285
ISSN 1063-7826, Semiconductors, 2016, Vol. 50, No. 3, pp. 285–288. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © Z.A. Dzhakhangirli, T.G. Kerimova, N.A. Abdullaev, 2016, published in Fizika i Tekhnika Poluprovodnikov, 2016, Vol. 50, No. 3, pp. 289–292.
Ab Initio Calculations of Phonon Dispersion in ZnGa
2
Se
4
Z. A. Dzhakhangirli
a, b
*, T. G. Kerimova
a
, and N. A. Abdullaev
a, b
**
a
Institute of Physics, Azerbaijan National Academy of Sciences, Baku, Az-1143 Azerbaijan
b
Azerbaijan Technical University, Baku, Az-1073 Azerbaijan
*e-mail: cahanzakir@yahoo.com; **e-mail: abnadir@mail.ru
Submitted June 8, 2015; accepted for publication June 10, 2015
Abstract—In the context of density functional theory, the phonon density of states and phonon dispersion are
calculated for ZnGa
2
Se
4
. The temperature dependence of the heat capacity of ZnGa
2
Se
4
in the temperature
range 5–400 K is obtained. The calculated frequencies and symmetries of phonon modes in the center of the
Brillouin zone are in good agreement with experimental data obtained by Raman spectroscopy and infrared
spectroscopy.
DOI: 10.1134/S1063782616030088
1. INTRODUCTION
(II = Zn, Cd; III = In, Ga; VI = S,
Se, Te) compounds that crystallize in the space
group are attracting attention due to the possibility of
the use of these materials in semiconductor device
engineering. The characteristic features of these com-
pounds are birefringence, large coefficients of nonlin-
ear susceptibility, high photosensitivity, and bright
photoluminescence. In combination with a wide band
gap (2.4–4.5 eV), the above-listed properties puts
these compounds into the series of materials that offer
promise as a basis for the production of nonlinear
optoelectronic converters and devices [1, 2]. There-
fore, studying the physical properties of these com-
pounds is an important challenge. A significant place
is occupied by both theoretical and experimental stud-
ies of electron and phonon states. Knowledge of pho-
non spectra and their dependences on temperature,
pressure, and other external factors is important for
interpreting the mechanisms of heat capacity, thermal
expansion, thermal conductivity, sound absorption,
etc. [3]. Combined theoretical and experimental stud-
ies of phonon spectra and lattice dynamics provide a
means for obtaining data on phonon frequencies at the
center of the Brillouin zone and constants of inter-
atomic bonding, on phonon–phonon and phonon–
electron interactions, etc.
Optical phonons in ZnGa
2
Se
4
were explored by
infrared and Raman spectroscopies [4–6]. In [6], the
optical phonon frequencies were identified in accor-
dance with symmetry types, and with the use of the
symmetrized displacements of atoms in the unit cell, it
was established which frequencies relate to corre-
sponding atomic displacements in the unit cell.
In this paper, we report the results of ab initio cal-
culations of the phonon density of states (DoS) and
phonon dispersion for high-symmetry points and
lines of the Brillouin zone of the compound
ZnGa
2
Se
4
. In addition, the results for the temperature
dependence of the heat capacity of this compound are
reported.
2. CRYSTAL STRUCTURE AND METHOD
OF CALCULATION
Figure 1 schematically shows the crystal lattice of
ZnGa
2
Se
4
. This compound is a crystal-chemical ana-
log of compounds that crystallize in the zinc blende
(T
d
) and chalcopyrite ( ) structures. In the crystal
lattice, each cation atom is surrounded by four anion
atoms. From X-ray diffraction studies, the crystal-lat-
tice parameters are determined. The crystal-lattice
parameters and the interatomic bond lengths calcu-
lated for ZnGa
2
Se
4
in accordance with [7] are given in
Table 1. In compounds (the space
group), chemical bonding is of the ion–covalent type.
In the ZnGa
2
Se
4
compound, as well as in the CdGa
2
S
4
[8] and CdGa
2
Se
4
[9] isostructural compounds, the
force constant of II–VI interatomic bonds, f(II–VI),
is much larger than the force constant f(III–VI) of
II–VI interatomic bonds [10].
In the unit cell of ZnGa
2
Se
4
, there are seven atoms.
The atomic coordinates are as follows: Zn (0, 0, 0),
Ga
1
(1/2, 1/2, 0)a, Ga
2
(0, 1/2, η/2)a, Se
1
(x, y , zη)a,
Se
2
(1 – x, 1 – y , zη)a, Se
3
(1/2 + x, ½ – y , (1/2 –
z)η)a, and Se
4
(1/2 – x, ½ + y , (1/2 – z)η)a. Here η =
c/a, where c and a are the crystal-lattice parameters.
II III VI
2 4
A B C
2
4
S
12
2d
D
II III VI
2 4
A B C
2
4
S
NONELECTRONIC PROPERTIES OF SEMICONDUCTORS
(ATOMIC STRUCTURE, DIFFUSION)