Optik - International Journal for Light and Electron Optics 203 (2020) 163952

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Optik
journal homepage: www.elsevier.com/locate/ijleo

Original research article

Collective effects and optical characteristics of CdSexTe1-x

T
N. Bouarissaa,*, H. Algarnib,c, M. Ajmal Khanb, O.A. Al-Haganb, T.F. Alhuwaymeld
a
Laboratory of Materials Physics and Its Applications, University of M'sila, 28000, M'sila, Algeria
b
Department of Physics, Faculty of Science, King Khalid University, P. O. Box 9004, Abha, 61413, Saudi Arabia
c
Research Center for Advanced Materials Science (RCAMS), King Khalid University, P. O. Box 9004, Abha, 61413, Saudi Arabia
d
National Centre for Nanotechnology, King Abdulaziz City for Science and Technology (KACST), P. O. Box 6086, Riyadh, 11442, Saudi Arabia

A R T IC LE I N F O ABS TRA CT

Keywords: Collective effects and some response characteristics such as piezoelectric stress and strain con-
Optical properties stants, Fröhlich coupling parameter, optical electronegativity and exciton properties of CdSexTe1-
Piezoelectric properties x common-cation ternary alloys have been investigated. The calculations are carried out using a
Exciton properties pseudopotential approach under a modified virtual crystal approximation that takes into account
Ionicity
the alloy disorder effect, combined with the Adachi model. Generally, a good accord is obtained
Fröhlich coupling parameter
CdSexTe1-x alloys
between our results and those available in the literature. The composition dependence of the
features of interest shows that the Fröhlich coupling parameter remains almost constant, the
piezoelectric properties vary almost linearly and the optical properties exhibit a non-linear be-
havior.

1. Introduction

The II-VI ternary semiconducting alloys are interesting materials in connection with applications in optoelectronics in the spectral
region ranging from blue to near-ultraviolet. These materials have potential use in numerous fields such as white light emitters, laser
diodes and solar cells [1–8]. This is essentially attributed to their wide and direct energy band gap. CdSexTe1-x belong to the II-VI
ternary semiconducting alloys and have applications in photovoltaic's or photo electro-chemical devices. They are also used for
photo-assisted decomposition of water [2,9–12].
The knowledge of the fundamental properties of semiconducting alloys is important for guiding the successful design and fab-
rication of optoelectronic devices. The piezoelectric and optical properties are among the fundamental properties which represent key
properties of the material parameters for a variety of research investigations and device applications. In spite of the importance of
these properties, only limited data have been reported on them for CdSexTe1-x common-cation semiconducting ternary alloys [13].
This has prompted us to undertake such a study of these properties for such alloys. The objective of this contribution is to show how
the ionicity, piezoelectric constants and optical properties behave when varying the alloy composition x in CdSexTe1-x. The calcu-
lations are based on a pseudopotential approach under a modified virtual crystal approximation (VCA) that includes the composi-
tional disorder effect combined with the Adachi model in which the Phillips ionicity concept has been considered. Our results are
compared where possible with the known data in the literature. Other case, they are predictions.

⁎
Corresponding author.
E-mail address: nadir.bouarissa@univ-msila.dz (N. Bouarissa).

https://doi.org/10.1016/j.ijleo.2019.163952
Received 1 October 2019; Accepted 30 November 2019
0030-4026/ © 2019 Elsevier GmbH. All rights reserved.
N. Bouarissa, et al. Optik - International Journal for Light and Electron Optics 203 (2020) 163952

Table 1
Energy band gaps (in eV) for CdTe and CdSe fixed in the fits.
Compound EГ-Г EГ-X EГ-L

CdTe 1.5045a 3.48b 2.47b

CdSe 1.69c 3.875d 3.612d

a
Expt. Ref. [24].
b
Theor. Ref. [25].
c
Expt. Ref. [26].
d
Theor. Ref. [27].

2. Computational method

The calculations are performed using the empirical pseudopotential method (EPM) [14–16] under the VCA combined with the
Adachi model [17]. The VCA is known to give band gap bowing parameters which disagree usually with those of experiment [18–20].
For that, an improvement to the VCA has been done where the compositional disorder effect is taken into account [21–23]. In the
EPM one has to adjust a set of pseudopotential form factors (PPFFs) so as to reproduce some selected experimental or theoretical
(when the experimental data are not available) energy band gaps. In this contribution, the selected band gap energies for CdTe and
CdSe fixed in the fits are given in Table 1. The PPFFs are optimized using a non-linear least-squares method as described in Refs.
[28–30]. The final adjusted PPFFs and used lattice parameters for CdTe and CdSe binary compounds are listed in Table 2.
The alloy lattice parameter is calculated using Vegard's rule.

3. Results and discussion

The physics of the chemical bonding is very useful in making a general distinction between covalent and ionic bonding in
semiconducting materials [31–34] and hence it is an important part of research for new materials. One of the successes of the
dielectric theory [31] is the ascription, in a systematic manner, of an ionicity factor, fi, to each semiconductor. Based on the concept
of the Phillips ionicity [31], the variation in fi as a function of the alloy composition x for the common-cation ternary alloys CdSexTe1-
x is displayed in Fig. 1. Note that as the Se content increases on going from CdTe (x = 0) to CdSe (x = 1), fi decreases monotonously
and linearly indicating that the alloy system of interest becomes less ionic when adding more Se atoms into CdTe. The quadratic fit of
our obtained fi versus x using a least-squares procedure gives the following relation,

fi (x ) = 0.717 − 0.018x + 9.801 × 10−17x 2 (1)

The quadratic term in Eq. (1) stands for the ionicity bowing parameter which is very weak (negligible) indicating the linear
behavior of fi versus x.
The II-VI semiconducting materials crystallizing in the zinc-blende structure are good candidates for exhibiting piezoelectric and
related effects [17]. This is due to the lack of center of symmetry in these materials. In this work, the piezoelectric stress constant e14
has been calculated using the recent approach of Bouarissa [35] that was based on the Adachi's model [17] and the concept of Phillips
ionicity scale [31]. Our results concerning e14 yielded values of 0.0735 and 0.0684 C/m2 for CdTe and CdSe, respectively. The former
value for CdTe seems to be larger than that of 0.0335 quoted by Adachi [17]. For CdSe, our calculated e14 is a prediction due to the
lack of both experimental and theoretical data regarding e14 in the literature, to the best of our knowledge. The variation in e14 as a
function of Se concentration for CdSexTe1-x is illustrated in Fig. 2. We observe that e14 is diminished when increasing the Se con-
centration x. The behavior seems to be monotonic. This indicates that by enhancing the Se content in CdSexTe1-x, the contributions of
the ionic and electronic polarizations as well as the strain-dependent ionicity to the piezoelectricity decreases. A polynomial
quadratic fit of our results concerning e14 using a least-squares procedure is written as,

e14 (x ) = 0.0735 − 0.0052x + 5.8275 × 10−5x 2 (2)

e14 in Eq. (2) is expressed in C/m2. The quadratic term in that equation is weak indicating the almost linear behavior of e14 versus x.
The knowledge of e14 has allowed us to determine the strain constant d14. In these calculations, the elastic constant C44 is obtained
using a methodology similar to that used by Bouarissa in Ref. [36]. Our findings yielded values of 2.92 and 1.92 (10−12 m/V) for
CdTe and CdSe, respectively. The d14 obtained for CdTe appears to be larger than that of 1.68 × 10−12m / V quoted by Adachi [17]. As

Table 2
Pseudopotential parameters for CdTe and CdSe.
Compound Form factors (Ry) Lattice constant (Å)

VS(3) VS(8) VS(11) VA(3) VA(4) VA(11)

CdTe −0.396388 0.198275 0.459548 0.1311 0.28 0.708145 6.48

CdSe −0.404199 0.174645 0.340923 0.1311 0.28 0.572395 6.052

2
N. Bouarissa, et al. Optik - International Journal for Light and Electron Optics 203 (2020) 163952

Fig. 1. Ionicity factor versus Se content for CdSexTe1-x ternary alloys.

Fig. 2. Piezoelectric stress constant versus Se content for CdSexTe1-x ternary alloys.

far as d14 of CdSe is concerned, our result is only for reference since there is no data in the literature to compare with, to the best of
our knowledge. The compositional dependence of d14 for CdSexTe1-x is shown in Fig. 3. By observing Fig. 3, one can note that by
enhancing the alloy composition x on proceeding from CdTe (x = 0) to CdSe (x = 1), d14 decreases monotonously. The polynomial
quadratic fit of our results concerning d14 versus x using a least-squares procedure is given by,

d14 (x ) = (2.92 − 1.13x + 0.13x 2) × 10−12 (3)

d14 in Eq. (3) is expressed in m/V. The quadratic term in that equation suggests an almost linear behaviour of d14 versus x in
CdSexTe1-x.
In ionic crystal semiconducting materials, the Coulomb interaction between a conduction electron and lattice ions leads to a
strong coupling between the electron and phonons. The strength of the interaction between electron and phonon is expressed by the
so-called Fröhlich coupling parameter (αF ) [37–40]. In this work, αF has been obtained using the Adachi relation that is related to the
ionicity factor fi as described in Ref. [17]. Our findings yielded values of αF = 0.55 and 0.54 for CdTe and CdSe, respectively. These

Fig. 3. Piezoelectric strain constant versus Se content for CdSexTe1-x ternary alloys.

3
N. Bouarissa, et al. Optik - International Journal for Light and Electron Optics 203 (2020) 163952

Fig. 4. Optical electronegativity versus Se content for CdSexTe1-x ternary alloys.

values are very close to each other which makes the evolution of αF versus alloy composition x insignificant. Our results showed that
αF varies in the range 0.54-0.55 as x increases from 0 to 1. As compared to the results of the literature, Adachi [17] quoted a value of
αF = 0.35 for CdTe. This value is smaller than that obtained in our case. For CdSe, our result is prediction which may serve as a
reference for future works.
The accurate knowledge of the optical properties of semiconducting materials is important in the optimization of devices per-
formances [41,42]. The optical electro negativity concept has a direct bearing on that of chemical bonding which males it useful in
the estimation of many physico-chemical parameters of semiconducting materials [43]. In this regard, the optical electronegativity
( Δχ ) is calculated using the Duffy model as described in Refs. [44,45]. Our results yielded values of Δχ = 0.40 and 0.45 for CdTe and
CdSe, respectively. The variation in Δχ as a function of Se content x for CdSexTe1-x is shown in Fig. 4. We observe that as the alloy
composition x is increased from 0 to 1, Δχ varies non-linearly from 0.40 to 0.45. Interestingly, the value of Δχ for CdSe is larger than
that of CdTe. Δχ is an indication of the nature of the bonding in semiconductors. Thus, one may expect that CdSe is more ionic (less
covalent) than CdTe. This is not consistent with the Phillips ionicity scale as discussed above but agrees with the Pauling ionicity scale
[46] where fi is reported to be 0.58 for CdSe and 0.52 for CdTe. Our findings as regards Δχ have been fitted by a least-squares method
giving the following relation,
Δχ (x ) = 0.33 − 0.09x + 0.24x 2 (4)
3D
The exciton properties in CdSexTe1-x have also been investigated. For that purpose, the exciton binding energy (G ) is calculated
using the modified relation of Bouarissa et al. [47] which is mainly based on that of Adachi's proposed expression [17]. Our cal-
culated G3D for CdTe and CdSe are 10.49 and 13.47 meV, respectively. Our obtained value of G3D for CdTe is in excellent accord with
that of 10.5 meV quoted in Ref. [17]. Due to the lack of data regarding G3D for CdSe, our value is a prediction which can serve for a
reference for future studies. The evolution of G3D versus Se concentration for CdSexTe1-x is plotted in Fig. 5. We observe that by
adding more Se atoms into CdTe, G3D varies non-linearly and non-monotonously. This behaviour is due to the compositional disorder
effect which was found to be very important in CdSexTe1-x [12]. Using a least-squares procedure, our results concerning G3D versus x
are fitted giving the following expression,
G3D (x ) = 7.44 − 6.35x + 13.83x 2 (5)
G in Eq. (5) is expressed in meV. The high value of the quadratic term in that equation confirms the non-linear behaviour of G3D
3D

versus x.

Fig. 5. Exciton binding energy versus Se content for CdSexTe1-x ternary alloys.

4
N. Bouarissa, et al. Optik - International Journal for Light and Electron Optics 203 (2020) 163952

Fig. 6. Exciton Bohr radius versus Se content for CdSexTe1-x ternary alloys.

Among the interesting properties of excitons is the exciton Bohr radius (aB3D). This parameter has been calculated for CdSexTe1-x
using the modified relation of Bouarissa et al. [47] that was essentially based on the Adachi's proposed expression [17]. Our results
concerning aB3D are found to be 64.98 and 57.18 Å for CdTe and CdSe, respectively. The value of aB3D obtained for CdTe is in
excellent accord with that of 65 Å quoted by Adachi in Ref. [17]. The larger value of aB3D for CdTe as compared to that of CdSe
indicates that CdSe is more suitable for photovoltaic applications than CdTe as regards the electron-hole recombination process. The
evolution of aB3D as a function of Se content in CdSexTe1-x is plotted in Fig. 6. By observing Fig. 6, one can note that aB3D varies non-
monotonously with varying the alloy composition x. Our data regarding aB3D versus x are fitted using a least-squares procedure giving
the following analytical expression,
aB3D (x ) = 82.75 + 14.65x − 47.44x 2 (6)
3D
where aB is expressed in Å. Again the huge value of the quadratic term in Eq. (6) confirms the non-linear behaviour of aB3D versus x.

4. Conclusions

In conclusion, the piezoelectric and optical properties of zinc-blende CdSexTe1-x common-cation ternary semiconducting alloys
were studied. The compositional dependence of all features of interest was examined and discussed. The calculations were performed
using a pseudopotential approach within the VCA which takes into consideration the effect of compositional disorder, combined with
the Adachi model in which the Phillips concept of ionicity was considered. Our results were generally found to be in good accord with
those available in the literature. The Fröhlich coupling parameter was found to remain almost constant when varying the alloy
composition x. The piezoelectric stress and strain constants were found to decrease almost linearly with x, whereas the behavior of
the optical electronegativity, exciton binding energy and exciton Bohr radius was found to be non-linear.

Acknowledgement

The authors extend their appreciation to the Deanship of Scientific Research at King Khalid University, Abha, Saudi Arabia for
funding this work through research groups program under grant number R.G.P. 2/24/40.

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