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Ab initio investigations of the strontium gallium nitride ternaries Sr3GaN3 and Sr6GaN5:

promising materials for optoelectronic

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2013 Semicond. Sci. Technol. 28 085005

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IOP PUBLISHING SEMICONDUCTOR SCIENCE AND TECHNOLOGY
Semicond. Sci. Technol. 28 (2013) 085005 (11pp) doi:10.1088/0268-1242/28/8/085005

Ab initio investigations of the strontium

gallium nitride ternaries Sr3GaN3 and
Sr6GaN5: promising materials for
optoelectronic
Souraya Goumri-Said 1,5 , Haci Ozisik 2 , Engin Deligoz 3
and Mohammed Benali Kanoun 4
1
Physical Science Engineering division, King Abdullah University of Science and Technology
(KAUST), Thuwal 23955-6900, Saudi Arabia
2
Faculty of Education, Department of Computer and Instructional Technologies Teaching,
Aksaray University, 68100, Aksaray, Turkey
3
Department of Physics, Aksaray University, 68100, Aksaray, Turkey
4
KAUST Catalysis Center, King Abdullah University of Science and Technology (KAUST),
Thuwal 23955-6900, Saudi Arabia
E-mail: Souraya.Goumri-Said@kaust.edu.sa

Received 30 January 2013, in final form 11 April 2013

Published 31 May 2013
Online at stacks.iop.org/SST/28/085005

Abstract
Sr3GaN3 and Sr6GaN5 could be promising potential materials for applications in the
microelectronics, optoelectronics and coating materials areas of research. We studied in detail
their structural, elastic, electronic, optical as well as the vibrational properties, by means of
density functional theory framework. Both of these ternaries are semiconductors, where
Sr3GaN3 exhibits a small indirect gap whereas Sr6GaN5 has a large direct gap. Indeed, their
optical properties are reported for radiation up to 40 eV. Charge densities contours, Hirshfeld
and Mulliken populations, are reported to investigate the role of each element in the bonding.
From the mechanical properties calculation, it is found that Sr6GaN5 is harder than Sr3GaN3,
and the latter is more anisotropic than the former. The phonon dispersion relation, density of
phonon states and the vibrational stability are reported from the density functional perturbation
theory calculations.
(Some figures may appear in colour only in the online journal)

1. Introduction
The investigation of novel nitrides is a growing area of
solid-state chemistry in the search for new materials and
properties due to their technological applications [1–4]. Unlike
their analogous oxides, sulfides, or phosphides, the synthesis
of those ternary nitrides is quite challenging, because both
reactants and products are often readily hydrolyzed or oxidized
when exposed to the air [5]. DiSalvo and co-workers reported
several compounds with nitridogallate anions in the past
10 years which often show novel structures [5–9]. In fact,
many ternary metal nitrides, which contain alkaline earth
5 Author to whom any correspondence should be addressed.
metals and main group metals, exhibit structural features that
are quite different from those in metal oxides [5–9]. A few
years ago, a new ternary of strontium gallium nitride family,
Sr3GaN3 and Sr6GaN5, have been synthesized as single crystals
by reaction in the Na flux method [10]. These compounds
contain an isolated triangular anion of [GaN3]6− surrounded
by Sr2− cations [10].
This work is devoted to the chemical and physical
properties of the two strontium gallium nitride compounds
Sr3GaN3 and Sr6GaN5, using the density functional theory and
density functional perturbation theory. Specifically, we address
their crystal parameters, mechanical, electronic, optical and
lattice dynamical properties. The electronic structure and
chemical bonding characterization will then provide an overall

0268-1242/13/085005+11$33.00 1 © 2013 IOP Publishing Ltd Printed in the UK & the USA
Semicond. Sci. Technol. 28 (2013) 085005
(a)
Figure 1. Crystalline structures of Sr3GaN3 (a) and (b) Sr6GaN5.
view of electro-structural information that is needed for
tailoring and improving the electronic features of these
systems. As these compounds contain nitrogen, it is important
to calculate their mechanical properties from the elastic
constants. In addition, the optical properties, such as the
absorption spectrum and the dielectric function, can be
studied to determine the optical band gap and electronic
dielectric constants, which are fundamental in the modeling
of the conduction band offsets, leakage current and dielectric
breakdown. Furthermore, the knowledge of lattice dynamical
properties plays a key role in understanding the structural,
phase transition, infrared (IR)/Raman vibration, optical and
thermodynamic properties. However, theoretical studies of
the lattice dynamical and thermodynamic properties of
Sr3GaN3 and Sr6GaN5, such as heat capacity and Debye
temperature, have rarely been referenced.
The outline of the paper is as follows. In section 2 we
give a brief review of the computational schemes used. The
calculations of the structural and geometry optimization are
developed in section 3.1. The computation of the single-
crystal elastic constants is described in section 3.2. In
section 3.3, we examine the electronic structure, densities of
states and bonding characterization. As we are dealing with
semiconductors, we will devote section 3.4 to the optical
properties, by computing the imaginary and real parts of
the dielectric function, the optical absorption as well as
reflexion spectra. Then, the lattice dynamical properties and
thermodynamic properties will be detailed in section 3.5, while
conclusions will be drawn in section 4.
2. Computational details
Our calculations are performed within the framework of
the density functional theory (DFT) using the projector
augmented wave (PAW) method [11] as implemented in
the Vienna ab initio Simulation Package (VASP) [12]. The
exchange and correlation are treated within the generalized
gradient approximation using the parametrization obtained by
Perdew, Ernzerhof and Burke (GGA-PBE) [13]. The reference
configurations for strontium, gallium and nitrogen potentials
are 4s24p65s2, 4s24p1, and 2s22p3, respectively. We used a
kinetic energy cutoff of 500 eV for plane-wave expansion
2
S Goumri-Said et al
(b)
of the PAWs. Brillouin zone sampling has been done by
the Monkhorst–Pack [14] scheme with a k-point mesh of
8 × 8 × 8 for Sr3GaN3 and 6 × 6 × 4 for Sr6GaN5.
Geometry optimization is performed by conjugate-gradient
minimization of the Hellmann–Feynman forces on the atoms
and the stresses in the unit cell. Atomic coordinates and axial
ratios have been relaxed for different volumes of the unit cell.
Convergence minimum with respect to atomic relaxations is
assumed to have been attained when the energy difference
between two successive iterations is less than 10−6 eV per
unit cell and the forces acting on the atoms are less than
0.01 eV Å−1.
3. Results and discussion
3.1. Geometry optimization and structural properties
The crystal structures of Sr3GaN3 and Sr6GaN5 are shown in
figure 1. The synthesized Sr3GaN3 crystallizes in the space
group P63/m (no. 176) with a = 7.584 Å, c = 5.410 Å,
and Z = 2 [10]. The atomic positions are for Sr, 6h (xSr,
ySr, 14 ); for Ga, 2c( 13 , 23 , 14 ); for N, 6h(xN, yN, 14 ) where
xSr,N and ySr,N are the so-called internal coordinates. Their
crystal structure contains isolated trigonal planar [GaN3] units
where the ([GaN3]6−) anions are isolated from each other by
the Sr counteractions. The structure of this crystal is interpreted
in a specific way, often to emphasize certain aspects of the
structure (see figure 1(a)). An informative way to construct a
simplified perspective of the crystal structure is to introduce
polyhedral units, where the overall structure of Sr3GaN3 can
also be described as a systematic stacking of this basic pseudo-
octahedral unit. Then, Sr6GaN5 belongs to the hexagonal space
group P63/mcm (No. 193) with parameters a = 6.667 Å, c =
12.999 Å, and Z = 2 [10]. The atomic positions are for Sr,
12k(xSr, 0, zSr); for Ga, 2a(0, 0, 14 ); for N1, 6g(xN1, 0, 14 ); for
N2, 4d( 13 , 23 , 0) where xSr,N1 and zSr are the so-called internal
coordinates. The structure of this system can be schematically
described as a sequence of [GaN3] layers separated by layers
composed of edge-sharing octahedral units of [Sr6N] (see
figure 1(b)).
As the first step, we carried out the total energy versus cell
volume calculations to determine the equilibrium structural
parameters for the considered Sr3GaN3 and Sr6GaN5. The
Semicond. Sci. Technol. 28 (2013) 085005
Table 1. Calculated equilibrium lattice parameters (a, and c in Å),
internal coordinates (xSr,N, ySr,N, zSr), formation energies (Ef in
eV/f.u.) along with the available experimental data for Sr3GaN3 and
Sr6GaN5.
Sr3GaN3 Sr6GaN5
This work Exp. [10] This work Exp. [10]
a 7.650 7.584 6.734 6.667
c 5.441 5.410 13.085 12.999
V 275.43 269.51 513.26 500.37
xSr = 0.3571
xSr,N xSr = 0.3571 xSr = 0.5920 xSr = 0.5953
ySr = 0.2869
ySr,N ySr = 0.2869 zSr = 0.1234 zSr = 0.1237
zSr xN = 0.9081 xN = 0.9081 xN1 = 0.2882 xN1 = 0.2843
yN = 0.3987 yN = 0.3987
Ef −2.509 −2.417
calculated values are gathered in table 1 as well as the
experimental data [10] for comparison. The deviations from
experimental values for a and c lattice parameters are
overestimated about 1.47% and 1.53%, respectively. The
relaxed structure is excellent agreement compared to depart
from the ideal stacking as is observed in the experiment (see
table 1). Formation energies (Ef) of these nitrides, calculated
from the difference between their total energies and the sum of
the isolated atomic energies of the pure constituents, are also
reported in table 1. Ef values are always negative, indicating
that the formation of Sr3GaN3 and Sr6GaN5 is exothermic and
that they are intrinsically stable.
3.2. Elastic properties
The elastic constants are important due to their role in of
providing a link between mechanical and dynamical behavior
of crystals, and give important information concerning the
nature of the forces operating in solids [15]. The calculated
elastic tensor for rigid ions has been determined by performing
six finite distortions of the lattice and deriving the elastic
constants from the strain–stress relationship [16]. In this
way, the values of the five independent elastic constants (Cij,
namely C11, C12, C13, C33, C44; while C66 = (C11−C12)/2) are
summarized in table 2.
The mechanically stable phases or macroscopic stability is
dependent on the positive definiteness of the stiffness matrix
[17]. For a stable hexagonal structure, its five independent
elastic constants should satisfy the well-known Born stability
criteria [18]: C11 > 0, C33 > 0, C11−|C12| > 0, C44 > 0, and
(C11 + 2C12)C33 − 2C122 > 0. Clearly, the calculated elastic
constants satisfy the Born stability criteria for considered
structures, suggesting that these compounds are mechanically
stable. After obtaining elastic constants, the polycrystalline
bulk modulus (B), shear modulus (G) are calculated from the
Voigt–Reuss–Hill (VRH) approximations [19]. The Young’s
modulus E and Poisson’s ratio t are calculated through E =
9BG/(3B + G) and ν = (3B − 2G)/2(3B + G). Exploring
the mechanical properties, the results calculated from our ab
initio calculations have been summarized in table 2.
The bulk and shear moduli provide the elastic response of
the material to the isotropic hydrostatic pressure against the
volume deformation and the measure of the material rigidity
3
S Goumri-Said et al
against the shape deformation, respectively. In these systems,
the value of shear modulus is less than the bulk modulus, which
indicates that the shear modulus limits the mechanical stability
of Sr3GaN3 and Sr6GaN5. We observe that the bulk modulus
value of the Sr3GaN3 is higher than the Sr6GaN5 one. As
the bulk modulus represents the resistance to volume change
against external forces. Our results indicate that the highest
average bond strength will be achieved for strontium gallium
nitrides. On the other hand, the obtained bulk modulus for
materials is smaller than 100 GPa, and therefore these systems
should be classified as a relatively soft materials. Note also
that the shear modulus of Sr6GaN5 is smaller than Sr3GaN3. In
addition, the Young’s modulus of materials is defined as the
ratio of linear stress and linear strain, which gives information
about their stiffness. In this context, due to the higher value
of its Young’s modulus, Sr3GaN3 is relatively stiffer than
Sr6GaN5. Poisson’s ratio can formally take values between −1
and 0.5, which corresponds, respectively, to the lower bound
where the material does not change its shape and to the upper
bound when the volume remains unchanged. Value of the
Poisson’s ratio, ν, for covalent materials is small (ν ∼ 0.1),
whereas for ionic materials a typical value of ν is 0.25 [20]. Our
calculated Poisson’s ratio values are higher than 0.20, which
means that Sr3GaN3 and Sr6GaN5 are affected by a certain
amount of ionic contributions.
We are also able to measure the brittleness or ductility
of these materials with the G/B ratio, by already developed
criteria [21]. According to Pugh formulation [21], low G/B
values, i.e., <0.5, are associated with malleability, while
higher values indicate brittleness. In our case, according to
this indicator (table 2), our considered systems will behave
as brittle materials. Indeed, our calculated Debye temperature
is also given in table 2, following the procedure detailed in
[22, 23]. These calculations find that the Debye temperature
of Sr6GaN5 is substantially lower than that of Sr3GaN3, a
consequence of the smaller computer elastic constants of
Sr6GaN5.
The elastic anisotropy of crystals reflects a different
bonding character in different directions and has an important
implication since it correlates with the possibility to induce
microcracks in materials [24]. We have estimated the elastic
anisotropy for the examined materials using the anisotropy
factor [25] defined as A = 4C44/(C11 + C33 − 2C13). The
anisotropic factors obtained from our theoretical studies are
given in table 2. For an isotropic crystal, A is equal to 1, while
any value smaller or larger than 1 indicates elastic anisotropy.
The magnitude of the deviation from 1 is a measure of the
degree of elastic anisotropy possessed by the crystal. It is
interesting to note that the examined systems are characterized
by a profound and larger anisotropy. The elastic anisotropy of
the low-symmetry crystal can be described by the percentage
anisotropy in compressibility (AB) and shear (AG) [19]. For (AB)
and (AG), the values of 0 and 1 (100%) represent the elastic
isotropy and the largest anisotropy. Comparing the average
AB = 2.10% with AG = 0.82% for Sr3GaN3, we find it less
anisotropic in compression and elastically isotropic shear. For
Sr6GaN5, the AB = 2.50% with AG = 5.41% indicate its lower
anisotropy in compression and great anisotropy in shear. We
can deduce that Sr3GaN3 is less anisotropic than Sr6GaN5.
Semicond. Sci. Technol. 28 (2013) 085005 S Goumri-Said et al

(a)

(b)

Figure 2. Calculated band structure and density of states of (a) Sr3GaN3 and (b) Sr6GaN5.

Table 2. The calculated elastic constants (Cij in GPa) bulk modulus (B in GPa), shear modulus (G in GPa), Young’s modulus (E in GPa),
Poisson’s ratio (ν), anisotropic factors (A) and Debye Temperature (D in K).
C11 C12 C13 C33 C44 C66 B G E ν G/B D A

Sr3GaN3 173.9 54.5 30.1 126.2 39.3 59.7 76.5 50.3 123.7 0.23 0.65 407.7 0.66
Sr6GaN5 147.1 48.0 23.1 129.4 27.5 49.5 67.4 40.6 101.4 0.25 0.60 365.7 0.48

3.3. Electronic structure, bonding and atomic charges
analysis
In order to explain the electronic structure, we calculate the
band structure and total density of states for Sr3GaN3 and
Sr6GaN5 along the high symmetry directions in the first
Brillouin zone (BZ) using the optimized lattice parameters,
as shown in figure 2. Sr6GaN5 is a direct band gap material
with both the valence band maximum and the conduction band
minimum at  (see figure 2(a)). The calculated fundamental
band gap is 0.32 eV. Sr3GaN3 has an indirect band gap with a
value 0.55 eV, as the valence band maximum occurs at the K
point, with the conduction band minimum occurring at  (see
figure 2(b)).
From the eigenvalues and eigenvectors solved at sufficient
number k-points in the BZ, the total DOS can be projected into
its partial components (PDOS) with respect to different atoms.
Figures 3(a) and (b) show the calculated partial densities of

4
Semicond. Sci. Technol. 28 (2013) 085005 S Goumri-Said et al

(a) (b)

Figure 3. Calculated partial densities of states of (a) Sr3GaN3 and (b) Sr6GaN5.

(a) (b)

Figure 4. Calculated valence charge density of (a) Sr3GaN3 and (b) Sr6GaN5.

states for Sr3GaN3 and Sr6GaN5. For both systems there are
four regions: the lowest energy band of valence band extends
over a small interval of energy around −33 eV, and is mainly
composed of the Sr s states; the next band occurs between −17
and −15 eV mostly due to Sr p and N s states with a minor
admixture of Ga d states. The other band occurs around −12 eV
mostly due to N s states with a minor admixture of Ga s, Ga
p and S p states. The upper valence band from −5 eV up to
Fermi level consists of hybridized N p states and Ga d states,
with small contribution of Sr d states. The energy region just
above the Fermi level is dominated by unoccupied N p, Sr d
and Ga p states.
In order to visualize the nature of the bonding character
and to explain the charge transfer in Sr3GaN3 and Sr6GaN5,
we calculate the valence charge density by using the full
potential method [26]. The valence charge density is displayed
in the (1 0 1) plane containing Sr, Ga and N atoms (see
figures 4(a) and (b). It can be seen that there is an increase of the
electron density around the N atoms especially for Sr6GaN5.
The charge density contours are more spherical for Sr atoms

5
Semicond. Sci. Technol. 28 (2013) 085005
(a)
(c)
Figure 5. Optical properties of Sr3GaN3. (a) Imaginary and real parts of the dielectric constants. (b) Imaginary and real parts of the optical
conductivity. (c) Refractive index and extinction coefficient. (d) Reflectivity.
in Sr6GaN5 than in Sr3GaN3, showing a strong directional
charge distribution from Ga to N atoms and a decrease of
electron density at the Sr atoms for the second compound.
This bonding is ionic as was observed in former studies on
the GaN semiconductor [27, 28]. In fact, a displacement
of the bonding charge increases as the difference between
the electronegativity values of the two atoms increases.
The spherical shape of the charge surrounding the N atom
suggests a highly ionic bonding, and a charge transfer from
Ga to N in both compounds. Consequently, these charge
rearrangements reflect the electronegative nature of N. It
reveals an ionic contribution to the bonding that adds to a clear
insulating character. According to the density of states analysis
mentioned above, we have also attributed to these two nitrides
a covalent character due to the strong hybridization between N
and Ga states [28]. Therefore, our results demonstrate that the
6
S Goumri-Said et al
(b)
(d)
bonds of Sr3GaN3 and Sr6GaN5 show a mixture of covalent
and ionic bonding.
Now we turn to the charges analysis from the electronic
structure using CASTEP code [29]. Albeit the Mulliken
population analysis [30] suffers from some shortcomings, it
is still meaningful for some qualitative purposes in which
chemists are interested [31]. On the other hand, it is well
known that the Mulliken charge strongly depends on the atomic
basis; we adopted Hirshfeld charge [32, 33] to get a better
understanding of the Sr–N and Ga–N bonding character and
their variation from the first to the second system. In table 3,
we list Mulliken and Hirshfeld charges for both materials.
We may observe that the tendency in charges [29] is the
same for both Mulliken and Hirshfeld schemes. Moreover,
the difference in charges between Sr and N atom is more
than that between Ga and N atom, so we may conclude that
Semicond. Sci. Technol. 28 (2013) 085005 S Goumri-Said et al

(a) (b)

(c) (d)

Figure 6. Optical properties of Sr6GaN5. (a) Imaginary and real parts of the dielectric constants. (b) Imaginary and real parts of the optical
conductivity. (c) Refractive index and extinction coefficient. (d) Reflectivity.

Sr–N bond possesses more ionic character than Ga–N bond, Table 3. Calculated Hirshfeld, Mulliken charges and Bonds
i.e. the Sr–N bond possesses more covalent nature than the populations for Sr3GaN3 and Sr6GaN5.
Ga–N bond. Although it is difficult to put a figure on the level Hirshfeld Mulliken
of ionicity and covalency using the effective valence concept Elements charges charges Bonds Populations
[33], the type of bonding and its level can be determined Sr3GaN3 N −0.43 −1.03 N–Ga 0.74
by calculating the Mulliken bond population as reported in Ga 0.28 0.29 N–Sr 0.20
table 3. A high positive bond population indicates a high Sr 0.34 0.93 Ga–Sr −2.11
degree of covalency in the bond, and positive and negative Sr6GaN5 N1 −0.53 −1.09 N–Ga 0.65
values indicate bonding and antibonding states, respectively. N2 −0.41 −1.06 N1–Sr 0.26
From our results, the negative values (and then the antibonding Ga 0.24 0.31 N2–Sr 0.09
Sr 0.34 0.84 N–Ga –
states) are found in the Sr3GaN3, between the Ga–Sr atoms.
It appears that Sr6GaN5 is more covalent than Sr3GaN3; and
also the bond population between N–Ga in Sr6GaN5 is smaller 3.4. Optical properties
than that of Sr3GaN3. The high covalency of Sr6GaN5 may
be induced by the greater bond population between Sr–N in The interaction of a photon with an electron can be described
Sr6GaN5 compared to Sr3GaN3. as the time-dependent perturbations of the ground electronic

7
Semicond. Sci. Technol. 28 (2013) 085005 S Goumri-Said et al

(a)

(b)

Figure 7. The calculated phonon dispersions, total and partial density of states of (a) Sr3GaN3 and (b) Sr6GaN5.

state in quantum mechanics. Transitions between occupied The zero-frequency limit of the real component ε1 (ω) is
and unoccupied states arise from the photon absorption or equal to n20 and is related to the integration of ε2 (ω) weighted
emission. DFT electronic band structure calculations and by 1/ω:

electron energy loss spectroscopy [34] experiments enable one 2 +∞ ε2 (ω)
to determine the dielectric function ε(ω) = ε1 (ω) + iε2 (ω) n20 = ε1 (0) + dω.
π 0 ω
of a material, from which n and k are deduced [35]. These
Consequently, as k(ω) or ε2 (ω) becomes larger and as
parameters are functions of the incident light energy ω.
the optical gap becomes smaller, the refractive index becomes
The imaginary component ε2 (ω) represents the absorption
larger. The calculated optical spectra such as the real and the
power of a material per unit volume at a given incident light
imaginary parts (ε1 (ω) and (ε2 (ω)) of the dielectric function,
energy. The zero-frequency limit of n(ω), commonly used
absorption coefficient α(ω), refractivity index n(ω), reflectivity
as an indicator of the refractive index in the visible range
R(ω) for Sr3GaN3 and Sr6GaN5 are respectively displayed in
for insulators, is related to the integration of the extinction
figures 5 and 6. We show that for Sr3GaN3 and Sr6GaN5 the
coefficient k(ω), weighted by the inverse of the excitation
imaginary part of the dielectric function has four prominent
energy, 1/ω. That is
 peaks at different photon energies in two crystallographic
2 +∞ k(ω) ([1 0 0] and [0 0 1]) directions, which are due to the interband
n0 ≡ n0 = 1 + dω.
π 0 ω transitions between valence and conduction bands.

8
Semicond. Sci. Technol. 28 (2013) 085005
Figure 8. Temperature dependence of internal, free energy, entropy and heat capacity of Sr3GaN3 and Sr6GaN5.
The rest of the optical properties, namely the refractive
and extinction indices n(ω), k(ω), the reflectivity R(ω) and
the optical conductivity σ (ω) are related to the dielectric
constants and then all the peaks in each of these spectra
correspond to the peaks observed in the imaginary part. The
refractive index of a crystal is closely related to the electronic
polarizability of ions and the local field inside the crystal. The
values of n(0) along two crystal directions are found to be
2.95 (along [1 0 0]) and 2.34 (along [0 0 1]) for Sr3GaN3 and
found to be 2.60 (along [1 0 0]) and 2.48 (along [0 0 1]) for
Sr6GaN5, indicating the low optical anisotropy of the studied
compounds. We also report the reflectivity spectrum R(ω)
for both crystal directions. The found values of R(0) are
0.24 along [1 0 0] and 0.16 along [0 0 1] for Sr3GaN3 and
0.20 along [1 0 0] and 0.17 along [0 0 1] for Sr6GaN5. The
anisotropy is more observed in the first compound from 0
to 15 eV than from 15 eV of incoming photon energy; the
compound has an isotropic behavior. The most prominent
peaks are observed at 2.90 and 6.39 eV along the directions
[1 0 0] and [0 0 1], respectively, for Sr3GaN3. For Sr6GaN5,
these peaks are situated at 3.94 and 25 eV for [1 0 0] and [0 0 1]
directions. In range of [11, 22] eV, both of the compounds show
a reflectivity less than 0.15 and refractive index (<2.20), so
Sr3GaN3 and Sr6GaN5 can be used as antireflection coatings in
optoelectronic devices. Our calculations show that from two
compounds with the same elements composition Sr, Ga and
9
S Goumri-Said et al
N, we may be able to tune their optoelectronic properties by
changing their stoichiometry.
3.5. Lattice dynamical properties
Systemic studies on lattice dynamics and thermodynamics of
transition metal-based nitride materials are of great importance
and in demand. The phonon dispersion curve provides
important information about the dynamical properties of
materials. Many physical properties of solids depend on their
phonon properties, such as specific heat, thermal expansion,
free energy, heat conduction, sound velocity and electron-
phonon coupling. In addition, low frequency modes can
be associated with phase transformations, while imaginary
frequencies show that the calculated structure is not stable.
The phonon dispersion curves of the considered
Sr3GaN3 and Sr6GaN5 systems are calculated by using the
PHONOPY code [36, 37]. PHONOPY code is compatible
with VASP code which determines the Hessian matrix (matrix
of second derivatives) using density functional perturbation
theory (DFPT). We used a 2 × 2 × 1 supercell approach
to calculate second derivatives as input information for
generating the phonon dispersion and the phonon density
of states. The obtained phonon dispersion curves and the
corresponding one-phonon DOS for these compounds along
the high symmetry directions are illustrated in figure 7. Our
Semicond. Sci. Technol. 28 (2013) 085005 S Goumri-Said et al

phonon dispersion curves do not contain soft modes at any Thermodynamic properties such as the free energy, enthalpy,
wave vectors, which confirm the dynamical stability of these entropy and heat capacity were also successfully predicted
systems. On the right side of the phonon dispersion curves the and analyzed with the help of phonon dispersion. Finally, it
corresponding total and partial density of phonon states are is found that the internal energy, entropy and specific heat
also plotted in figure 7. We observe that the main contribution increase with temperature while free energy decreases with
to the low-frequency regions (about below 7 THz) comes from temperature. If experimentally confirmed, our predictions
the Sr vibrational modes with a small hybridization of Ga and may have a significant impact on the way the strontium
N atoms, the high-frequency regions (about above 7 THz) stem gallium nitride ternaries-based devices may be designed
from the N vibrational modes. This is expected because the N in the future in order to optimize their optoelectronic
atom is lighter than the Sr and Ga atoms. performance.
We use phonon densities of states to estimate the
temperature dependence of the internal energy, free energy, References
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