of the present work is the capability of half-Heusler
compounds in thermoelectric and piezoelectric applications. Recently, research
of some ternary half-Heusler compounds with MgAgAs structure has become
very significant for improving the applications such as thermoelectric perfor-
mance [1–4], optoelectronic technology [5, 6], and piezoelectric energy harvest-
ing [7–9]. The stoichiometric composition of these compounds corresponds to
the formula ABC, where A and B atoms are the transition or rare-earth element
and C atom is a heavy metal element. On the criterion of the number of valence
electrons, half-Heusler semiconductor compounds (HH) [10] are divided into two
groups, the first of which consists of 18 valence electron numbers (VEN = 18)
and the other of 8 valence electron numbers (VEN = 8); for thermoelectric appli-
cations, VEC = 18 half-Heusler compounds were considered promising. The
small bandgap of VEC = 18 half-Heusler compounds at the Fermi level affects
the thermoelectric properties. Gautier et  al. [10] have synthesize the HfIrSb,
TaIrSn, ZrIrSb compounds by powder X-ray diffraction that are predicted to be
thermodynamically stable and have interesting functionalities through transmis-
sion electron microscopy (TEM) measurements. Also, Zakutayev et al. [11] have
confirmed experimentally the TaCoSn compound’s predicted zinc blende-derived
crystal structure.
Besides, Haque et  al. have been studied theoretically [12] mechanical and
thermodynamics properties of the TaCoSn compound. Other theoretical studies
[13–16] reported the thermoelectric performance of TaRhSn and TaIrSn com-
pounds through the first-principles density-functional theory. Thus, the present
work is to study the structural and electronic properties of TaXSn (X = Co, Rh
and Ir) compounds by mean possibilities of the full potential linearized aug-
mented plane wave (FP-LAPW) concept [17] within the framework of density-
functional theory (DFT) [18] implemented in the WIEN2k code [19].
Furthermore, the ground-state properties such as lattice parameter, bulk
modulus and its pressure derivative as well as formation enthalpy and cohesive
energy were calculated using GGA-PBEsol approach [20], and also compared to
the available experimental and theoretical works reported in the literature. Since
calculations using standard local-density (LDA) or generalized gradient approxi-
mation (GGA) schemes for the exchange–correlation potential underestimate
the bandgaps of semiconductors, we have employed the modified GGA known
as the Tran–Blaha modified Becke–Johnson potential (TB-mBJ) [21] to prevent
the shortcoming of the underestimation of the energy gaps. The calculations of
thermoelectric properties are very sensitive to electronic structure calculations.

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Furthermore, we combine the electronic structure calculations with Boltzmann

transport theory [22] as incorporated in BoltzTraP code [23]. In addition, to
obtain reasonable results for electron relaxation time, we have used the defor-
mation potential theory [24], where we can calculate the intrinsic lattice thermal
conductivity via the bulk and shear moduli of these materials using Slack’s equa-
tion [25].
To study and introduce the application of our compounds for the piezoelectric
devices, we calculated within the framework of modern theory of polarization and
density-functional perturbation theory DFPT [26, 27] as implemented in the open-
source ABINIT software package [28–30]. To our knowledge, there are no previous
theoretical or experimental data on the piezoelectric properties of TaXSn (X = Co,
Rh and Ir) compounds. Consequently, we compared our findings included of pie-
zoelectric constant ­(e14) with the experimental measures of GaAs compound [31],
and we take into consideration this work as a theoretical prediction of piezoelectric
effect in these compounds.
The remaining part of this paper is organized as follows after this introduction,
the theoretical prediction methodology is expressed in Sects. 2 and 3 presents the
results and a discussion. Conclusion that summarizes the results obtained is given in
Sect. 4.

2 Theoretical Methodology

In our investigation, the exchange–correlation energy is adopted by the general-

ized gradient approximation (GGA-PBEsol) to study the ground-state properties
of TaXSn (X = Co, Rh and Ir) type a half-Heusler compounds such as lattice con-
stants, bulk modulus and its pressure derivatives, formation energy and cohesive
energy. The archetype of crystalline structure is in cubic MgAgAs-type structure
with a space group (F-43  m, N ­ o 216, C­ 1b), which can be regarded as four inter-
penetrating face-centered cubic (FCC) lattice are in Wyckoff positions 4a (0, 0, 0),
4d (1/2, 1/2, 1/2) and 4c (1/4,1/4, 1/4) fully occupied with Ta, (X = Co, Rh and Ir),
and Sn atoms, respectively. The electronic configurations of the studied elements
are ­Kr5s24d105p2 for Sn, A
­ r4s23d7 for Co, ­Kr5s14d8 for Rh, X
­ e6s24f145d7 for Ir and
2 14 3
­Xe6s 4f 5d for Ta.
The iterative calculation process is repeated until the convergence of the total
energy is stable at less than 0.1 mRyd. For the Brillouin zone sampling, we
use a Monkhorst and Pack [32, 33] mesh of (14 × 14 × 14) k-points for all com-
pounds. In addition, the recent Tran and Blaha-modified Becke–Johnson poten-
tial (TB-mBJ) is also used to avoid the well-known GGA underestimation of the
bandgap. The transport phenomena in these compounds are predicted with the
constant relaxation time and rigid band approximations. In BoltzTrap code the
relaxation time is taken to be a constant because it cannot be determined from
band structure calculations. Accordingly, we have applied a very dense grid of
(45 × 45 × 45) k-points mesh in the whole Brillouin zone of each compound for
a self-consistent (FP-LAPW) calculation to estimate the (ZTe) without the lattice
thermal conductivity. Moreover, the relaxation time (τ) was evaluated by using

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deformation potential theory [24] on the basis of effective mass approximation.

We calculate the internal lattice thermal conductivity to obtain a reasonable
value of figure of merit (ZT). The following diagram shows the complete steps
of our calculation.

Next, the prediction of piezoelectric coefficients of these compounds were

carried out using the modern theory of polarization and density-functional per-
turbation theory (DFPT) as implemented in the open-source ABINIT code based
on plane waves and pseudo-potentials (PP-PW). In the framework of modern
theory of polarization where the strains are treated as perturbations and the elas-
tic, dielectric and piezoelectric tensors are estimated by the second derivatives
of the total energy with respect to the atomic displacement. In order to analyze
the piezoelectric properties the ANADDB tool (analysis of derivative data base)
in the ABINIT package was used to extract the dielectric (𝜀ij ) , elastic (Cij ) and
piezoelectric (eij ) tensors.
Optimized pseudo-potentials [34, 35] basis set for all atoms in this calculation
are generated using the OPIUM package to describe the interactions between the
valence electrons and the nuclei and core electrons, while the exchange–correla-
tion energy was evaluated in the generalized gradient approximation (GGA) the
scheme of Perdew–Burke–Ernzerhof [36]. For the crystal structure relaxation,
elastic, dielectric and piezoelectric the convergence has been reached for both
codes with an energy tolerance of ­10−6 eV with ­Ecut = 50 Hartree and an 8 × 8 × 8
mesh grid for Brillouin zone sampling.

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3 Results and Discussion

3.1 Ground‑State Properties

Firstly, the results of structural properties of TaXSn (X = Co, Rh and Ir) compounds
in cubic MgAgAs-type structure are summarized in Table  1, together with some
available theoretical and experimental data. These results were adjusted by the Mur-
naghan equation of state [37]. Overall, a good agreement is found with the experi-
mental values of TaIrSn compound reported by Gautier et  al. [10] and Zakutayev
et  al. [11]. The atomic positions in cubic MgAgAs-type structure are not affected
by the optimization, because they are fixed by the high-symmetry F-43m shown in
Fig. 1. Additionally, the formation enthalpies are calculated in order to examine the
stability of our compounds using the following relation:
[ TaXSn ( b )]
Etot − ETa + EXb + ESnb
TaXSn
ΔH for = , (1)
3
TaXSn is the total energy of compound, whereas E b  , E b and E b are the
where Etot Ta X Sn
ground-state energies of the stable bulk phase of tantalum crystallize in body cubic
centered structure with space group (Im3m ­ No 229), tin with a body-centered

Table 1  The optimized lattice constants a (Å), bulk moduli B (GPa), bulk modulus pressure derivative
B′, formation energy ΔHf (eV/atom found in literature of TaXSn (X = Co, Rh, and Ir) compounds with
cubic MgAgAs-type ­C1b structure using GGA-PBEsol calculations
Compound a (Å) B (GPa) Bʹ Eg (eV) ΔHf (eV/atom) Ec (eV/atom)

TaCoSn
 This work 5.8918 186.2674 4.1104 1.148  − 0.300 -5.0423
 Exp 5.94 [11] – – – − 0.323 [39]
 Other 5.95 [12] 1.09 [13]
5.95 [13] 1.07 [13]
5.97 [10] 1.16 [16]
1.107 [12]
1.153 [12]
1.37 [10]
 > 1 [11]
TaRhSn
 Our work 6.1268 183.6625 4.8520 1.160  − 0.395  − 5.7504
 Exp – – – –  − 0.484 [39]  − 5.99 [39]
 Other 6.207 [14] 154.6 [14] 4.67 [14] 1.25 [14]  − 0.310
6.201 [10] 1.40 [10]
TaIrSn
 Our work 6.1692 199.8019 4.8608 1.331  − 0.473 − 8.4192
 Exp 6.175 [11] – – – − 0.548 [39]
 Other 6.233 [10]
6.251 [15] 178.9 [15] 4.45 [15] 1.14 [15]
1.55 [11]

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Fig. 1  Crystal structure of
TaXSn (X = Co, Rh and Ir)
half-Heusler (MgAgAs structure
type, called Juza–Nowotny
compounds), group (F-43 m, ­No
216, ­C1b), [38, 40]

tetragonal structure (I41/amd ­No 141), rhodium in face-centered cubic structure

(Fm3m ­No 225), iridium in face-centred cubic structure (Fm3m N ­ o 225) and cobalt
o
in hexagonal structure (P63/mmc N ­ 194). Our results of the energy formations of
these compounds energy are also listed in Table 1. Interestingly, the predicted val-
ues of the formation energies have a negative sign which confirms the exothermic
nature of synthesis process of materials and indicate to assume that these ternary
compounds are energetically favorable and could be experimentally obtained. Fur-
ther, we calculated the cohesive energy of our compounds at zero pressure exactly at
the balance volume. The cohesive energy is defined as the binding energy of atoms
to form the solid, can be calculated as the difference between the total energy of the
atom and that of the solid, per atom, which is defined as:
[ TaXSn ( )]
Etot − ETa + EX + ESn
TaXSn
Ecoh = , (2)
3
where ETa , EX and ESn are the total energies of isolated of Ta, (X = Co, Rh and Ir)
and Sn atoms and Etot TaXSn is the total energy of TaXSn (X = Co, Rh and Ir) com-

pounds in the cubic MgAgAs-type structure that are systematically calculated using
the first-principles calculations. These results show that the TaXSn (X = Co, Rh
and Ir) compounds imply the structural stability in this phase and suggest that they
can be prepared and stabilized experimentally. Also, we can see from Table 1 that
the binding energy in the TaIrSn compound is larger than the binding energy in the
TaCoSn and TaRhSn compounds.

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3.2 Electronic Band Structures and Density of State (DOS)

The electronic band structures with the (TB-mBJ) approximation of TaXSn (X = Co,
Rh and Ir) compounds along symmetry directions are displayed in Fig. 2. We remark
that our compounds exhibit semiconductor behavior with indirect bandgap. The cal-
culated band energies at the (Г-X) points are given in Table 1 and compared with
other theoretical and experimental investigations. In addition, the highly flat band
along (Г-X) in the valence band gives a significant effective mass, which is good for
thermoelectric performance.
Further, to elucidate the electronic structure of these compounds, we have calcu-
lated total and partial density of states for all the investigated compounds and rep-
resented the same in Fig.  3 within the energy interval from (− 10 to 10) eV. The
PDOS plots of TaXSn (X = Co, Rh and Ir) show that the lowest valence in the range
of (− 10 to − 7.5) eV, is derived from the Sn-p state, and very low contribution of
the other atoms. Figure  3a shows the total and partial electronic state densities of
the TaCoSn compound. It is clear that the valence band between (− 2 to − 5.90) eV
mainly consists of the Co-d states with the contribution of Ta-d states, and mainly
dominated by Ta-d state just near the Fermi level, and very low contribution of the
Sn-p state. The conduction band in the range of (0 to 5) eV is dominated by Ta-d
states, and less than by the Co-d states. The Sn-p states have been very low partici-
pation, whereas the same participation of the three atoms states located at (5 to 9)
eV from the conduction band.
As shown in Fig. 3b, a sharp peak at the valence band between − 3 eV originates
from the hybridization between Ta-d; Rh-d and Sn-5p states, while the lower part is
mainly from the Sn-p orbital near the Fermi level.
From Fig. 3c, a sharp peak at the valence band of TaIrSn compound is observed
in the range of valence band in the range of (− 5.90 to – 2) eV. These peaks origi-
nate from the Ir-d and d-Ta states. Other sharp peaks are derived from the both Ta-d

Fig. 2  Bandgap energy of all compounds TaCoSn (a), TaIrSn (b) and TaRhSn (c)

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Fig. 3  Total and partial densities of states (DOS) for TaCoSn (a), TaIrSn (b) and TaRhSn (c)

and Ir-d states and located at (− 2 to 0) eV. The contribution of the Ta-d band is the
highest in the range of (0 to 5) eV in the conduction band, and the same contribution
of d-Ta, d-Ir and p-Sn states in the range of (5 to 9) eV.
In general, the dense electronic states of these compounds at the vicinity of Fermi
level suggest a large Seebeck coefficient and hence also the thermoelectric power
factor, which will be discussed in the next subsection.

3.3 Thermoelectric Properties

The efficiency of thermoelectric materials governed by the dimensionless figure of

merit should be equal to or greater than one (ZT ≥ 1), which can be expressed as:

S2 𝜎T
ZT = , (3)
𝜅e + 𝜅in

where S, σ , 𝜅e , 𝜅in , and T are the Seebeck coefficient, electrical conductivity, elec-
tronic thermal conductivity, intrinsic lattice thermal conductivity and absolute tem-
perature, respectively. In this section, we first present the results of the semi-clas-
sical Boltzmann transport equation (BTE) for electrons which requires knowledge
of the electron density of states (DOS) as incorporated in BoltzTraP code. Under

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rigid band approximation (RBA) the Fermi level will move up the bandgap or down
through the chemical potential (μ) depending on doping type, but the underlying
band structure is not allowed to change. Within the constant scattering time approxi-
mation (CSTA), the relaxation time (τ) is independent of the energy levels and
k-points and assuming to be ~ 10–14 s. The output of BoltzTraP includes the dimen-
sionless figure of merit ZTe as shown in Eq. 4, while BoltzTraP is mainly thought of
as a tool to evaluate only the electronic contribution to the thermal conductivity 𝜅e
of TaXSn (X = Co, Rh and Ir) compounds are being calculated with respect to the
relaxation time (τ).

S2 𝜎T
ZTe = . (4)
𝜅e

Figures  4, 5, 6, 7, 8 show the thermoelectric properties such as Seebeck coef-

ficient, electrical conductivity, thermopower factor (PF = S2 𝜎) electronic thermal
conductivity 𝜅e , and figure of merit ZTe ; respectively, versus the chemical poten-
tial (μ) eV in the range of − 0.2 eV to 0.2 eV at three constant temperatures 300 K,
500 K and 700 K. We first illustrate in Fig. 4 the change of Seebeck coefficient with
the chemical potential (μ) as well as temperatures, we can see that the almost same
value of thermopower (252 μV· K ­ −1) at room temperature for all compounds, which
are very close to with a numerical approach (243 μV·K−1) value of TaCoSn com-
pound predicted by Haque [12]. Indeed, the overall feature for these half-Heusler
have Seebeck coefficients greater than the value to that of the well-known thermo-
electric material PbTe calculated by Singh [36] with Boltzmann transport calcula-
tions which was found to be below 150 μV·K−1 = K at room temperature. We con-
clude that the large Seebeck coefficients obtained with p-type are higher than the

Fig. 4  Seebeck coefficient of TaXSn (X = Co, Ir and Rh) compounds

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Fig. 5  Electrical conductivity TaCoSn (a), TaIrSn (b) and TaRhSn (c)

Fig. 6  Electronic thermal conductivity TaCoSn (a), TaIrSn (b) and TaRhSn (c)

values with n-type, which reveals that the large Seebeck coefficient originates from
the corrugated (Г-X) in valence band.
The electrical conductivity with respect to relaxation time (σ/τ) with the varying
Fermi level at temperatures 300 K, 500 K and 700 K is also calculated and shown
in Fig. 5. It is observed that the electrical conductivity of these compounds at high
positive value of chemical potential rises slightly with the increase in temperature.

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Fig. 7  Power factor of all compounds TaCoSn (a), TaIrSn (b) and TaRhSn (c)

Fig. 8  Figure of merit of all compounds TaCoSn (a), TaIrSn (b) and TaRhSn (c)

The carrier density enhances with temperature which improves the electrical con-
ductivity. The value of electrical conductivity is large at positive values of chemical
potential as compared to negative values, which shows that the n-type structure has
better electrical conductivity than p-type doping.
Moreover, the potential to produce efficient electrical power for a material is
measured by its power factor (PF). Figure  6 demonstrates our calculated results
of power factors PF with respect to the relaxation time, which results from the
product of the square of Seebeck coefficient and electrical conductivity (PF = S2

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σ/τ). We observed that the highest value of power factor of TaCoSn, TaRhSn
and TaIrSn compounds takes the values of 19 × 1011 W·m−1·K−2·s−1, 18 × 1011
W·m−1·K−2·s−1 and 17 × 1011 W·m−1·K−2·s−1, respectively, and is studied for
p-type doping at 700 K. Our analysis of (PF) potently accords with the results of
Seebeck coefficient and electrical conductivity. Hence, one can expect TaCoSn to
have higher electrical conductivity than TaRhSn and TaIrSn compounds, which is
another factor responsible for the large power factor.
On the other hand, Fig.  7 displays the electronic thermal conductivity calcu-
lated for TaXSn (X = Co, Ir and Rh) compounds with chemical potential (μ) at
different temperatures. It is clearly observed that TaCoSn compound has high
value of electronic thermal conductivity at high temperature and high chemical
potential as compared to TaRhSn and TaIrSn compounds. This fact is due to the
increase of both free electrons energy and vibrational energy in these compounds
as temperature is raised, because the freely moving valance electrons are not only
transferring the electric current but also heat energy.
Figure 8 shows the variation of the figure of merit (ZTe ) at 300 K, 500 K and
700  K versus chemical potential (μ). From this figure, it is noted that at room
temperature 300  K, the TaIrSn compound has value around unity but TaRhSn
and TaCoSn compounds the maximum value of (ZTe ) is about 0.99 and 0.98,
respectively. One might speculate that the origin of this large (ZTe ) around the
mentioned points is due to the power factors (PF) and low thermal conductivity.
Figure of merit (ZTe ) increases abruptly from 0.05 eV value of chemical potential
and the peak value is obtained, which occurs at the chemical potential around
Fermi level and 0.05  eV for these compounds, but the value of figure of merit
decreases sharply after downward at the vicinity of Fermi level and upward from
0.05 eV. Overall, these compounds are good thermoelectric candidates in values
of chemical potential ranging from near Fermi level to 0.05 eV for n-type doping
is due to the large Seebeck coefficient and low thermal conductivity.
The purpose of the next step is to calculate the intrinsic lattice thermal con-
ductivity via the bulk and shear moduli of the material using Slack’s equation to
obtain a reasonable estimate for (ZT) . These half-Heusler materials are consid-
ered a suitable high-mobility solar material due to their effective mass less than
1.5m0 [41]. It is widely known that if the photo-generated carrier’s effective mass
is smaller, the carriers will be more likely to achieve the surface response sites
in their lifetime. The mobility difference of electrons and hole is greater when
the relative ratio of ­mh*/me*, which is far from 1 and thus the recombination rate
of electron–hole photo-generated pairs is small [42]. The following formula can
obtain the effective mass of an electron or a hole:
( 2 )−1
d E(k)
m∗e(h) = ℏ2 , (5)
dk2

where ћ is the reduced Planck’s constant, k is the wave vector, and E(k) is the elec-
tronic energy for the wave vector. Effective mass of hole obtained using both effec-
tive mass of heavy-hole and light-hole is shown in the following formula [43]:

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√
3 ( )2
m∗h = m∗HH 3∕2 + m∗LH 3∕2 . (6)

First consideration is given to the effective electron mass near the CBM. The
calculated effective masses of the heavy-hole and light-hole band of our com-
pounds are listed in Table  2. This table shows clearly that the effective mass of
hole is higher than the effective mass of electrons, which indicates that these
compounds represent p-type semiconductors. In our obtained result, we find that
the electron–hole recombination is weak for the TaCoSn compound. We can
deduce that TaCoSn compound will have a greater potential to separate photo-
excited pairs of electron–hole compared to both TaRhSn and TaIrSn compounds.
The edges of the energy bands flatten with increasing temperature, which means
that the energy bands become heavier. This leads to an increased effective mass
of carriers that affects the material’s transport properties.
The mobility of the charge carriers 𝜇 is calculated using the following formula
[43]:
√
2 2𝜋eℏ4 c11
𝜇= , (7)
3(kB T)3∕2 m∗ 5∕2 VDP
2

where e is the electron charge, ℏC11 is reduced Planck’s constant, is one of the three
independent elastic constants, kB is the Boltzmann constant, and VDP is the deforma-
tion potential constant which is calculated using:
dEedge
VDP = (8)
d𝛼

a − a0
𝛼=
a0
, (9)

where Eedge is the energy at the valence band maximum (VBM) or conduction band
minimum (CBM), 𝛼 is the uniaxial strain along the direction of the lattice vector
a . The strain is defined by varying a with respect to the calculated equilibrium lat-
tice constant a0 . The carrier mobility will change with changing temperature, which
induces the relaxation time values. The relaxation time has been calculated with dif-
ferent temperatures (T = 300 K, 500 K and 700 K), using the following formula:

Table 2  Effective mass of Compounds TaCoSn TaRhSn TaIrSn

electron m∗e and heavy-hole
(HH) m∗HH of TaXSn (X = Co, m∗HH /m0 heavy-hole 0.12787 0.10415 0.09366
Rh and Ir) compounds
m∗LH /m0 light-hole 0.07316 0.04694 0.04775
m∗H /m0 hole 0.16251 0.12422 0.1152
m∗e/m0 electron 0.06768 0.06988 0.07864

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𝜇m∗
𝜏= . (10)
e
Results of relaxation time with dependence of temperature effect are calculated as
the following equation:
√
2 2𝜋ℏ4 C11
𝜏= . (11)
3(kB T)3∕2 m∗ 3∕2 VDP
2

The most robust conclusion from Table  3 is that the relaxation time 𝜏 of elec-
tron is greater than of hole. In the other hand, the Seebeck coefficient of material
increases with increasing in the effective mass of the carrier.
The intrinsic thermal conductivity of materials can be calculated in different
ways. Naydenov [43] revealed a mathematical formula for calculating intrinsic lat-
tice thermal conductivity via the bulk and shear moduli of the material using Slack’s
equation is given by the following equation:
1∕3
𝜃D3 Va mav
𝜅in = A , (12)
𝛾 2 n2∕3 T
where 𝜃D , Va , mav , 𝛾 and n are the Debye temperature, the volume per atom (in Å),
the average atomic mass, the Gruneisen parameter and the number of atoms in the
unit cell, respectively. The parameter A is given by the following equation:

2.43 × 10−6
A= 0.514 0.228
. (13)
1− 𝛾
− 𝛾2

The Gruneisen parameter can be obtained from the Poisson ratio 𝜐 in the follow-
ing way:
( )
3 1+𝜐
𝛾= . (14)
2 2 − 3𝜐
Table  4 gathered these parameters for TaXSn (X = Co, Rh and Ir) com-
pounds. Intrinsic thermal lattice conductivity 𝜅in of TaXSn (X = Co, Rh and Ir)

Table 3  Relaxation time Relaxation time 300 K 500 K 700 K

𝜏(T) × 10−18 s at different 𝜏(T) × 10−18 s
temperatures (300 K, 500 K and
700 K) of TaXSn (X = Co, Rh e
𝜏TaCoSn 1.33335 0.61968 0.37409
and Ir) HH compounds
h
𝜏TaCoSn 0.35835 0.16654 0.10054
e
𝜏TaRhSn 1.04087 0.48375 0.2920
h
𝜏TaRhSn 0.43917 0.20411 0.12321
e
𝜏TaIrSn 0.95711 0.44482 0.26853
h
𝜏TaIrSn 0.53982 0.25088 0.15145

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International Journal of Thermophysics (2021) 42:5 Page 15 of 19  5

Table 4  The Gruneisen parameter 𝛾 , A coefficient, Debye temperature 𝜃D , volume per atom Va (in Å), the
average atomic mass mav (in amu), the number of atoms n in the unit cell and Poisson ratio 𝜐
Components 𝛾 A 𝜃D Va mav n v
–4 –22
TaCoSn 1.677 3.136 × 10 356.335 68.5238 5.9546 × 10 3 0.284
244 [46]
TaRhSn 1.742 3.115 × 10–4 328.026 76.66 6.6848 × 10–22 3 0.295
1.7 [13] 313.02 [13]
TaIrSn 1.932 3.056 × 10–4 299.717 78.265 8.167 × 10–22 3 0.324
1.29 [14] 312.54 [14] 0.31 [14]

half-Heusler compounds is depicted in Fig. 9. The intrinsic thermal lattice con-

ductivity of TaCoSn is higher than TaRhSn and TaIrSn compounds, which is
due to the higher Debye temperature. The intrinsic lattice thermal conductivity
decreases with increasing temperature. Finally, Fig. 10 has the information of the
temperature dependence of the dimensionless figure of merit (ZT) and (ZTe), indi-
cating that the conductivity effect of the induced thermal lattice shows a signifi-
cant difference between (ZT) and (ZTe) of TaXSn (X: Co, Rh and Ir) compounds
in the range of [300–600]. This difference between (ZT) and (ZTe) is small at
high temperature, which is due to the effect of temperature on the internal lat-
tice thermal conductivity. Our calculations show that TaXSn(X: Co, Rh and Ir)
compounds are candidate thermoelectric materials with (ZT) close to 0.8 at high
temperature.

Fig. 9  The intrinsic lattice thermal conductivity of all compounds when obtained by Slack’s equation

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 5  Page 16 of 19 International Journal of Thermophysics (2021) 42:5

Fig. 10  Temperature dependence of the dimensionless thermoelectric figure of merit (ZT) and (ZTe) for
TaXSn (X = Co, Rh and Ir) half-Heusler compounds

3.4 Piezoelectric Properties

In this section, we will also examine the possible piezoelectric effect in TaXSn
(X = Rh,Co and Ir) half-Heusler compounds using the pseudo-potential plane
wave (PP-PW) approach in the framework of the (DFT) and the (DFPT) within
GGA exchange–correlation energy functional. Therefore, these calculations are
defined as the second derivative of the total energy with respect to the atomic
displacement within the framework of first-principles calculation. Among the
five symmetry classes belonging to the cubic system, only Hextetrahedral crystal
(43  m) and tetartoidal form (23) are noncentrosymmetric structures and hence,
they are good candidates for piezoelectric, for the others structures such as hex-
octahedral (m3m), gyroidal (432) and diploidal (m3), the piezoelectric effect
is absent, because of the centrosymmetric nature. For the cubic AgMgAs-type
structure F-43m symmetry, there are three independent elastic constants ( C11 , C12
and C44 ) and the piezoelectric tensor (eij ) contains only one constant ­e14 (in the
direct piezoelectric effect).
The calculated results of lattice parameter, the linear bulk piezoelectric, die-
lectric and elastic constants were carried out by using the ANADDB module of

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International Journal of Thermophysics (2021) 42:5 Page 17 of 19  5

Table 5  The calculated lattice constants a (Å), elastic constant ( C11 , C12 and C44 ) in (GPa), piezoelectric
coefficients ­(e14 (C/m2) and d­ 14 (pc/N)), electromechanical coupling coefficient k14 and zero-stress static
dielectric constant 𝜀0 using GGA​calculations
Compo- a0 (Å) C11 C12 C44 e14 d14 ϵ0 k14
nents

TaRhSn 6.197 248.8 124.46 73.6 0.69309 9.41 29.137 0.16

6.207 [15] 239.9 [15] 114.9 [15] 81.0 [15]
TaCoSn 5.967 303.78 95.97 75.38 1.176 15.61 32.10 0.254
5.95 [12] 382.2 [12] 148 [12] 88.8 [12]
TaIrSn 6.23 273.12 136.9 80.81 0.82 10.10 27.52 0.185
6.251 [14] 244.20 146.30 101.89
[14] [14] [14]
GaAs 5.51 99.103 41.430 50.852 0.221 6.390 15.833 0.114
5.654 [45] 106.5 [45] 53.3 [45] 60.2 [45] 0.16 [31] 14.84 [45]
5.653 [44] 0.292 [44]

the ABINIT package and are summarized in Table 5. Indeed, our theoretical lat-
tice constants obtained with PP-PW method are in excellent agreement with those
obtained with FP-LAPW method within GGA-PBEsol calculations and the avail-
able experimental data and previous theoretical works are reported in Table  1.
Our results of elastic constants for these compounds should satisfy Born’s criteria
to prove its mechanical stability C44 > 0, C11 + 2C12 > 0 and C11 − C12 > 0 . Over-
all, a good agreement of elastic constants of TaXSn (X = Rh,Co and Ir) compound
is found with compared to [12, 15, 44]. In addition, the converse piezoelectric
coefficient d14 it is usually expressed in pC/N (unit charge/Newton), is related to
the elastic constant C44 and the direct piezoelectric coefficient ­e14, by the follow-
ing formula given below:
d14 = e14 ∕C44 . (15)
The calculations of static dielectric (relaxed ions) constant by mean of linear-
response calculations are defined as the second derivative of the total energy with
respect to the atomic displacement, from which we obtain the zero-stress static
dielectric constant 𝜀0 . Thus, these results determine the conventional figure of
merit for piezoelectric performance k14 using the following formula given below:
√
k14 = ||e14 ||∕ C44 𝜀fs 𝜀0 , (16)

where εfs = 8.85 E−12 is the permittivity of free space [45]. We present these pre-
dictions first for all compounds in the cubic MgAgAs-type structure, are included
in Table 5. We find that TaCoSn compound are of good the electromechanical cou-
pling coefficient k14 being in the order of 0.254 within GGA approach, and can be
candidate for piezoelectric applications. As a guide for experimental investigation of
piezoelectric half-Heusler compounds, we highlight a selection of candidate com-
pounds chosen according to the relevant practical considerations.

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 5  Page 18 of 19 International Journal of Thermophysics (2021) 42:5

4 Conclusion

In summary, the details of structural stability, electronic and thermoelectric proper-

ties of TaXSn (X = Co, Rh and Ir) half-Heusler with cubic MgAgAs-type structure
are being reported using calculations within density-functional theory combined
with semi-classical Boltzmann theory. We found that our compounds exhibit semi-
conductor behavior with indirect bandgap and provides very good figure of merit
(ZT) and can be used as candidates for electricity production. Furthermore, our den-
sity-functional perturbation theory calculations reveal that the TaCoSn half-Heusler
compounds materials have values of piezoelectric stress constant more than (0.16
C·m−2), the experimentally measured value of gallium arsenide (GaAs). A promis-
ing direction for further theoretical studies can be useful for experimental investi-
gations on thermoelectric and piezoelectric energy-harvesting technology of these
half-Heusler compounds.

Compliance with Ethical Standards 

Conflict of interest  The authors declare that there are no conflicts of interest regarding the publication of
this paper.

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Affiliations

Z. A. A. R. Almaghbash1 · O. Arbouche2,6   · A. Dahani3,6 · A. Cherifi1,6 ·

M. Belabbas1 · A. Zenati2 · H. Mebarki4 · A. Hussain5
1
Technology Laboratory of Communication, University of Saïda - Dr. Moulay Tahar,
20000 Saïda, Algeria
2
Laboratory Physico‑Chemistry of Advanced Materials, Djillali Liabes University of Sidi
Bel-Abbes, 22000 Sidi Bel Abbès, Algeria
3
Laboratoire de Physique Computationnelle des Matériaux, Djillali Liabès University of Sidi
Bel-Abbès, 22000 Sidi Bel Abbès, Algeria
4
Department of Materials Sciences, Laghouat University, PO Box 37, 03000 Laghouat, Algeria
5
Department of Physics, Government College University Faisalabad (GCUF), Allama Iqbal
Road, Faisalabad 38000, Pakistan
6
Department of Electronics, Faculty of Technology, Dr. Tahar Moulay University of Saïda,
20000 Saïda, Algeria

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