Chemical Physics 525 (2019) 110399

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Chemical Physics
journal homepage: www.elsevier.com/locate/chemphys

High-temperature and high-pressure thermophysical properties of AlP T

semiconducting material: A systematic ab initio study
Salah Daouda, Nadir Bouarissab, , Nadhira Bioudc,d, Pawan Kumar Sainie
⁎

a
Laboratoire Matériaux et Systèmes Electroniques, Université Mohamed Elbachir El Ibrahimi de Bordj Bou Arreridj, Bordj Bou Arreridj 34000, Algeria
b
Laboratory of Materials Physics and its Applications, University of M'sila, 28000 M'sila, Algeria
c
Laboratoire d'Optoélectronique et Composants, Université Ferhat Abbas Sétif 1, Sétif 19000, Algeria
d
Faculté des sciences et de la technologie, Université Mohamed Elbachir El Ibrahimi de Bordj Bou Arreridj, Bordj Bou Arreridj 34000, Algeria
e
Department of Physics, Government College, Hansi, Haryana 125033, India

ARTICLE INFO ABSTRACT

Keywords: The finite temperature thermophysical quantities are one of the most important properties of solids and have
Quasi-harmonic Debye model become the subject of significant interdisciplinary interest in recent years. We report a detailed theoretical
Thermophysical properties investigation on the equation of state (EoS) parameters, electronic polarizability and finite temperature ther-
Electronic polarizability mophysical properties of aluminum phosphide using plane-wave pseudopotential approach in the framework of
Aluminum phosphide
the density functional theory within the generalized gradient approximation. Our results regarding EoS para-
High-pressure
meters and electronic polarizability are found to be in good accord with previous data reported in the literature.
Moreover, using the model of the quasi-harmonic Debye approximation plus empirical energy corrections, the
thermophysical properties for temperatures up to 2000 K are examined and discussed. Our findings show that the
thermophysical properties vary monotonically with either temperature or pressure which is consistent with the
trends previously reported in the literature.

1. Introduction
The thermodynamic properties of materials may play an important
role in physics of solid state matter, because of their direct relation with
other physical properties [1]. The good knowledge of these properties
allows the extension of our understanding of their specific behavior
when undergoing severe constraints of high pressure and high tem-
perature [2–4]. In consequence, the accurate knowledge of these
properties at severe constraints is very important for technological
applications of the materials under extreme conditions of pressure and
temperature [1].
Most conventional III-V compounds are wide optical gap semi-
conductors; they are solids with an electrical conductivity between that
of metals and insulators. These compounds are the subject of recent
theoretical and experimental studies due to their important physical
properties such as good mechanical properties, high corrosion re-
sistance and high thermal conductivity [5]. Shinde et al. [6] studied the
pressure induced phonon stiffening and softening in III-V phosphide
using the rigid ion and deformation bond approximation models. Phy-
sical properties of AlN and AlSb semiconductor compounds under hy-
drostatic compression have also been reported recently by Saib et al.
[7] and Algarni et al. [8]. At ambient conditions, most of III-V semi-
conductors (including AlP compound) crystallize in the zinc-blende
structure; other phases such as the wurtzite (B4) structure is not pos-
sible in the bulk form of some III-V semiconductors (such as AlP, BP,…
etc) but can exist in other morphological structures such as nano-
particles and nanowires [9]. The material of interest has several ap-
plications, especially in the industry of the infrared photo-detectors and
light emitting diodes [5].
In order to find other applications at high pressures for AlP semi-
conducting material, several works on different physical properties of
AlP were performed. As a matter of fact, the effects of pressure and
temperature provide new fundamental properties for the semi-
conducting materials under load [10–12]. Arbouche et al. [13] found
that AlP transforms from the cubic ZnS-type (B3) to NaCl-type (B1)
structure at a pressure of around 11.87 GPa, and from the B1 to CsCl-
type (B2) structure at a pressure of around 33.76 GPa. Agaya and Soma
[14] have studied the dynamical elastic constants and the phonon
dispersion curves of AlP material and some other III-V compounds and
found that the elastic constants of AlP are slightly higher than those of
AlAs and AlSb materials. The same authors have reported the thermal
properties of some III-V and II-VI tetrahedral semiconducting

⁎
Corresponding author.
E-mail address: n_bouarissa@yahoo.fr (N. Bouarissa).

https://doi.org/10.1016/j.chemphys.2019.110399
Received 23 February 2019; Received in revised form 2 May 2019; Accepted 6 June 2019
Available online 06 June 2019
0301-0104/ © 2019 Elsevier B.V. All rights reserved.
S. Daoud, et al.
compounds using the lattice dynamical method [15]. Their results
showed a similar behavior of the heat capacity CV for AlX (X = P, As,
and Sb) compounds. The mechanical behavior, the piezoelectric coef-
ficients, and some other electronic properties of AlP under pressure
were also investigated by Daoud et al. [16] and Daoud [17]. Never-
theless, it seems that investigations concerning the thermodynamic
properties of AlP material are still scarce. Thus, in the present con-
tribution, we report first principles calculations of temperature and
pressure effects on the thermodynamic properties of AlP in B3 structure
using the plane wave-pseudopotential (PW-PP) method within the fra-
mework of the density functional theory (DFT) [18]. In addition, the
equation of state (EoS) parameters, microhardness, and electronic po-
larizability are also determined.
2. Computational details
The study of the physical properties of any material should begin
with the choice of the computational method, which can give a good
description of the different interactions in the material itself. The EoS
parameters calculated in the present study are carried out using the
ABINIT code [19] based on the PP-PW approach in the framework of
DFT. The pseudo-potentials of Troullier-Martins generated in the
FHI98PP code [20] are used to describe the interactions between the
valence electrons, nuclei and the core electrons. The exchange corre-
lation potential of the total energy is evaluated using the generalized
gradient approximation (GGA) in the scheme of Perdew-Burke-Ern-
zerhof (PBE) [21]. The total energy is converged near the energy cutoff
of 100 Ha, while the Brillouin zone is sampled by (8x8x8) Monkhorst
Pack mesh of k points [22]. The error of the total energy is less than
1 × 10−6 Ha. In the geometry optimization, the atoms are allowed to
fully relax when the force on each atom is less than 2.5 × 10−3 eV/Å.
In order to obtain the pressure and temperature dependence of the
thermophysical properties of AlP, the quasi-harmonic Debye model
approximation plus empirical energy corrections (EEC) are applied
through the GIBBS code as described in Refs. [23,24]. The thermal
model applied here is the Debye-Slater approach, where the Debye
temperature is calculated assuming that the material of interest is an
isotropic solid. In the quasi-harmonic Debye model approach, the vi-
brational Helmholtz free energy F is expressed as follows [23],
9 D D T
F D, T = nkT + 3 ln 1 e D D T
8 T (1)
where D(θD/T) is the Debye integral. The Debye temperature θD is given
by the following expression [23],
1
1
3 Bs
D = 6 2V 2n f( )
k M (2)
where = h 2 , h is the Planck constant, BS is the adiabatic bulk
modulus, M is the mass of the unit cell, and is the Poisson’s ratio. The
latter is taken to be 0.25, which corresponds to a Cauchy solid [23].
This can be justified by the fact that for AlP semiconducting compound,
the experimental elastic constants C12 and C44 are close to each other
(C12 = 61.2 GPa ≈C44 = 61.5 GPa [25]). The adiabatic bulk modulus
BS is expressed as follows,
BS = BT (1 + T) (3)
where, BT is the isothermal bulk modulus, α is the volumetric expansion
coefficient, and γ is the Grüneisen parameter. These parameters are
expressed by the following relations,
BT = V ( p V ) = V ( 2 F V 2 )T (4)
= (1 V )( V T)p (5)
= ln D (V ) lnV (6)
where p is the pressure, V is the volume, and T is the temperature.
2
Chemical Physics 525 (2019) 110399
Besides, the volumetric expansion coefficient α and the Grüneisen
parameter γ are related by: γ = αBTV/CV, where CV is the heat capacity
at constant volume, which is given by,
nk( D T)
CV = 12nkD D T T
(e D 1) (7)
The constant pressure heat capacity Cp is expressed as a function of
the enthalpy H as follows,
Cp = ( H T )P (8)
Similarly to the adiabatic bulk modulus BS and the isothermal bulk
modulus BT, the vibrational constant pressure heat capacity Cp and the
constant volume heat capacity CV are related by: Cp = CV (1 + α γ T).
The entropy S is related to the temperature T and the Debye tempera-
ture θD by the following expression,
S = nk [4D ( D T) 3 ln (1 e D T
)] (9)
where n is the number of atoms per primitive cell, and k is the
Boltzmann constant.
It is to be noted that in the Gibbs2 program reported in Refs.
[23,24], the quasiharmonic approximation is based on the harmonic
approximation and, as such, accurate only at temperatures of the order
or below the Debye constant. However, several thermophysical prop-
erties of semiconductor materials, e.g. MgO were calculated at tem-
peratures up to 2000 K, which are well above the Debye temperature
[23,24] without affecting much the quality of the results.
3. Results and discussion
3.1. EoS parameters
The formation of solids (bulk, thin films…, etc) is essentially de-
termined by the forces between the atoms, which are directly related to
the chemical composition and the structural parameters of the crystal
lattice. Within ab initio calculations, the structural properties are very
important for understanding the material properties from the micro-
scopic point of view. The EoS parameters can be predicted from ab initio
calculation using the electronic ground-state energy as a function of
volume (E-V) [26]. The equilibrium volume V0, the bulk modulus B0
and the pressure derivatives of the bulk modulus B0′ can be obtained
using the Murnaghan equation of state. Our predicted results regarding
the equilibrium lattice parameter a0, bulk modulus B0, and its pressure
derivative B0′ of AlP compound in B3 structure are summarized in
Table 1, and compared with other theoretical results. It is important to
note that the lattice parameter is one of the fundamental structural
quantities for a solid which is directly related to bond length; it is de-
termined by the density of valence electrons between the atoms of
crystal. Our obtained value of 5.5053 Å for a0 is overestimated with
respect to that of 5.43 Å calculated using PP-PW method within the LDA
approach [27], but seems to agree well with that of 5.51 Å obtained
from FP-LAPW + lo method within the GGA approach [13].
The rigidity of the material can be characterized by an elastic
modulus (bulk modulus or coefficient of incompressibility) [5]; this
quantity controls the change in volume under compression of an elastic
body with small deformation. The compressibility of a material is
Table 1
EoS parameters of AlP semiconducting material.
EOS parameter Present work Other Works
a0 (Å) 5.5053 5.51a, 5.43b
B0 (GPa) 79.50 83.23a, 90.46b
B0′ 4.03 4.02a, 3.72b
a
Ref. [13] FP-LAPW+lo method with GGA calculation.
b
Ref. [27] PP-PW method with LDA calculation.
S. Daoud, et al. Chemical Physics 525 (2019) 110399

directly related to the nature of the bonding of atoms in the solid, which investigations on the finite temperature thermophysical properties
is accomplished by the Coulomb forces between the atomic nuclei and under high pressure and at elevated temperatures in the literature is
the electrons of the material. A larger value of bulk modulus indicates a very clear. In this part of the present work, we focus our attention on
better capability of resistance to volume change in the solid [5]. As far the dependence of the thermodynamic properties of AlP compound on
as B0 and B0′ are concerned, our calculated values appear to be closer to pressure and temperature. Luo et al. [35] have mentioned that the
those reported by Arbouche et al. using the GGA approach [13] than empirical energy corrections (EECs) are able to improve considerably
those published by Aouadi et al. [27] within the LDA approach. This is the thermodynamic properties of materials at very high temperature.
an expected result since in the present work the exchange-correlation One of the methods used to correct the systematic errors in the static
potential has been calculated within the GGA approach. energy Esta (V) is called BPSCAL EEC [24]. This interesting feature of
In addition to the bulk modulus, the mechanical behavior of solids the empirical energy corrections was successfully applied for cubic
can also be characterized by means of the microhardness. It is well boron arsenide (BAs) semiconducting compound [26] and the wurtzite
known that the microhardness of a material change considerably as a (B4) phase beryllium oxide (BeO) material [35]. Using the BPSCAL
function of dislocation density. For some cubic III-V and II-VI com- correction, the static energy can be modified as follows [23,24]
pounds, Adachi [28] has proposed many formulas that are related to
the microhardness H and other mechanical moduli. He also proposed a Bexp Vexp V0
E sta (V ) = Esta (V0 ) + Esta V Esta (V0 )
simple relationship between the Knoop microhardness H and the bulk B0 V0 Vexp (12)
modulus B, which is expressed as follows,
where V0 and B0 are the calculated static equilibrium properties,
H = aB + b (10) whereas Vexp and Bexp are the experimental ones.
where both B and H are expressed in GPa. For III-V semiconductors In order to apply the BPSCAL correction to AlP compound, it is
group [28], the a and b values are 0.16 and −5.74 GPa, respectively. required to know the values of Vexp and Bexp of the material of interest.
Eq. (10) shows a linear proportionality between the Knoop micro- The experimental values of the volume Vexp and the bulk modulus Bexp
hardness H and the bulk modulus B in cubic III-V and II-VI semi- used here to correct the total energy are those quoted by Van Camp and
conductors. This indicates that the larger bulk modulus (smaller com- Van Doren [36], which are equal to ∼274.5 (a.u)3 and 86 GPa, re-
pressibility) materials having higher microhardness, and vice versa. spectively [36]. Fig. 1 presents the variation of the corrected and un-
Using the value of the bulk modulus B0 predicted in our present corrected total energies as a function of the unit cell volume of AlP
work, the Knoop microhardness H of AlP semiconductor is found to be compound in the B3 structure.
6.98 GPa. This value is in very good accord with that of 7.0 GPa re- The effect of pressure and temperature on the isothermal and iso-
ported by Yang et al. [5], but it deviates by less than 8% from that of baric lattice parameter a of AlP is presented in Fig. 2(a) and (b), re-
7.54 GPa reported by Liu et al. [29]. spectively. Note that the lattice parameter decreases with increasing
pressure at all temperatures of interest. The reduction of a under
pressure is due to the decrease of the bond-length. Inversely, its in-
3.2. Electronic polarizability
crease at elevated temperatures can be explained by the expansion of
the bond-length under the temperature effect. The best fit of the lattice
It is well known that the majority of the physical properties of
parameter a for AlP at various pressures obeys to the following quad-
materials change when an external electric field takes place. Under the
ratic expressions,
effect of external electric field, the nucleus and the electrons can be
displaced in opposite directions of the dielectric medium, creating a a = 5.45 + 4.29 × 10 5 T+ 2.84 × 10 8T2 (p=0 GPa) (13a)
dipole moment in the material. Some contributions [30–32] proposed
different models to calculate the electronic polarizability αp of several a = 5.41 + 4.49 × 10 5 T+ 1.84 × 10 8T2 (p=2 GPa) (13b)
materials. Reddy et al. [30] proposed a simple expression between the
a = 5.34 + 4.06 × 10 5 T+ 0.11 × 10 8T2 (p=6 GPa) (13c)
electronic polarizability αp and the bulk modulus B of several com-
pounds as follows, a = 5.28 + 3.54 × 10 5 T+ 0.87 × 10 8T 2 (p=10 GPa) (13d)
p = 0.395 × 10 24 [(X 1) (X+ 2)] (M ) (11) where T is expressed in K, and a in Å.
3 The mechanical parameters can provide information about the
where ρ denotes the density which is expressed in g/cm , M denotes the
characteristics of the bonding forces in the crystal [37,38]. The electron
molecular weight that is expressed in g/mol, and the quantity X is re-
lated to the bulk modulus B as X = (5.563–0.033B)2, B here is expressed -234.5
in GPa [28].
Using the values of the lattice constant (a = 5.5053 Å) and the bulk bpscalPBE
-235.0 Uncorrected PBE
modulus (B = 79.5 GPa) obtained in this work, the electronic polariz-
ability αp of AlP material is estimated to be around 7.12 Å3. This value
is somewhat larger than the previously published values of 6.21 Å3 and -235.5
Energy (eV)

6.88 Å3 reported by Reddy et al. [31] using the energy gap directly and
Kumar et al. [32] using the plasma oscillations theory of solids, re-
-236.0
spectively. Nevertheless, it is in very good accord with the value of
7.08 Å3 reported in the Ref. [33], which was evaluated from optical
electronegativities, where the two values deviate by less than 1%. -236.5

3.3. Thermodynamic properties -237.0

The energy of ions due to their vibration at non-zero temperature -237.5

affects the mechanical and thermophysical properties of solids [25]. 25 30 35 40 45 50 55
3
Therefore, the investigation of the thermophysical properties of solids Volume (Å )
such as the heat capacity, thermal expansion coefficient and entropy is
necessary for many applications [25,34]. Although there are many Fig. 1. Corrected and uncorrected total energies versus volume of AlP com-
studies on AlP material, scarcity of theoretical and experimental pound.

3
S. Daoud, et al. Chemical Physics 525 (2019) 110399

5.64 126
T= 0 K
(a) T= 300 K (a)
5.58 T= 1200 K 112
Lattice parameter (Å)

T= 2000 K
5.52 98

BT (GPa)
5.46 84

5.40 70
T= 0 K
5.34 56 T= 300 K
T= 1200 K
5.28 42 T= 2000 K
0 2 4 6 8 10
0 2 4 6 8 10
Pressure (GPa)
Pressure (GPa)
5.64
P = 0 GPa (b) 126
P = 2 GPa
5.58 P = 6 GPa
Lattice parameter (Å)

P = 10 GPa 108
5.52

BT (GPa)
90
5.46

5.40
5.34
5.28
0 400 800 1200
Temperature (K)
Fig. 2. Lattice parameter of AlP versus pressure and temperature.
localization function (ELF) is one of the significant tools used to explore
the bonding nature in the crystals [5]. The bulk modulus is an im-
portant mechanical parameter of materials; it decreases usually with
raising the temperature. The variation of the isothermal bulk modulus
BT as a function of pressure P and temperature T of AlP is shown in
Fig. 3(a) and (b). We observe that BT increases almost linearly with the
applied pressure at temperatures of T = 0, 300, and 1200 K, whereas at
T = 2000 K it increases non-linearly. The increase of BT with pressure P
reflects the increase of the rigidity of the material in question under
pressure. We note also that at a given pressure P, the isothermal bulk
modulus BT decreases with increasing the temperature. Interestingly,
the effect of pressure P on BT seems to be more important than that of
temperature T, especially at low temperatures (0 and 300 K). At zero-
pressure and T = 0 K, the obtained value of BT is around 87.3 GPa. The
latter decreases with T and becomes equal to 83.9 GPa at T = 300 K,
whereas at T = 2000 K it becomes equal to 39.9 GPa. Similar qualita-
tive behavior has been reported for BT versus pressure for BAs com-
pound [26], BSb semiconductor [39], and cubic rock-salt AlN com-
pound [40]. The best fit of BT versus pressure for AlP at various
temperatures is found to obey to the following quadratic expressions,
BT = 87.27 + 3.93 p 1.96 × 10 2p2 ( T= 0K)
BT = 83.85 + 4.06 p 2.45 × 10 2p2 (T=300 K)
BT = 65.72 + 5.20 p 7.10 × 10 2p2 (T=1200 K)
BT = 40.27 + 7.93 p 2.05 × 10 1p2 (T=2000 K)
where both BT and p are expressed in GPa.
72
P = 0 GPa
54 P = 2 GPa
P = 6 GPa (b)
P = 10 GPa
1600 2000 36
0 400 800 1200 1600 2000
Temperature (K)
Fig. 3. Calculated isothermal bulk modulus as a function of pressure and
temperature for AlP.
The specific heat capacity CV of a material is one of the most im-
portant thermodynamic parameters, which is a measure of the phonon
density; it does not only provide essential information about the vi-
brational properties of the substance, but it has also importance in
many applications [41]. The variation of the heat capacity at constant
volume CV as a function of pressure at various temperatures (300, 600,
1200, and 2000 K), and versus temperature at various pressures (0, 2, 6
and 10 GPa) for AlP compound is illustrated in Fig. 4(a) and (b), re-
spectively. It can be seen from Fig. 4 that the heat capacity CV increases
exponentially with the temperature for T < 800 K, while for high
temperatures > 800 K, it approaches the DuLong-Petit limit (CV = 3 k
per atom, k is the Boltzmann's constant). Similar qualitative behavior
has been reported for CV versus temperature for high pressure cubic
rock-salt AlN compound [40], NbN2 material [41], thallium gadolinium
dichalcogenides TlGdX2 (X = S, Se, Te) alloys [42], Al2Sc and Al2Y
compounds [43] and in both cubic zinc-blende and rock-salt platinum
carbide (PtC) obtained within the GGA and harmonic approximation
[44]. At zero pressure and T = 300 K, our obtained value of CV for AlP
compound is around 42.2 J mol−1 K−1 (728 J kg−1 K−1) which is close
(14a) to the value of 736 J kg−1 K−1 of cubic rock-salt aluminium nitride
material [40]. Fig. 5(a) and (b) show the calculated heat capacity at
(14b) constant pressure Cp as a function of pressure at various temperatures
(300, 600, 1200, and 2000 K), and as a function of temperature at
(14c) various pressures (0, 2, 6 and 10 GPa), respectively for AlP compound.
It can be seen from Fig. 5 that the heat capacity Cp increases also ex-
(14d)
ponentially with the temperature for T < 800 K, and varies linearly for
T ˃ 800 K. At P = 0 and T = 300 K, the obtained value of Cp for AlP is

4
S. Daoud, et al. Chemical Physics 525 (2019) 110399

50 72
T= 300 K
68 T= 600 K
49 (a) T= 1200 K
64 T= 2000 K
48 60

Cp (J/mol K)
Cv (J/mol K)

47 56

T= 300 K 52
42 T= 600 K
(a) T= 1200 K 48
41 T= 2000 K
44
40 40
0 2 4 6 8 10 0 2 4 6 8 10
Pressure (GPa) Pressure (GPa)
50 76.5
68.0
40 59.5
51.0

Cp (J/mol K)
Cv (J/mol K)

30 42.5
P = 0 GPa
P = 2 GPa 34.0
(b) P = 6 GPa
20
P = 10 GPa 25.5
17.0 P = 0 GPa
10 P = 2 GPa
8.5 (b) P = 6 GPa
P = 10 GPa
0 0.0
0 400 800 1200 1600 2000
0 400 800 1200 1600 2000
Temperature (K)
Temperature (K)
Fig. 5. Variation of Cp of AlP material as a function of pressure and tempera-
Fig. 4. Constant volume heat capacity CV versus pressure and temperature for ture.
AlP.

observe that the entropy increases very quickly with rising the tem-
around 43.1 J mol−1 K−1 (0.744 J g−1 K−1). This value is in agreement
perature T and hence the behavior of S as a function of temperature
with that of 42.13 J mol−1 K−1 (0.727 J g−1 K−1) reported by Adachi
becomes more like a sub-linear behavior. For the different values of
[28]. The small difference between our result and that reported in Ref.
pressure (0, 2, 6 and 10 GPa), the behavior of S as a function of tem-
[28] may be due to the contributions of the vacancy and other lattice
perature remains qualitatively almost the same for AlP. Comparing our
defects existing in the real solid. The difference between Cp and CV is
results with previous published data in the literature, a similar trend
called the dilatometric term. At zero-pressure and T = 300 K, the cal-
was observed in the cases of III-phosphide (BP, AlP, GaP, and InP)
culated value of the dilatometric term (Cp – CV) of AlP is around
semiconducting compounds [25], high pressure rock-salt AlN com-
0.9 J mol−1 K−1. It is to be noted that the heat capacities CV and Cp of
pound [40], both cubic zinc-blende and rock-salt platinum carbide
AlP semiconductor were also calculated at T = 300 K from statistical
(PtC) compound [44], and boron–carbon-nitrogen (BCN) material [46].
moment method [45]. The values of CV and Cp obtained by Ha et al.
In the quasi-harmonic Debye model approximation, the Debye
[45] are 5.20 cal mol−1 K−1 (21.77 J mol−1 K−1), and
temperature θD is one of the fundamental parameters, which plays an
5.21 cal mol−1 K−1 (21.81 J mol−1 K−1), respectively. These two va-
important role in the prediction of other quantities such as the vibra-
lues are much lower than those obtained in the present work for both CV
tional Helmholtz free energy F and the entropy S. It is closely related to
and Cp parameters. They are also much smaller than the values of CV
several other physical properties of solids, such as melting temperature,
and Cp reported by Ehsanfar et al. [25] and Adachi [28], respectively. It
specific heat, and other dynamic properties [46]. Fig. 7(a) shows the
is very difficult to justify this big discrepancy between the results re-
calculated Debye temperature θD as a function of pressure at various
ported by Ha et al. [45] and the other data (obtained here and reported
temperatures (0, 300, 1200, and 2000 K), whereas the dependence of θD
by Ehsanfar et al. [25] and Adachi [28]). If we multiply their results of
on temperature T up to 2000 K at different pressures (0, 2, 6, and
CV and Cp per 2, we obtain the values of 43.54 J mol−1 K−1 and
10 GPa) is shown in Fig. 7(b). It can be seen from Fig. 7(a) that the
43.62 J mol−1 K−1, respectively, which are in good agreement with our
Debye temperature increases monotonically with increasing pressure.
obtained data and those reported by Ehsanfar et al. [25] and Adachi
At a fixed pressure, the Debye temperature decreases with rising tem-
[28].
perature for AlP compound. The best fit of our data regarding the Debye
The variation of the entropy S as a function of pressure at various
temperature θD for AlP at various pressures obeys to the following
temperatures (300, 600, 1200, and 2000 K), and versus temperature at
quadratic expressions,
various pressures (0, 2, 6 and 10 GPa) of AlP compound are displayed in
Fig. 6(a) and (b), respectively. At low temperature and P = 0, one can D = 567.07 2.50 × 10 2 T 1.50 × 10 5T 2 ( p= 0GPa) (15a)

5
S. Daoud, et al. Chemical Physics 525 (2019) 110399

144 665

126 630

Debye temperature (K)

108 595
S (J/mol K)

90 T= 300 K T= 1200 K 560

T= 600 K T= 2000 K (a)
72 525
T= 0 K
490 (a) T= 300 K
54
T= 1200 K
455 T= 2000 K
36
0 2 4 6 8 10
0 2 4 6 8 10
Pressure (GPa)
Pressure (GPa)
680
150

Debye temperature (K)

P = 0 GPa 640
P = 2 GPa (b)
120 P = 6 GPa
P = 10 GPa 600

90
S (J/mol K)

560

60 520
P = 0 GPa
480 P = 2 GPa (b)
30 P = 6 GPa
P = 10 GPa
440
0 400 800 1200 1600 2000
0
0 400 800 1200 1600 2000 Temperature (K)
Temperature (K) Fig. 7. Variation of the Debye temperature of AlP as a function of pressure and
temperature.
Fig. 6. Pressure and temperature dependent entropy S of AlP material.

2 546 K reported by Wang [48] and Ma et al. [49], respectively. In ad-

D = 590.03 2.62 × 10 T 0.98 × 10 5T 2 (p=2 GPa)
dition, the obtained value (559 K) of θD at 300 K lies in the range
(15b) 479–673 K reported by Kumar et al. [50].
= 630.76 2.41 × 10 2 T 0.61 × 10 5T 2 (p=6 GPa) (15c) In the Debye model, the sound velocity VS and the Debye tem-
D
perature θD are related by the following expression [51],
= 666.89 2.16 × 10 2 T 0.48 × 10 5T 2 (p=10 GPa)
D
VS = kB D
3
6 2 3N V (16)
(15d)
where N/V represents the concentration of atoms in a solid. Fig. 8(a)
where both θD and T are expressed in K. At zero-pressure and zero-
and (b) show the calculated sound velocity (VS) as a function of pres-
temperature, the obtained value of θD for AlP compound is around
sure at various temperatures (0, 300, 1200, and 2000 K), and as a
565.7 K. In order to check the accuracy of our calculation, we have
function of temperature at various pressures (0, 2, 6, and 10 GPa), re-
compared our calculated value of θD with the experimental one of 588 K
spectively. It can be seen from Fig. 8(a) that the sound velocity VS for
measured in the low-temperature limit θD (0) quoted in Ref. [28]. The
AlP increases monotonically with increasing pressure, whereas at a
calculated value of θD is slightly lower than the experimental one re-
fixed pressure, VS decreases with rising temperature. The best fit of our
ported by Adachi [28], where a slight deviation of about 3.8% is ob-
data regarding VS as a function of temperature at various pressures (0,
served. This small deviation may be due to the fact that DFT calcula-
2, 6 and 10 GPa) obeys to the following quadratic expressions,
tions with GGA overestimate the structural parameter (large
equilibrium lattice parameters) and underestimate the cohesive en- VS = 5191.0 0.178 T 1.24 × 10 4T 2 (p=0 GPa) (17a)
ergies and the equilibrium bulk modulus [35]. Another reason may be
due to the defects existing in the real material; thus, because in practice VS = 5361.8 0.188 T 0.79 × 10 4T2 (p=2 GPa) (17b)
the majority of the physical quantities (thermal conductivity, micro-
hardness, … etc) are strongly depending on the imperfections (point
VS = 5658.0 0.171 T 0.48 × 10 4T2 (p=6 GPa) (17c)
defects and extended defects such as: grain boundaries, dislocations,
VS = 5914.6 0.151 T 0.37 × 10 4T2 (p=10 GPa) (17d)
interstitials, vacancies, …etc) existing in semiconductor crystals. Most
of these defects are electrically active and introduce deep levels in the where VS and T are expressed in m/s and K, respectively. Using the
semiconductor band gap [47]. In terms of theoretical calculations, our values of the lattice constant (a = 5.464 Å), and the Debye temperature
calculated value (565.7 K) of θD is in better agreement with the ex- (θD = 559 K) determined at zero-pressure and T = 300 K, the sound
periment [28] than other previous theoretical results of 558.15 K and velocity VS of AlP material was found to be around 5131 m/s, which is

6
S. Daoud, et al. Chemical Physics 525 (2019) 110399

6000
2.2 T= 0 K
T= 300 K
5700
(a)
T= 1200 K

Grüneisen parameter
2.1
Sound velocity (m/s)

T= 2000 K
5400 2.0

5100 1.9

4800 1.8
T= 0 K
4500 (a) T= 300 K 1.7
T= 1200 K
T= 2000 K
4200 1.6
0 2 4 6 8 10 0 2 4 6 8 10
Pressure (GPa) Pressure (GPa)
2.3
6000 P = 0 GPa
2.2 P = 2 GPa
(b)

Grüneisen parameter
5700 P = 6 GPa
Sound velocity (m/s)

2.1 P = 10 GPa
5400
2.0

5100 1.9

4800 1.8
P = 0 GPa
P = 2 GPa 1.7
4500 P = 6 GPa
(b)
P = 10 GPa
1.6
4200
0 400 800 1200 1600 2000 0 400 800 1200 1600 2000

Temperature (K) Temperature (K)

Fig. 8. Sound velocity VS versus pressure and temperature for AlP. Fig. 9. Grüneisen parameter of AlP compound versus pressure and temperature.

in very good agreement with the theoretical average acoustic velocity
5015 m/s reported by Ma et al. [49]. Our obtained value of VS over-
estimates the value of 5015 m/s calculated by Ma et al. [49] by only
around 2.3%.
The Grüneisen parameter is a quantity which is used to under-
stand the variation of temperature in a reversible adiabatic process, to
determine the thermal state, to predict the occurrence of convection,
and to describe the alteration in a crystal lattices vibration frequency
[46,52–54]. A large value of signifies an intense anharmonicity in the
material under load, which is a consequence of the soft bonding in its
crystal structure [46,53]. The Grüneisen parameter is directly related to
the equation of state of the material [46]; it can be reasonably used to
predict the anharmonic properties of a solid, such as the temperature
dependence of phonon frequencies and lattice volume [46]. Fig. 9(a)
shows the variation of the thermodynamic Grüneisen parameter as a
function of pressure at various temperatures (0, 300, 1200, and
2000 K), whereas the temperature dependence of at different pres-
sures (0, 2, 6, and 10 GPa) is shown in Fig. 9(b). It can be seen from
Fig. 9 that remains constant in the temperature range of 0–50 K.
Beyond this temperature, it decreases with increasing pressure. The
decrease is monotonic. A similar behavior was also observed for BAs
semiconductor [26] and cubic ZnS-type AlN compound [2]. Applied
pressure reduces for the material of interest, showing a decrease in
anharmonicity with pressure [54]. At zero pressure and zero tempera-
ture, the obtained value of for AlP compound is around 1.82. This
value is slightly higher than the theoretical ones of 1.49 and 1.36 re-
ported by Adachi [28] and Rodriguez et al. [55], respectively.
Furthermore, our determined value of (1.82) for AlP compound is
smaller than the value of ∼1.87 reported for both rock-salt AlN com-
pound [40] and ternary boron-carbon-nitrogen (BCN) alloy [46], and
the value of 2.269 reported for cubic ZnS-type InN semiconducting
compound [56]. This result indicates that the anharmonicity in AlP
compound is almost the same as that of cubic rock-salt AlN compound
and (BCN) material. The key difference between the Grüneisen para-
meter (1.82) of AlP as calculated in this work and the values of 2.269
reported for cubic ZnS-type InN compound [56] and 2.43 reported for
CuX (X = Cl, and Br) compounds [1] is perhaps due to the nature of the
bonding in each material, since the ionicity of AlP is around 0.307 [28],
that of InN material is around 0.578 [28], and that of CuCl and CuBr
semiconductors is around 0.7 [57]. As a matter of fact, the ionicity of
the bonding in solids can be described by a static effective ion charge.
In III-V and I-VII binary compounds, the degree of ionicity increases
with increasing the difference in electronegativity of their constituents
[58].
The thermal expansion coefficient is used for describing the tem-
perature effect on the size of an object (dimensions change with a
change in temperature) [46]. Fig. 10(a) shows the variation of the cubic
thermal expansion coefficient α as a function of pressure at various
temperatures (300, 600, 1200, and 2000 K) of AlP compound. The de-
pendence of α on the temperature T up to 2000 K at different pressures
(0, 2, 6, and 10 GPa) is shown in Fig. 10(b). The behavior seems to be
similar to that observed for the constant volume heat capacity and the
entropy. Our calculations show that α increases monotonically with
increasing temperature. It is to be noted that a similar qualitative be-
havior has been reported for α versus temperature for cubic ZnS-type

7
S. Daoud, et al. Chemical Physics 525 (2019) 110399

The ground state properties such as a0, B0, and B0′ were calculated and
Thermal expansion coefficient (10 /K)

10 T= 300 K compared with available data. The Knoop microhardness and the
(a)
-5

T= 600 K electronic polarizability were also predicted and discussed. The iso-
9 T= 1200 K thermal and isobaric volumes, the bulk modulus, the heat capacity at
T= 2000 K constant volume, the Debye temperature, the Grüneisen parameter and
8 some other thermodynamic properties under high pressure up to
10 GPa and various temperatures up to 2000 K were also determined
7
and analyzed in detail. In general, our calculated results are in a rea-
6 sonable accord with the available experimental and previous theore-
tical results reported in the literature. The thermophysical properties
5 and sound velocity of AlP material were found to vary monotonically
with temperature and/or pressure. At zero-pressure and T = 300 K, our
4 present calculations yielded a Debye temperature θD of 565.7 K and
3 sound velocity VS of 5131 m/s for AlP semiconducting compound.

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