Solid State Sciences 40 (2015) 92e100

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Solid State Sciences

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Systematic study on the anisotropic elastic properties of tetragonal

XYSb (X ¼ Ti, Zr, Hf; Y ¼ Si, Ge) compounds
U.F. Ozyar a, E. Deligoz a, *, K. Colakoglu b
a
Aksaray University, Department of Physics, 68100 Aksaray, Turkey
b
Gazi University, Department of Physics, Teknikokullar, 06500 Ankara, Turkey

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

Article history: The anisotropic elastic properties of XYSb (X ¼ Ti, Zr, Hf; Y ¼ Si, Ge) compounds have been investigated
Received 30 May 2014 by using first-principles calculations based on density functional theory. The calculated lattice param-
Received in revised form eters are in excellent agreement with the available experimental data. The computed elastic constants
29 December 2014
indicate that all compounds are mechanically stable according to the elastic stability criteria under
Accepted 1 January 2015
Available online 2 January 2015
pressure. We have calculated the bulk modulus, shear modulus, Young's modulus, Poisson's ratio, Debye
temperature, and anisotropy value from the obtained elastic constants according to the VoigteReuss
eHill approximation. Additionally, the ductility and brittleness are characterized with the estimation
Keywords:
Anisotropic elastic properties
from Pugh's rule (B/G) and Poisson's ratio. Furthermore, the elastic anisotropy have been visualized in
Ab initio calculations detail by plotting the directional dependence of compressibility, Young's and shear moduli.
© 2015 Elsevier Masson SAS. All rights reserved.

1. Introduction reactions. Dashjav and Kleinke [10] have studied the crystal and
electronic structures of TiGeSb and HfGeSb. Recently, TiGeSb
Ternary antimonides have attracted much attention for their compound has been synthesized by Lam and Mar [11]. They [9e11]
excellent chemical and physical properties. They are among the have reported that this compound crystallizes in the tetragonal
parent compounds in crystal chemistry, and their great variety of ZrSiS-type structure (space group P4/nmm, Z ¼ 2).
some physical properties originating from the variable composi- According to our knowledge, no systematic researches have
tions makes them interesting materials in metallurgy and solid been reported on anisotropic elastic properties of XYSb (X ¼ Ti, Zr,
state science [1]. These compounds are useful materials for opto- Hf; Y ¼ Si, Ge) compounds until now. Therefore, we have presented
electronic and microelectronic technology [2]. They are also being a detailed investigation of the structural and anisotropic elastic
considered as potential materials for modern thermoelectric de- properties of these compounds. The bulk modulus, elastic con-
vices [3e8]. Therefore, there is an increasing interest for the stants, Young's modulus, shear modulus, Poisson's ratio, anisotropy
investigation of new compositions and crystal structures of the factor, sound velocities, Debye temperature of XYSb compounds
ternary antimonides. have been estimated and discussed in detail for the first time.
XYSb (X ¼ Ti, Zr, Hf; Y ¼ Si, Ge) compounds are members of the
family of ternary antimonides. ZrGeSb and ZrSi0.7Sb1.3 have been
2. Computational method
synthesized by Lam and Mar [9] through reaction of the elements at
950  C and its structure has been determined by single-crystal X-
The first-principles calculations were performed using the VASP
ray diffraction methods. ZrSi0.7Sb1.3 can be formed by direct reac-
code [12,13]. The electroneion interaction and the exchange cor-
tion of the elements at most compositions except those that are Si-
relation energy were described under the Projector-augmented
rich, in which case formation of the binary ZrSi2 predominates [9].
wave (PAW) [14] method and the generalized gradient approxi-
They have also reported that ZrGeSb system, the thermodynami-
mation (GGA) of PerdeweBurkeeErnzerhof (PBE) [15] scheme,
cally more stable phase, ZrGe2, was the major product in all Ge-rich
respectively. The energy cut off for the plane wave basis set was
fixed to 500 eV for all calculations. Brillouin-zone sampling has
been done in the Monkhorst-Pack [16] scheme with 8  8  4 k-
* Corresponding author. point grid. The calculations are converged to 107 eV/cell and the
E-mail address: [email protected] (E. Deligoz). structures are relaxed until the largest force becomes less than

http://dx.doi.org/10.1016/j.solidstatesciences.2015.01.001
1293-2558/© 2015 Elsevier Masson SAS. All rights reserved.
 U.F. Ozyar et al. / Solid State Sciences40 (2015) 92e100 93

103 eV/Å. Table 2

The calculated atomic positions for XYSb compounds.

3. Results and discussion Atom Wyckoff position x y z

Ti 2c 0.25 0.25 0.2404

3.1. Structural properties Si 2a 0.75 0.25 0.00
Sb 2c 0.25 0.25 0.6175
We have assumed that XGeSb (X ¼ Ti, Zr, Hf) compounds crys- Ti 2c 0.25 0.25 0.2476
tallize in the ZrSiS-type structure. The unit cell of the tetragonal Ge 2a 0.75 0.25 0.00
structure of XGeSb contains six atoms occupying three two-fold Sb 2c 0.25 0.25 0.6173
positions: X on 2c (1/4, 1/4, z1), Ge on 2a (3/4,1/4, 0), and Sb on Zr 2c 0.25 0.25 0.2433
2c (1/4, 1/4, z2). XSiSb (X ¼ Ti, Zr, Hf) are hypothetical compounds, Si 2a 0.75 0.25 0.00
and we have considered that these compounds have the same Sb 2c 0.25 0.25 0.6094
structure with XGeSb (X ¼ Ti, Zr, Hf) compounds. Zr 2c 0.25 0.25 0.2404
The total energies versus changed volumes are fitted to the Ge 2a 0.75 0.25 0.00
Murnaghan's equation of state [17] in order to determine the Sb 2c 0.25 0.25 0.6121

equilibrium lattice parameter, bulk modulus, and its pressure de- Hf 2c 0.25 0.25 0.2420
rivative for each material. Our results are presented in Table 1. It is Si 2a 0.75 0.25 0.00
Sb 2c 0.25 0.25 0.6112
seen that the present lattice parameters of XGeSb (X ¼ Ti, Zr, Hf)
compounds are in excellent agreement with the experimental Hf 2c 0.25 0.25 0.2420
values [9e11]. Unfortunately, there are no theoretical or experi- Ge 2a 0.75 0.25 0.00
Sb 2c 0.25 0.25 0.6138
mental results for XSiSb (X ¼ Ti, Zr, Hf) compounds for comparing
with the present work. According to Table 1, HfSiSb has the largest
bulk modulus (114.07 GPa) while the ZrGeSb has the smallest Table 3
The calculated elastic constants (Cij in GPa).
(97.60 GPa) one. The calculated atomic positions are given in
Table 2. The obtained atomic positions are in excellent agreement Material C11 C12 C13 C33 C44 C66 C11/C33
with the experimental values [9e11]. TiSiSb 210.63 72.82 57.72 213.5 101.23 119.99 0.986
TiGeSb 181.98 73.19 48.91 200.62 79.55 98.24 0.907
3.2. Mechanical properties ZrSiSb 189.79 60.38 63.58 209.55 91.43 111.61 0.905
ZrGeSb 163.36 67.99 53.14 193.69 73.03 93.56 0.843
HfSiSb 187.72 75.96 67.81 217.47 94.22 103.71 0.863
Knowledge of the elastic constants of solids is essential to un- HfGeSb 166.69 80.18 58.24 209.03 73.39 95.75 0.797
derstand many of their fundamental physical properties and gives
important information concerning the nature of the forces oper-
ating in solids. They provide information on the mechanical sta- elasticity in shape. According to the Table 3, the value of C33 is
bility, stiffness, strength, hardness and ductile or brittleness higher than C11 for all compounds; this means that XYSb com-
behavior of materials [18]. The elastic constants are obtained using pounds should be more easily compressible along the x-axis than
strainestress relationship [19]. Technically, IBRION ¼ 6, ISIF ¼ 3, along the z-axes [21]. This can explain that lattice constant (c) is
and PSTRESS are used for calculation of elastic constants, as less sensitive to pressure or temperature than other lattice constant
implemented in VASP (5.2) version. PSTRESS allows the user to (a). In the present case, TiSiSb has the largest C11, C33, C44, and C66. In
converge to a specified external pressure. Our results are tabulated addition, C44 is lower than C66 implies that the [1 0 0](0 0 1) shear is
in Table 3. For the mechanically stable tetragonal crystal, the elastic easier than the [1 0 0](0 1 0) shear for all compounds [22].
constants satisfy the following conditions [20]. The calculated elastic constants as a function of pressure are also
shown in Fig. 1. It is found that these compounds in considered
C11 > 0; C33 > 0; C44 > 0; C66 > 0; ðC11  C12 Þ > 0; structure satisfy the mechanical stability criteria within 60 GPa. It
ðC11 þ C33  2C13 Þ > 0; ð2C11 þ C33 þ 2C12 þ 4C13 Þ > 0: can be seen from Fig. 1 that C12, C13, C44, and C66 are less sensitive
for pressure increment as compared to C11 and C33.
As shown in Table 3, the calculated elastic constants for XYSb
The polycrystalline bulk modulus (B) and shear modulus (G) are
compounds satisfy the mechanical stability criteria. It indicates that
calculated from the Voigt-Reuss-Hill (VRH) approximations
all compounds of considered structure are mechanically stable. As
[23e25]. The Voigt (V) approximation [24] assumes uniform strain
it is well known, the elastic constants C11 and C33 indicate the re-
in the structure and gives the upper limit for the parameters that
sistances to linear compression in x and z directions, respectively,
are expressed in terms of the elastic coefficients Cij. In the Reuss (R)
while the elastic constants C12, C13, C44, and C66 are related to the
approximation [25], a uniform stress distribution is assumed, giv-
ing the lower limit through the elastic compliance tensor Sij. It is
Table 1
Calculated equilibrium lattice parameters (a and c in Å), bulk moduli (B in GPa), and known that Reuss and Voigt estimates of bulk and shear moduli are
the pressure derivative of bulk modulus (B0 ) along with the available experimental close to lower and upper bounds of true polycrystalline bulk and
data. shear moduli. The average of these two limits, known as the Hill
Material a c B B0 Refs. approximation [23], provides a realistic representation of poly-
crystalline bulk properties. In Voigt approximation, the bulk (BV)
TiSiSb 3.634 8.203 112.23 4.488 Present
TiGeSb 3.727 8.249 99.82 4.586 Present and shear moduli (GV) were estimated as:
3.706 8.209 (Exp.) Ref. [13].
3.702 8.214 (Exp.) Ref. [14]. BV ¼ ð2ðC11 þ C12 Þ þ C33 þ 4C13 Þ=9 (1)
ZrSiSb 3.756 8.692 106.71 4.39 Present
ZrGeSb 3.841 8.715 97.60 4.447 Present
3.845 8.634 (Exp.) Ref. [12]. GV ¼ ðM þ 3C11  3C12 þ 12C44 þ 6C66 Þ=30 (2)
HfSiSb 3.740 8.603 114.07 4.389 Present
HfGeSb 3.825 8.616 104.08 4.488 Present and in Reuss approximation, the bulk (BR) and shear moduli (GR)
3.810 8.550 (Exp.) Ref. [13].
were estimated as:
94 U.F. Ozyar et al. / Solid State Sciences40 (2015) 92e100

Fig. 1. Pressure dependence of elastic constants of XYSb compounds.

Table 4
The calculated isotropic bulk modulus (B in GPa), shear modulus (G in GPa), Young's modulus (E in GPa), Poisson's ratio (v), hardness (Hv in GPa), density (r in g/cm3) Debye
temperature (QD in K), and longitudinal, transverse, average sound velocities (vl, vt and vm, in m/s).

Material B G E n B/G Hv r QD vl vt vm

TiSiSb 112.3 92.5 217.7 0.18 1.21 19.9 6.06 488 6233 3905 4300
TiGeSb 100.7 76.3 182.8 0.20 1.32 15.4 7.03 405 5368 3296 3637
ZrSiSb 107.0 84.0 199.7 0.19 1.27 17.4 6.53 430 5790 3585 3953
ZrGeSb 96.5 69.4 167.9 0.21 1.39 13.4 7.38 363 5060 3065 3388
HfSiSb 112.8 81.7 197.4 0.21 1.38 15.2 9.07 363 4946 3002 3317
HfGeSb 103.6 69.0 169.5 0.23 1.5 12.6 9.83 316 4461 2650 2934

.
BR ¼ C2 M (3) n ¼ ð3B  2GÞ=2ð3B þ GÞ (8)
Our results for mechanical properties have been summarized in
. .  Table 4. The calculated bulk moduli from the elastic constants are
GR ¼ 15 ð18BV Þ C2 þ 6=ðC11  C12 Þ þ 6=C44 þ 3=C66 (4)
very close to those obtained from Murnaghan's equation of state.
This similarity may serve as an estimate of the reliability and ac-
where M ¼ C11 þ C12þ2C33e4C13 and C2 ¼ ðC11 þ C12 ÞC33  2C213 the curacy of this theoretical estimation of the elastic constants. Ac-
VoigteReusseHill (VRH) approximation [23e25] was used to esti- cording to Table 4, the calculated values of bulk moduli for XGeSb
mate the effective bulk and shear moduli by arithmetic mean of the are less than XSiSb compounds, indicating that they are not as
above Voigt and Reuss limits: incompressible as XSiSb.

BH ¼ ðBV þ BR Þ=2 (5) Table 5

The calculated shear anisotropic factors (A1, A2 and A3), percent anisotropy in the
compression and shear (AB and AG), and universal anisotropic index (AU).
GH ¼ ðGV þ GR Þ=2 (6)
Material A1 A2 A3 AB (%) AG (%) AU
The Young's modulus (E) and Poisson's ratio (n) were calculated TiSiSb 1.31 1.16 1.74 0.03 1.92 0.196
as follows: TiGeSb 1.12 1.00 1.80 0.008 1.80 0.185
ZrSiSb 1.35 1.15 1.72 0.13 2.03 0.210
E ¼ 9BG=ð3B þ GÞ (7) ZrGeSb 1.17 0.98 1.96 0.07 2.37 0.244
HfSiSb 1.4 1.24 1.86 0.10 2.62 0.271
HfGeSb 1.16 1.02 2.13 0.076 3.34 0.348
and
 U.F. Ozyar et al. / Solid State Sciences40 (2015) 92e100 95

Fig. 2. Pressure dependence of anisotropic factors and universal anisotropy index of XYSb compounds.

possesses relatively highest Young's and shear moduli among these

Table 6 compounds, implying its high hardness and strong bonding.
The calculated anisotropic longitudinal and transverse sound velocities (vl and vt; in
m/s).
Poisson's ratio can formally take values between 1 (B << G)
and ½ (B >> G), which corresponds respectively to the lower limit
Material [100] [010] [001] [010] [001] [100] [110] [11 0] yt2
where the material does not change its shape, and to the upper
yl yl yt1 yt2 yl yt1 yl
limit when the volume remains unchanged [28]. For central force
TiSiSb 5893 5893 4086 4448 5933 4448 6569 3371 solids Poisson's ratio is bounded by the lower limit of 0.25 and the
TiGeSb 5090 5090 3365 3739 5344 3739 5670 2783
upper limit of 0.5 [29]. The value of the Poisson's ratio is small
ZrSiSb 5391 5391 3741 4134 5664 4134 6020 3148
ZrGeSb 4705 4705 3146 3561 5123 3561 5325 2542 (n ¼ 0.1) for covalent materials, whereas for ionic materials a typical
HfSiSb 4551 4551 3224 3382 4898 3382 5097 2483 value of n is 0.25 [30]. The calculated value of about 0.20, suggests
HfGeSb 4118 4118 2733 3121 4578 3121 4722 2098 that interatomic forces in XYSb are not central in nature and ionic
contributions in inter atomic bonding are dominant. The value of
It is known that the large value of shear modulus indicates Poisson's ratio of HfGeSb (0.23 GPa) is the largest, suggesting that
pronounced directional bonding between atoms [26]. We have when it is compressed, it shows larger lateral expansion [31]. In
found that the shear modulus of TiSiSb (92.5 GPa) is the largest, and addition, the stability against shear is also measured by the Pois-
the same value of HfGeSb (69.0 GPa) is the lowest. Hence, direc- son's ratio. We note that the small value of Poisson's ratio indicates
tional bonding of TiSiSb between atoms is quite notable. If the value that TiSiSb is relatively stable against shear. The values of Poisson's
of E increases, the covalent nature of the material also increases ratio are also indicating that a considerable volume change is
[27]. The order of the calculated E for these compounds is: associated with elastic deformation for XYSb compounds.
TiSiSb > ZrSiSb > HfSiSb > TiGeSb > TiGeSb > HfGeSb > ZrGeSb. According to Pugh rule [32], ductility and brittleness are asso-
Therefore, it can be expected that covalent bonding component of ciated with high and low B/G values, respectively. The critical value
TiSiSb is more dominant than that of other compounds. of 1.75 separates ductile and brittle behavior. In our case, the values
The Young's modulus is a measure of the stiffness of an elastic of the B/G are smaller than 1.75, which indicates their brittle nature.
material. When the value of Young's modulus is large, the material Relatively the higher value of G/B for TiSiSb indicates that the
is stiff. In this context, TiSiSb is the stiffest due to the largest Young directionality of the bonding in TiSiSb is stronger than that of the
modulus (217.7 GPa), while ZrGeSb has the smallest stiffness due to other compounds [33]. In fact, the value of B/G ratio reflects the
the lowest Young modulus (167.9 GPa). It can be noted that TiSiSb hardness of a solid indirectly. The general trend is the lower the B/G
96 U.F. Ozyar et al. / Solid State Sciences40 (2015) 92e100

Fig. 3. 3D directional dependence of the compressibility of XYSb compounds.

ratio, the higher hardness [34]. From the calculated B/G ratios, we calculated hardness for all compounds are higher than 10 GPa,
conclude that the hardness of TiSiSb is higher than that of other hence, XYSb compounds can be classified as hard materials. TiSiSb
compounds. has the largest hardness (19.9 GPa) and the HfGeSb has the smallest
Recently, Chen et al. [35] have proposed an empirical model for (12.6 GPa) one. The hardness and shear modulus have relatively the
Vickers hardness (HV) based on a large sample of measured values same variation tendency. We can conclude that shear modulus is
from the literature as follows: more closely related to the hardness than the bulk modulus.
The Debye temperature (qD) is known as an important funda-
 0:585 mental parameter closely related to many physical properties such
Hn ¼ 2 k2 G 3 (9) as specific heat and melting temperature [39]. At low temperature
the vibrational excitations arise solely from acoustic vibrations.
where k and G are Pugh's modulus ratio (k ¼ G/B) and shear Hence, at low temperature, the Debye temperature can be esti-
modulus, respectively. The bulk and shear moduli are still the most mated from the average sound velocity (vm) by the following
important parameters for identifying the hardness. The high equation [40].
hardness requires that the bulk modulus and shear modulus must
  
be as large as possible [36,37]. Generally speaking, the shear h 3n NA r 1=3
qD ¼ vm (10)
modulus is a significantly better qualitative predictor of hardness k 4p M
than the bulk modulus [38]. The calculated values of micro-
hardness for XYSb are given in Table 4. It can be seen that the where h is Planck's constant, k is Boltzmann's constant, NA is
 U.F. Ozyar et al. / Solid State Sciences40 (2015) 92e100 97

Fig. 4. 3D directional dependence of the Young's modulus of XYSb compounds.

Avogadro's number, n is the number of atoms per formula unit, M is average sound velocities and density are also tabulated in Table 4. In
the molecular mass per formula unit, r(¼M/V) is the density, and vm our present case, among the compounds, TiSiSb has the highest
is given [41] as Debye Temperature (488 K). This value for TiSiSb implies, relatively,
a better thermal conductivity and strength of chemical bonding in
" !#1=3 the crystal structure. Furthermore, strength chemical bonding leads
1 2 1
nm ¼ þ (11) to higher melting temperature and higher hardness. HfGeSb has the
3 n3t n3[
lowest Debye Temperature (316 K) and higher B/G ratio that in-
dicates metallic bonding for HfGeSb is weaker than others [38]. As
where vl and vt, are the longitudinal and transverse elastic wave expected, hardness and Debye temperature exhibit similar trend
velocity, respectively, which are obtained from Navier's equation for these compounds. From Table 4, it can be also seen that the
[42]. longitudinal sound velocities of all compounds are much faster
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi than transverse sound velocities.
3B þ 4G
n[ ¼ ; (12)
3r 3.3. Elastic anisotropy

and Another interesting physical parameter related to the elastic

sffiffiffiffi properties of solids is the elastic anisotropy. The elastic anisotropy
G reflects different bonding natures in different crystallographic di-
nt ¼ (13) rections and has important implications because it is correlated
r
with the possibility of inducing micro cracks in materials [21]. A
The obtained Debye temperature, the longitudinal, transverse, proper description of an anisotropic behavior has an important
98 U.F. Ozyar et al. / Solid State Sciences40 (2015) 92e100

Fig. 5. 3D directional dependence of the of the shear modulus of XYSb compounds.

implication in engineering science as well as in solid state science.

The shear anisotropic factors are computed via the following
expression [22]:and

. 
A1 ¼ C44 ðC11 þ 2C13 þ C33 Þ C11 C33  C213 for the ð010Þ or ð100Þ plane; (14)

.   
A2 ¼ C44 ðCL þ 2C13 þ C33 Þ CL C33  C213 for the 110 plane; (15)
 U.F. Ozyar et al. / Solid State Sciences40 (2015) 92e100 99

directional dependence of the compressibility, Young's moduli, and

A3 ¼ 2C66 =ðC11  C12 Þ for the ð001Þ plane (16) shear moduli of XYSb compounds are obtained using EAIM code
[47]. This code is an analytical tool for calculation and visualisation
where CL ¼ C66þ(C11 þ C12)/2. of anisotropic elastic properties. Three-dimensional (3D) mathe-
The obtained anisotropic factors are listed in Table 5. For an matical expression of the directional dependence of the
isotropic crystal, the values of A1, A2 and A3 equal to 1, while any compressibility, Young's moduli, and shear moduli have been
value smaller or greater than 1 is a measure of the degree of shear calculated in terms of the computed data by using the relation
anisotropy possessed by the crystal [43]. In our present case, all given in Ref. [47]. The results are shown in Figs. 3e5.
compounds exhibit small anisotropy for the ð11 0Þ plane, while the In a 3D representation, an isotropic system exhibits a spherical
anisotropy is very obvious for the (010), (100) and (001) planes. Its shape, and the deviation from a spherical shape indicates the de-
highest value (2.13) is belong to HfGeSb for the (001) plane. We gree of anisotropy [21]. As shown in Figs. 3 and 4, all the XYSb
have also calculated the percent elastic anisotropy in shear (AG) and compounds exhibit relatively the elastic anisotropy since the shape
compression (AB) by the following common relation given in of the compressibility and Young's modulus representation de-
Ref. [43]. viates from a spherical shape, especially for HfGeSb. It can be noted
that significant anisotropy exists in x and y planes in Figs. 3 and 4.
AB ¼ ðBV  BR Þ=ðBV þ BR Þ (17)
The anisotropic property of compressibility of these compounds is
less prominent than Young's modulus.
AG ¼ ðGV  GR Þ=ðGV þ GR Þ (18) Their elastic anisotropic nature can be explained by the ratios of
C11/C33 [48]. It is known that if C11/C33 is higher (lower) than 1.0, the
where, the subscripts V and R represent the Voigt and Reuss ap-
z (x) axis is more compressible than the x (z) axis. A larger deviation
proximations, respectively. These values can range from zero,
of C11/C33 ratio from 1.0 means the larger difference in linear
which represents perfect isotropy, to 100%, which represents the
compression along the x and z axes [48]. From Table 3, it can be
largest anisotropy. The percentages of bulk and shear anisotropies
seen that C11/C33 ratios for all compounds lower than 1.0, and the
for XYSb compounds are tabulated in Table 5. The calculated AG for
order of deviation of C11/C33 is
all compounds is higher than AB, meaning that shear anisotropy is
HfGeSb < ZrGeSb < HfSiSb < ZrSiSb < TiGeSb < TiSiSb. Therefore,
larger than compressibility anisotropy. It is obvious that HfGeSb
HfGeSb has the highest elastic anisotropy.
exhibits relatively high shear, while ZrSiSb exhibits relatively high
We have also plotted shear modulus in different planes for XYSb
compressibility among these compounds.
in Fig. 5. One can see that the shear modulus exhibits less anisot-
Another index that allows us to estimate the anisotropy is the
ropy in the z plane (blue (in web version) maximum, green (in web
so-called universal anisotropy index AU [44]. Universal index is
version) minimum) while the x and y planes exhibit relatively
equal to zero for isotropic materials. The deviation of AU from zero
elastic anisotropy. In addition, it is worth noting that the calculated
defines the extent of elastic anisotropy. AU is defined as follow:
anisotropic indexes or factors are in agreement with these graphs.

AU ¼ 5GV =GR þ BV =BR  6 (19)

4. Summary and conclusions
The obtained results are tabulated in Table 5. TiGeSb has the
smallest AU value (0.196), while HfGeSb has the highest AU value We have carried out the first-principles calculations of the
(0.348). The larger deviation of AU from zero may be due to larger anisotropic elastic properties of tetragonal XYSb compounds. The
GV/GR. The calculated anisotropic factors and universal anisotropy elastic constants are determined from the stressestrain relation-
index of all compounds as a function of pressure are shown in Fig. 2. ship. The calculated results have shown that these compounds are
It can be seen that the anisotropy characteristic is becoming more mechanically stable in considered structure. The polycrystalline
significant with the increasing of applied pressure. It is noted that elastic parameters have been further calculated within the scheme
anisotropic factors and universal anisotropy index for ZrSiSb are of VoigteReusseHill (VRH) approximation. XYSb compounds
more sensitive to pressure as compared other compounds. possess brittle in nature with respect to the B/G criterion. Moreover,
In the principal directions the longitudinal, transverse, average the calculated hardness has suggested that these compounds are
sound velocities for tetragonal structure are estimated using elastic potential hard materials, and TiSiSb has the largest hardness among
constants as follows [45,46]. the studied ternary antimonides. These compounds are a good

h i h i h i h i
100 n[ ¼ 010 n[ ¼ ðC11 =rÞ1=2 ; 001 nt1 ¼ ðC44 =rÞ1=2 ; 001 y[ ¼ ðC33 =rÞ1=2 ;
h i h i h i
100 yt1 ¼ 010 yt2 ¼ ðC66 =rÞ1=2 ; 110 y[ ¼ ððC11 þ C12 þ 2C66 Þ=2rÞ1=2 ; (20)
h i
110 yt2 ¼ ððC11  C12 Þ=2rÞ1=2

candidate for searching new hard materials. HfGeSb exhibits rela-

tively low thermal conductivity due to having the lowest Debye
The results are listed in Table 6. The anisotropic properties of Temperature, and it may be suitable to be used as good thermo-
sound velocities indicate relatively the elastic anisotropy for these electric material. The directional dependent sound velocities,
compounds. compressibility, Young’s and shear modulus are also computed and
Three-dimensional (3D) illustration of the elastic moduli is an discussed in detail. It can be concluded that the anisotropy of
effective method of visualizing the details of the elastic anisotropy HfGeSb is higher than the other compounds. We hope that our
of a material along its crystallographic directions [21]. The study will contribute to the ongoing research on new materials for
100 U.F. Ozyar et al. / Solid State Sciences40 (2015) 92e100

energy applications. [21] N. Guechi, A. Bouhemadou, R. Khenata, S. Bin-Omran, M. Chegaar, Y. Al-Douri,

A. Bourzami, Solid State Sci. 29 (2014) 12.
[22] M. Zeng, R. Wang, B. Tang, L. Peng, W. Ding, Model. Simul. Mater. Sci. 20
Acknowledgments (2012) 035018.
[23] R. Hill, Proc. Phys. Soc. 65 (1952) 349.
This work is supported by Aksaray University Research- Project [24] W. Voigt, Lehrbuch der Kristallpysik Taubner, 1928, p. 29. Leipzig.
[25] A. Reuss, Z. Angew, Math. Mech. 9 (1929) 49.
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