Computational Materials Science 38 (2006) 2938

www.elsevier.com/locate/commatsci

Elastic, electronic and optical properties of ZnS, ZnSe

and ZnTe under pressure
R. Khenata

a,b,*

, A. Bouhemadou c, M. Sahnoun b, Ali. H. Reshak d,

H. Baltache b, M. Rabah a

a
b

Applied Materials Laboratory (AML), Electronics Department, University of Sidi-Bel-Abbe`s, 22000, Algeria
Laboratoire de Physique Quantique et de Modelisation Mathematique (LPQ3M), Departement de Technologie,
Universite de Mascara, Mascara 29000, Algeria
c
Departement de Physique, Faculte des Sciences, Universite Ferhat Abbes, 19000 Setif, Algeria
d
Physics Department, Indian Institute of Technology, Roorkee 247667, India
Received 23 November 2005; received in revised form 25 December 2005; accepted 4 January 2006

Abstract
The results of rst-principles theoretical study of the structural, electronic and optical properties of zinc monochacogenides ZnS, ZnSe
and ZnTe, have been performed using the full-potential linear augmented plane-wave method plus local orbitals (FP-APW + lo) as
implemented in the WIEN2k code. In this approach the local density approximation (LDA) is used for the exchange-correlation
(XC) potential. Results are given for lattice constant, elastic constant, bulk modulus, and its pressure derivative. The band structure,
density of states, pressure coecients of elastic constants, energy gaps and refractive indices are also given. The results are compared
with previous theoretical calculations and the available experimental data.
2006 Elsevier B.V. All rights reserved.
PACS: 71.15.Ap; 78.40.Fy; 78.20.Ci
Keywords: FP-APW + lo; LDA; Elastic constants; Optical constants; Pressure eect

1. Introduction
The wide band gap semiconductors are attracting enormous technological interest because of their potential use in
device capable for operating at high powder level and high
temperature and because of need for optical materials
active in blue-green spectral. Among the wide band gap
semiconductors, ZnS, ZnSe and ZnTe constitute a family
of IIBVIA compounds, crystallizing in the cubic zincblende structure at ambient pressure. These compounds
*

Corresponding author. Address: Laboratoire de Physique Quantique

et de Modelisation Mathematique (LPQ3M), Departement de Technologie, Universite de Mascara, Mascara 29000, Algeria. Tel.: +213
045804162.
E-mail address: khenata_rabah@yahoo.fr (R. Khenata).
0927-0256/$ - see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.commatsci.2006.01.013

dier from the IIAVI compounds by the existence of a

metal d bands inside the main valence band in column
IIB. They have received a lot of attention as blue lasing
materials and could be used in the fabrication of modulated heterostructures and optical wave guides [13]. They
have also proved to be a particularity interesting dilute
semiconductors, when doped with Mn [46], with the possibility of being used as microelectronic magnetic when
alloyed with other elements such as BCC iron, nickel, manganese and cobalt [7,8].
These compounds have been extensively studied experimentally for their intrinsic optical properties [920]. The
structural phase transitions for these compounds were also
performed by many authors with various computational
methods and showing that the transitions to high pressure
phases occurs at about 15 GPa, 13.7 GPa and 9.5 GPa in

30

R. Khenata et al. / Computational Materials Science 38 (2006) 2938

ZnS (Refs. [2126]), ZnSe (Refs. [23,27,28]) and ZnTe

(Refs. [23,29]), respectively. The lattice and hyperne interactions in ZnSe at high pressure has been investigated by
Karzel et al. [30], using both X-ray diraction measurements and FP-LAPW calculations.
From a theoretical point of view, a several rst principles calculations were made for ZnS, ZnSe and ZnTe compounds by a variety of methods [3146]. Cheliokowsky and
Cohen [31], Wang and Klein [32], and Jansen and Sankey
[33] have been studied the electronic structure of these compounds by using the non local pseudopotential (NLPP), the
linear combination of Gaussian orbitals (LCAO) and the
ab initio linear combination of pseudo atomic-orbital
schemes, respectively. Christensen and Christensen [34]
have studied the electronic structure of ZnTe under pressure by means of the self-consistent linear muntin orbital calculation. In the beginning of 1990s, the linear
combination of Gaussian orbitals (LCGO) technique have
used by Gharamani et al. [35] and Jae et al. [36] to discussed the band structure of ZnSe and ZnTe compounds.
The role of d electrons in band structure of zinc-blende
ZnS, ZnSe and ZnTe have been discussed by Lee and coworkers [37] using the ab initio pseudopotential total
energy calculations. The semiempirical tight binding model
is used by Merad et al. [38] and Li and Potz [39] to study
the electronic structure of ZnTe and ternary ZnSeTe and
their binary constituents.
Recently, Ronnow et al. [40] have used the full potential
linear muntin orbitals FP-LMTO method to investigate
the eect of strain on the E1 electronic interband transitions for ZnSe and ZnTe. The band structure of ZnS is
investigated by Qteish [26] and Oshikiri and Aryasetiawan
[41], using the SIC-LDA and GW formalisms, respectively.
The FP-LAPW method coupled with the tight binding theory have been used by Rabah et al. [42] to calculate the
structural, electronic and optical properties of the quaternary MgZnSSe and their binary compounds. Kassali and
Bouarissa [43], Boukortt et al. [44], Benmakhlouf et al.
[45], and Al-Douri et al. [46] reported some band structure
results on ZnTe, ternary ZnSeS and quaternary ZnCdSSe
alloys and the binary constituents. The authors [4346]
used the empirical pseudopotential (EPM) method.
The elastic constants of zinc-chalcogenides have been
calculated more than 10 years ago by Singh and Singh
[47] and Shen [48] using the three-body force potential
and bond orbital calculations based on the tight binding
method, respectively. Recently, Casali and Christensen
[49] have been discussed the calculation of elastic constants
and their pressure dependence, using the full-potential linear muntin orbitals (FP-LMTO) method.
From the above it is clear that there is considerable
experimental and theoretical work on ZnX compounds.
We note that there exist a limited theoretical studies on
elastic and electronic properties under pressure. Moreover,
there appear to be no earlier calculations of the eect of
pressure on the static dielectric constants of these compounds. We therefore think it worthwhile to perform these

calculations. The aim of this work is to give a detailed

description of the behavior of elastic, electronic and dielectric properties of ZnX compounds under hydrostatic
pressure by using for the frame work the full-potential augmented plane wave plus local orbitals (FP-APW + lo)
method, in order to complete the exciting experimental
and theoretical works on these compounds.
2. Computational method
The semiconducting binary ZnX (X = S, Se, Te) compounds are crystallized in the zinc-blende structure. The
space group is F-43 m. The Zn atom is located at the origin
and the X atom is located at (1/4, 1/4, 1/4). The calculations
reported in this work were done with the WIEN2K program
developed by Blaha and co-workers [50]. This program uses
the full-potential linearized augmented plane wave plus local
orbitals [5153] approach (FP-APW + lo) based on density
functional theory [54]. In this method the space is divided
into an interstitial region (IR) and non overlapping (MT)
spheres centered at the atomic sites. In the IR region, the
basis sets consist of a plane wave. Inside the MT spheres,
the basis sets is described by radial solutions of the one particle Schrodinger equation (at xed energy) and their energy
derivatives multiplied by spherical harmonics.
In the calculations reported here, we use a parameter
RMTKmax = 9, which determines matrix size (convergence),
where Kmax is the plane wave cut-o and RMT is the smallest
of all atomic sphere radii. We have chosen the muntin
radii (MT) for Zn, S, Se and Te to be 2.2, 1.7, 1.9 and
2.2 a.u., respectively. XC eects are treated by LDA [55].
The self-consistent calculations are considered to be converged when the total energy of the system is stable within
104 Ry. The integrals over the Brillouin zone are performed
up to 30 k-points in the irreducible Brillouin zone (IBZ),
using the MonkhorstPack special k-points approach [56].
3. Results and discussions
3.1. Structural and elastic properties
The tting of the Murnaghan equation of state [57] to
the total energies versus lattice parameters, yields to the
equilibrium lattice parameter (a0), bulk modulus B0, and
the pressure derivative of the bulk modulus B 0 . In Table
1 we summarize our calculated structural properties (lattice
constant, bulk modulus and its pressure derivative) of ZnS,
ZnSe and ZnTe at ambient pressure. When we analyze
these results we nd that there is a good agreement between
our results and the reported theoretical investigations. In
comparison with the experimental data we nd that the lattice parameters are underestimated whereas the bulk modulus are overestimated. That is attributed to our use of the
local density approximation (LDA). To verify the accuracy
of these results, several tests have been performed using different muntin radius as well as dierent sets of special
k-point to ensure the convergence.

R. Khenata et al. / Computational Materials Science 38 (2006) 2938

Table 1
), bulk modulus (in GPa), pressure
Calculated lattice constant (in A
derivative (B 0 ) at equilibrium volume in zinc-blende (B3) structure for
ZnX compounds compared to experimental and other theoretical works
)
a0 (A
B0
B0
ZnS
Present
Expt.

5.342
5.412a
5.41b
5.3998
5.335
5.352
5.393
5.187

89.67
75a
77.1b
80.97
83.7
83.1
82
105.7

4.44
4.00a
4.00b

71.82
64.7g
69.3h
67.6
67.32
62.45
71.84

4.88
4.77g

TB-LMTOd
FP-LMTOc
NAOi
FP-LAPWj

5.624
5.667g
5.667h
5.618
5.666
5.666
5.578

ZnTe
Present
Expt.
SCR-LMTOl

6.00
6.103k
6.174

55.21
50.9k
51.2

4.60
5.04k
4.88

TB-LMTOc
FP-LMTOd
SIC-PPe
LDA-LMTOa
PPf
ZnSe
Present
Expt.

4.20
4.43
4.20

1
1d2

3
1

7
5

where V0 is the volume of the unstrained unit cell.

Finally, for the last type of deformation, we used the
volume-conserving rhombohedral strain tensor given by
2
3
1 1 1
d6
7
3
41 1 15
3
1 1 1

1
C S C 11  C 12
2

4.05
4.599

The second one involves applying volume conserving

tetragonal strains
0
0

For cubic crystal, the shear wave modulus is given by

4.67

B0 C 11 2C 12 =3

0
d

Ed E0 6C 11  C 12 V 0 d2 Od3

1
Ed E0 C 11 2C 12 4C 44 V 0 d2 Od3
6

To obtain the elastic constants of these compounds with

cubic structure we have used the numerical rst-principle
calculation by computing the compounds of the stress tensor d for small stains, using the method developed recently
by Charpin and integrated in WIEN2k code [50]. It is well
know that a cubic crystal has only three independent elastic
constants C11, C12 and C44. So a set of three equations is
needed to determine all the constants.
The rst equation involves calculating the elastic modulus (C11  C12) which are related to the bulk modulus B0

d
60
4

Application of this strain changes the total energy from its

unstrained value as follows:

This transforms the energy to

SIC-PP: self-interaction correction pseudo-potential; NAO: numerical

atomic orbital within LCAO; SCR-LMTO: self-consistent relativistic linear muntin orbital.
a
Ref. [18].
b
Ref. [58].
c
Ref. [23].
d
Ref. [49].
e
Ref. [26].
f
Ref. [59].
g
Ref. [60].
h
Ref. [61].
i
Ref. [27].
j
Ref. [62].
k
Ref. [63].
l
Ref. [34].

31

Another important parameter is the internal strain

parameter introduced by Kleinman [64] and describes the
relative positions of the cation and anion sublattices under
volume, conserving strain distortions for which positions
are not xed by symmetry. We use the following relation
[65,66]:
f

C 11 8C 12
7C 11 2C 12

Table 2
Calculated elastic constants Cij compared to experimental data and other
works of ZnS, ZnSe and ZnTe for the B3 phase
C11

C12

C44

118
104
123.7
120.46

72
65
62.1
56.46

75
46.2
59.7
46.9

0.715

FP-LMTOb
BOC-TBc
DLMf

94
85.9 0.03a
81.0d
84.0e
95.9
94.66
85.8

61
50.6 0.04a
48.8d
47.0e
53.6
44.46
50.8

64
40.6 0.02a
41.1d
20.8e
48.9
36.8
26.8

ZnTe
Present
Expt.a
BOC-TBc

82
71.7
98

42
40.7
31.8

55
31.2
23.3

ZnS
Present
Expt.a
FP-LMTOb
BOC-TBc
ZnSe
Present
Expt.

0.651; 0.93
0.598
0.746

0.63; 0.736
0.599

0.635
0.596

All of the pressures are in GPa. BOC-TB: bond orbital calculations based
on the tight binding method; DLM: De Launay model based on atomic
central forces.
a
Ref. [60].
b
Ref. [49].
c
Ref. [48].
d
Ref. [67].
e
Ref. [68].
f
Ref. [69].

32

R. Khenata et al. / Computational Materials Science 38 (2006) 2938

In Table 2, we summarized our calculated elastic constants

Cij and the internal-parameter f for the zinc-blende ZnS,
ZnSe and ZnTe in comparison with the experimental data
and previous theoretical calculations. Our calculated values
are in reasonable agreement with available theoretical and
experimental ones, except for C44, where the FP-APW
results are relatively larger than those obtained by using
the BOC-TB and DLM methods. The elastic constants increase in magnitude as a function of the anion chemical
identity as one moves upwards within period VI, i.e. from
Te to S.
The requirement of mechanical stability in this cubic
structure leads to the following restrictions on the elastic
constants, C11  C12 > 0, C44 > 0, C11 + 2C12 > 0. The
elastic constants in Table 2 obey these stability conditions,

including the fact that C12 must be smaller than C11. Our
calculated elastic constants also obey the cubic stability
conditions, meaning that C12 < B < C11.
Now we are interested to study the pressure dependence
of the elastic properties. In Fig. 1, we present the variation
of elastic constants and bulk modulus of ZnS, ZnSe and
ZnTe with respect to the variation of pressure. We clearly
observe a linear dependence in all curves of the zinc chalcogenides in the considered range of pressure, conrming the
idea of Polian and Grimsditch [70] and Harrera-Cabrera
et al. [71] of the no responsibility of the soft acoustic mode
on the phase transition. In Table 3, we listed our results for
the pressure derivatives oB0/oP, oC11/oP, oC12/oP, oC44/
oP and oCS/oP for all the considered compounds. It is easy
to observe that the elastic constants C11, C12, C44 and bulk

Fig. 1. Calculated pressure dependence of Cij, Cs and B for zinc-blende ZnS, ZnSe and ZnTe.

R. Khenata et al. / Computational Materials Science 38 (2006) 2938

33

Table 3
Calculated pressure derivatives of the elastic modulus for zinc-blende ZnX
compounds
Compounds
ZnS
Present
FP-LMTOa
FPMb
ZnSe
Present
Expt.c
FP-LMTOa
FPMb
ZnTe
Present
FPMb
Expt.c

oB0
oP

oC 11
oP

oC 12
oP

oC 44
oP

oC S
oP

4.44

3.86
4.25

4.85
4.32

3.78
0.64
3.08; 4.96

0.495

4.30
4.44
4.50

4.68
4.93
4.62

2.74
0.43
0.79
2.85; 3.94

0.190

3.83

4.89

2.92
3.14; 4.12
0.45

0.532

5.19; 6.23
4.55
4.77
4.17; 5.19
4.60
4.70; 5.65
5.04

FPM: three-body force potential method.

a
Ref. [49].
b
Ref. [47].
c
Ref. [60].

modulus increase when pressure is enhanced. Moreover,

the shear wave modulus CS decreases linearly with the
increasing of pressure for ZnS, ZnSe and ZnTe. We can
also remark that the calculated pressure derivatives of bulk
modulus B, C11 and C12 are in good agreements with the
available theoretical calculations and experimental data.
This agreement disappear in the case of C44, since its value
in FP-APW calculations is larger than the experimental
one. It is impossible for us to nd any raison for discrepancy between the experimental and our calculated results.
3.2. Electronic properties
Fig. 2a, shows the calculated band structure at equilibrium volume for ZnTe as a prototype since the band
proles are quit similar for all three compounds, with a
small dierence. The overall band proles are in fairly good
agreement with previous theoretical results [9,34,35,37,39].
In all cases, the valence band maximum (VBM) and conduction band minimum (CBM) are occurs at the C point.
Thus the energy gap is direct between the top of the (anion
p) valence band and the bottom of conduction band at C
point. Note that the chalcogen p bands shift up in energy
going from the sulphide to the telluride. This is the normal
behavior related to the increase of the lattice parameters,
which was also found for other IIVI compounds [72
74]. The important features of the band structure (main
band gaps and valence band widths) are given in Table 4.
It is clearly seen that the band gap are on the whole underestimated in comparison with experiments results. This
underestimation of the band gaps is mainly due to the fact
that the simple form of LDA do note take into account the
quasiparticle self energy correctly [75] which make it not
suciently exible to accurately reproduce both exchange
correlation energy and its charge derivative. It is important
to note that the density functional formalism is limited in

Fig. 2. Calculated band structure (a) and total density of state (b) of
ZnTe.

its validity (see. Ref [76]) and the band structure derived
from it cannot be used directly for comparison with
experiment.
In Fig. 2b, we show the density of states DOS for only
ZnTe because it is similar to that of ZnS and ZnSe with
a small dierence. It is further observed that the rst structure encountered in the total DOS is small but relatively
broad break centered at around 12.36 eV, 12.48 eV
and 11.36 eV for ZnS, ZnSe and ZnTe respectively. This
structure arise entirely from the chalcogen s states and correspond to the lowest lying band in (Fig. 2a) with its widths
arising from the dispersion in the region around the C point
in the Brillouin zone. The next structure is situated at about
6.20 eV, 6.56 eV and 7.09 eV below the zero of energy for
ZnS, ZnSe and ZnTe, respectively. It consists predominantly of Zn d states with a few contribution of p states
of the chalcogen atoms. From the band structure
(Fig. 2a), this structure corresponds to the at bands clustered at 7.09 eV. The near lack of dispersion of among
some of these bands gives rise to the very narrow nature
of the peaks. The structure hump between 5.50 and the
zero of the energy in these compounds which form the
upper VB correspond to the chalcogen p states partially
mixed with cations s states. Above the Fermi level, the
feature in the DOS originate mainly from the s and p states
of Zn partially mixed with little of chalcogen d states.

34

R. Khenata et al. / Computational Materials Science 38 (2006) 2938

Table 4
Electron band eigenvalues for the lowest conduction band and valence
band width for ZnS, ZnSe and ZnTe in zinc-blende phase
C15v  C1c

C15v  X1c

C15v  Llc

L3v  L1c

V.B.
width

ZnS
Present
Expt.a
EPMb

2.16
3.80
3.66

3.01
4.10
3.70

3.16
4.40
5.60

4.11

13.41

ZnSe
Present
Expt.
NLPMe
LCGOf
SE-TBMg

1.31
2.82c
2.76
1.83
2.82

2.63
4.3d
4.54

2.34
3.7d
3.96

3.36
4.7d
5.00

13.64

4.54

3.92

4.73

ZnTe
Present
Expt.h
MOPWi
OLCAOj
SE-TBMg,k

1.28
2.39
2.6
2.39
2.394; 2.398

2.11
3.3
3.8
3.01
3.8; 3.303

1.64
3.1
3.4
3.39
3.44; 3.095

2.65

12.25

3.9
4.08
3.38

All of the energies are in eV. EPM: empirical pseudopotential method;

NLPM: non-local pseudopotential; LCGO: linear combination of
Gaussian orbitals; MOPW: modied orthogonalized plane wave;
OLCAO: orthogonalized linear combination of atomic orbitals; SE-TBM:
semi empirical tight binding method.
a
Ref. [77].
b
Ref. [45].
c
Ref. [78].
d
Ref. [79].
e
Ref. [31].
f
Ref. [32].
g
Ref. [39].
h
Ref. [80].
i
Ref. [81].
j
Ref. [82].
k
Ref. [38].

Analysis of the width of peaks from these densities of states,

give a band width of valence band equal to 13.41 eV,
13.64 eV, 12.25 eV for ZnS, ZnSe and ZnTe, respectively.
The results show that the valence band width is maximum
for ZnSe. Showing that the wave function is more localized
for ZnS that ZnTe. This is in line with the usual trend in
which the valence band states become more localized as a
material becomes less covalent and more ionic, as it does
when we decrease the atomic number of the anion. It is also
noticed that the band gap between the lowest band (anion s
band) and the valence band is least in ZnTe due to the
higher energy position of the tellurium s band.
We aware that the LDA within the density functional
formalism does not accurately describe the eigenvalues of
the electronic states, which causes quantitative underestimations of band-gaps compared with experiment. However, despite this shortcoming of the LDA, the pressure
derivatives or the deformation potentials of band gaps
are accurately calculated in the LDA (or GGA) and do
not depend on the type or functional form of the
exchange-correlation potential [8385]. As such we have
investigated the eect of the pressure on the size of the
energy gap for zinc chalcogenides using the FP-APW

method within the local density approximations. In order

to achieve this, we have calculated at a dierent sets of
pressures the dierent direct and indirect gaps, then by a
polynomial t of Egap(P) curves we determined the linear
and quadratic pressure-coecients. Results of the linear
and quadratic pressure coecients are listed in Table 5.
Considering this table, we can remark that the linear pressure coecients increase with the increase of chalcogen
atoms. Also, we can notice that the direct energy gaps show
an increase with hydrostatic pressure, which is the behavior
commonly observed in binary tetrahedral semiconductors
[8688]. The negative linear pressure coecients indicates
that the indirect band gap (CX) decreases with increase
of the pressure. A crossover between the direct gap (CC)
and the indirect gap (CX) curves occurs at about
17.9 GPa for ZnS, 30 GPa for ZnSe and 8.9 GPa for ZnTe,
resulting in the energy minimum of indirect gaps for these
compounds. Our calculated linear coecient pressure
along (CC) direction are relatively closed to the experiment and to those of Refs. [18,45] obtained by the empirical pseudo-potential and relativistic linear muntin
orbital methods.
3.3. Optical properties
In calculations of the optical properties, a dense mesh of
uniformly distributed k-points is required. Hence, the Brillouin zone integration was performed with 116 and 172
points in the irreducible part of the Brillouin zone without
broadening. We nd a very small dierence in the two calculations. We present calculations with only 116 points in
this work. The frequency dependent complex dielectric
function e(x) = e1(x) + ie2(x) is known to describe the
optical response of the medium at all phonon energies
E = hx, using the formalism of Ehrenreich and Cohen
[92]. The imaginary part of the e(x) in the long wavelength
limit has been obtained directly from the electronic structure calculation, using the joint density of states (JDOS)
and the transition moments elements Mcv(k)
Z
e2 h X
2
e2 x
jM cv kj dxcv k  x d3 k
7
pm2 x2 v;c BZ
The integral is over the rst Brillouin zone, the dipole moments: Mcv(k) = huck j e $ j uvki where e is the polarization
vector of the electric eld, are matrix elements for direct
transitions between valence uvk(r) and conduction-band
uck(r) states, and hxcv(k) = Eck  Evk is the excitation
energy. The real part of e(x) can be derived from the imaginary part using the KramersKronig relations
Z 1 0
2
x e2 x0
e1 x 1 P
dx0
8
p
x02  x2
0
where P implies the principal value of the integral. The
knowledge of both the real and imaginary parts of the
dielectric function allows the calculation of important optical functions such as the refractive index n(x)

R. Khenata et al. / Computational Materials Science 38 (2006) 2938

35

Table 5
Calculated linear and quadratic pressure coecients of important band gap for ZnS, ZnSe and ZnTe compounds in zinc-blende phase
XX

CC
b
ZnS
Present
LMTOa
EPMb
Expt.a
ZnSe
Present
Expt.c
ZnTe
Present
SE-TBMd
Expt.e
Expt.f

LL

CL
c

5.19
6.22
6.35
6.35

18.26
11.4

1.6

5.40
7.0

15.16

1.78

3.24

1.50

2.76

4.26

11.42

2.24

3.62

7.03
7.7
10.3
10.5

16.02
21.3
24

2.85

10.20

3.01

18.00

5.01

14.22

3.58

6.32

2.28

1.59

CX

6.50

2.71

c
2.44

1.6

4.68

5.19
13.1

Ei p Ei 0 bp 12 cp2 , b = oEi/op in eV 102 GPa1, c = o2Ei/o2p in eV 104 GPa2.

a
Ref. [18].
b
Ref. [45].
c
Ref. [89].
d
Ref. [38].
e
Ref. [90].
f
Ref. [91].

"

e1 x

nx
2

p#1=2
e21 x e22 x
2

Fig. 3, displays the imaginary (absorptive) part of the

dielectric function e2(x) for ZnS, ZnSe and ZnTe at ambient and under 15 GPa pressure for a radiation up to 16 eV.
According to the KramersKronig dispersion relation the
real part of the dielectric function e1(x) is also obtained
but not presented. It is seen that the behavior of e2(x) is
rather similar for all three compounds and is in fairly good
agreements with previous theoretical results. The main difference between these spectra lies in the energies of the
transitions. Our analysis of the e2(x) curves show that
the rst critical points of the dielectric function occurs at
2.16 eV, 1.31 eV and 1.28 eV for ZnS, ZnSe and ZnTe,
respectively. These points are CvCc splitting which gives
the threshold for direct optical transitions between the
absolute fourth valence band maximum and the rst conduction band minimum. This is known as the fundamental
absorption edge. These critical points are followed by a
small structure localized at 4.46 eV in ZnS, 3.75 eV in ZnSe
and 3.03 eV in ZnTe, related to direct transitions (LL).
Note that in the experimental measurements these peaks
are splitted in two peaks by spin-orbit coupling for ZnSe
and ZnTe. The main peaks in the spectra of ZnS, ZnSe
and ZnTe are situated at 5.90 eV, 5.37 eV and 4.46 eV,
respectively. In all compounds, these peaks are mainly
due to the direct transitions along D and R directions.
The experimental measurements localised the critical
points at about 3.50, 2.7, 2.4 eV and the main or global
peaks 6.8 eV, 6.2 eV and 5.3 eV for ZnS, ZnSe and ZnTe
[9,20]. When compared to the experimental data, there is
an energy shift of about 1.20 eV for the threshold peaks.

The energy shift of the main peaks is about 0.8 eV. These
energy shifts mainly arise from the LDA, which give a
smaller band gap in comparison with experiment. The
main peaks are followed by pronounced peaks situated at
7.33 eV, 6.98 eV and 5.85 eV for ZnS, ZnSe and ZnTe,
respectively. These peaks are primarily due to direct transition between the upper valence band and the second conduction band above the Fermi energy at L-edge. When
these materials of interest are compressed, the position of
all critical points cited above are shifted with an increased
or decreased energy comparative to that at normal pressure. The raison lies on the enhancement of the (CC)
direct gaps and de-enhancement of other ones. Although
their positions are shifted under pressure, these points still
have the same type as that at zero pressure. It is worth
noting, moreover, that the main or global peaks are shifted
and their maximum has been increased under pressure in
going from ZnS to ZnTe.
Macroscopic dielectric constants e1(0) is given by the
low energy limit of e1(x). Note that we do not include phonon contributions to the dielectric screening, and e1(0)
corresponds to the static optical dielectric constant e/.
Our calculated optical dielectric constants e/ are listed in
Table 6 as well as other available theoretical and experimental ones.
Fig. 4 shows the calculated results for the pressure
dependence of the dielectric constant e/ for ZnS, ZnSe
and ZnTe in the LDA approximation obtained from relation (8). As can be seen the increase of the dielectric constants (refractive index) with pressure is practically linear
in all the compounds. The pressure derivative of the refractive index n of ZnS, ZnSe and ZnTe are determined by
a polynomial t. Our calculated pressure and volume

36

R. Khenata et al. / Computational Materials Science 38 (2006) 2938

Fig. 3. Calculated imaginary part with and without pressure of the dielectric function of ZnS, ZnSe and ZnTe.

Table 6
The calculated dielectric constants e/, pressure and volume coecients of refractive index for ZnS, ZnSe and ZnTe
1 dn
n0 dp

e/
ZnS
ZnSe
ZnTe
a
b

Present

TD-DFTa

LCAOb

Expt.a

6.18
7.40
9.02

5.71
6.74
7.99

5.63
5.56
5.24

5.2
5.9
7.3

(104 GPa1)

11.3
10.3
9.28

v0 dn
n0 dv

0.160
0.129
0.102

Ref. [93] and references therein.

Ref. [94].

coecients of refractive index are also listed in Table 6.

From this table, we can notice that increase of pressure

or the decrease of the size of the atom (from Te to S), lead

to the decrease of the refractive index and consequently to

R. Khenata et al. / Computational Materials Science 38 (2006) 2938

Fig. 4. Pressure dependence of e/ of ZnS, ZnSe and ZnTe.

the decrease of the microscopic polarisability which has the

same unity and characteristic of a volume. To our knowledge, there are no experimental or theoretical results for
the variation under pressure of the refractive indices available to us for these compounds. We can consider the present results of the linear pressure and volume coecients as
a prediction study for these compounds, hopping that our
present work will stimulate some other works on these
materials.
4. Conclusions
In our calculation we have used the local density
approximation LDA within the FPLAPW + lo method to
study the structural, electronic and optical properties at
normal and under pressure of ZnS, ZnSe and ZnTe in
zinc-blende structure. Our results for the band structure
and DOS, show that these compounds have similar structures with direct energy band gap. These energy band gaps
are decreases when we move from ZnS to ZnSe to ZnTe.
This attributed to the fact that the bandwidth of the conduction bands increases on going from ZnS to ZnSe to
ZnTe. The structural parameters, elastic constants and static dielectric constant are compared with previous theoretical results and experimental data. In comparison with the
experimental data we nd that the lattice parameters are
underestimated whereas the bulk modulus are overestimated. That is attributed to our use of LDA. The critical
point structure of the frequency dependent complex dielectric function was investigated and analyzed to identify the
optical transitions. The pressure dependence of the elastic
and optical constants is also investigated. To our knowledge, there are no earlier studies of the eect of pressure
on elastic properties and imaginary part of the dielectric
constant, so our calculations can be used to cover this lack
of data for these compounds.
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