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Non-local exchange correlation functionals impact on the structural, electronic and optical

properties of III–V arsenides

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2013 Semicond. Sci. Technol. 28 105015

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IOP PUBLISHING SEMICONDUCTOR SCIENCE AND TECHNOLOGY
Semicond. Sci. Technol. 28 (2013) 105015 (13pp) doi:10.1088/0268-1242/28/10/105015

Non-local exchange correlation functionals

impact on the structural, electronic and
optical properties of III–V arsenides
N Najwa Anua 1 , R Ahmed 1,3 , A Shaari 1 , M A Saeed 1 , Bakhtiar Ul Haq 1
and Souraya Goumri-Said 2
1
Department of Physics, Faculty of Science, Universiti Teknologi Malaysia, 81310 UTM Skudai, Johor,
Malaysia
2
Physical Sciences and Engineering Division, King Abdullah University of Science and Technology
(KAUST), Thuwal 23955, Saudi Arabia
E-mail: rashidahmed@utm.my, rasofi@hotmail.com and Souraya.Goumri-Said@kaust.edu.sa

Received 1 April 2013, in final form 11 June 2013

Published 19 August 2013
Online at stacks.iop.org/SST/28/105015

Abstract
Exchange correlation (XC) energy functionals play a vital role in the efficiency of density
functional theory (DFT) calculations, more soundly in the calculation of fundamental
electronic energy bandgap. In the present DFT study of III-arsenides, we investigate the
implications of XC-energy functional and corresponding potential on the structural, electronic
and optical properties of XAs (X = B, Al, Ga, In). Firstly we report and discuss the optimized
structural lattice parameters and the band gap calculations performed within different
non-local XC functionals as implemented in the DFT-packages: WIEN2k, CASTEP and
SIESTA. These packages are representative of the available code in ab initio studies.
We employed the LDA, GGA-PBE, GGA-WC and mBJ-LDA using WIEN2k. In CASTEP, we
employed the hybrid functional, sX-LDA. Furthermore LDA, GGA-PBE and meta-GGA were
employed using SIESTA code. Our results point to GGA-WC as a more appropriate
approximation for the calculations of structural parameters. However our electronic
bandstructure calculations at the level of mBJ-LDA potential show considerable improvements
over the other XC functionals, even the sX-LDA hybrid functional. We report also the optical
properties within mBJ potential, which show a nice agreement with the experimental
measurements in addition to other theoretical results.
(Some figures may appear in colour only in the online journal)

1. Introduction extensively in use as base materials in integrated circuits,

III–V semiconductors are essential for their unfailing
applications as base materials in electronic and optoelectronic
devices. Among these, XAs such as BAs, AlAs, InAs and
GaAs are of particular interest for their unique physical
properties such as wide band gaps, low density, high
thermal conductivities, and dielectric constants [1]. These
materials almost cover the whole visible spectrum from red
to violet light. These properties have made XAs materials
potential candidates for many advanced technologies, and are
3 Author to whom any correspondence should be addressed.
filters, lasers, photo detectors, modulators, light-emitting
diodes etc. At ambient temperature and pressure, XAs have
been recognized to be stable in zinc-blende (ZB) structure
and reported, in available experimental and theoretical studies,
indirect band gap structure for BAs and AlAs and direct
for GaAs and InAs. On account of their peculiar nature of
physical properties and substantial applications in commercial
technologies, in particular, electronic and optoelectronic
devices, XAs are widely explored.
Overall, all members of XAs demonstrate unique
electronic structure and corresponding physical properties:
BAs exhibits strong covalent nature [2], and has analogous

0268-1242/13/105015+13$33.00 1 © 2013 IOP Publishing Ltd Printed in the UK & the USA
Semicond. Sci. Technol. 28 (2013) 105015
electronic nature to silicon that makes it unique among
the other III–V compounds [3]. Being a wide band gap
semiconductor, BAs is considered a suitable partner for
alloying with GaAs and AlAs [4]. In a recent experimental
study [5], it has been used as a p-type electrode and
reported as a suitable candidate for photo-electrochemical and
photovoltaic applications. However, difficult synthesis of BAs
means its properties are still under debate [6]. Similarly GaAs,
owing to direct wide bandgap and having small electronic
effective mass, besides many other applications, is exploited
in ultra fast transistors especially where reliability is the main
concern. Like AlAs and InAs, it plays a fundamental role
as a part of many optoelectronic heterojunction devices and
systems.
Operating characteristics of the electronic and
optoelectronic devices not only depends on material
engineering at a practical level; it also demands clear
understanding of the electronic and optical properties
of these materials. To exploit their optimized potential,
further investigations are therefore crucial at both levels
(experimental and theoretical). As promising optoelectronic
materials, beside the experimental investigations, reports
on theoretical/computational studies are also available in
literature: Chimot et al [7] studied structural and electronic
properties of BAs, GaAs, InAs and their alloys within the
density functional theory (DFT) framework of virtual crystal
approximation. They recommended XAs materials and their
alloys as an alternative to the InP substrate, for the epitaxial
growth of nanostructures to fabricate field-effect transistors,
lasers and storable absorbers in the field of optoelectronics.
Zaoui et al [8] and Boudjemline et al [9] reported the
electronic and optical properties of BAs using LDA and
GGA-PBE within DFT. Using an FP-LAPW method Arabi
et al [10] studied structural and electronic properties of
GaAs in four different phases. Ahmed et al [11] have also
investigated structural and electronic properties of XAs using
LDA, GGA and GGA-EV. Amrani et al [12] studied the
structural parameters, electronic and optical properties at
normal and high pressure using FP-LAPW method at the level
of LDA. Ground state and high-pressure structural parameters
were also investigated by Wang et al [13] using full potential
linearized muffin-tin orbital (FP-LMTO) scheme at the level
of GGA. Similarly Hart et al [4] investigated ground state
as well as electronic properties of BAs, AlAs, InAs and
GaAs within DFT using LDA approximation. Most recently
Guemou et al [14] studied the structural, electronic and optical
properties of BAs, GaAs and their alloys using LDA and
GGA. Though a sizeable number of DFT investigations have
been reported in literature previously using different forms of
exchange correlation (XC) functional, mostly they reproduce
underestimated values of fundamental bandgap values,
especially in the case of semiconductors and insulators, and
corresponding optical properties.
Correct knowledge of fundamental and optical bandgap,
both theoretically and experimentally, is crucial because this
plays a decisive role for their applications as a base material
in electronics and optoelectronics devices, and to exploit
their potential for further applications such as solar cell
2
N N Anua et al
technology. Though DFT-based computer simulations have
made it possible now to investigate electronic bandstructure at
atomic scale and the corresponding fundamental properties
of materials in an amazingly short time and at low cost,
and have predicted the properties of materials not yet
synthesized, reproduction of accurate electronic bandgap
within conventional DFT is not straightforward. This is
because standard DFT XC functionals (LDA, GGA-PBE)
are basically designed to cope with ground state properties.
However, to overcome this difficulty a proper choice of
XC potential functional is crucial to reproduce electronic
band gap and optical properties comparable to experimental
measurements. One of them is the Tran–Blaha modified Becke
Johnson (TB-mBJ) XC potential, which has been reported in
several studies of semiconductors and insulators to calculate
the energy gap with high accuracy near to experimental value.
Highly accurate results at effectively low cost have proclaimed
mBJ as superior to other approaches. Similarly, the role of
hybrid functionals is also appreciated on a large scale.
Motivated by fascinating features of DFT computer
simulations, applications of XAs in cutting edge technologies
and the balanced role of mBJ-LDA exchange and correlation
potential to reproduce bandgap for semiconductors and
insulators, we investigate some of the fundamental properties
of XAs (X = B, Al, Ga, In) using FP-L(APW+lo) framed
within DFT [15, 16]. However, to investigate the response of
XC-potential to band gap calculation we also employ LDA,
GGA-PBE, WC-GGA, meta-GGA and sX-LDA in addition to
mBJ-LDA.
2. Theoretical approaches, methods and
computational details
As introduced, we opted for three robust packages: CASTEP,
SIESTA and WIEN2k. CASTEP and SIESTA codes use the
pseudo-potential descriptions for the crystal potential, where
the inner core electrons are ‘folded in’ with the nuclear
potential, which reduces the number of particles which must
be calculated explicitly and allows the use of plane-wave
basis sets. WIEN2k is based on the all-electrons approach
for calculations (called full potential method).
To carry out calculation of structural properties, we
applied GGA-WC [17]; GGA-PBE [18] and LDA [19]
as implemented in WIEN2k, where to investigate the
role of exchange and correlation potential on the DFT
results of electronic and optical properties, we use mBJ
[20] potential additionally. To perform our computations,
valence electrons of B(2s22p1), Al(3s23p1), Ga(3d104s24p1),
In(4d105s25p1) and As(3d104s24p3) are differentiated from the
core electrons of B(1s2), Al (1s22s22p6), Ga (1s22s22p63s23p6),
In (1s22s22p63s23p63d104s24p6), and As (1s22s22p63s23p6). To
model and simulate an FCC unit cell of XAs compounds
in ZB phase with space group F-43m, atomic positions are
considered inside a unit cell as: X at (0, 0, 0) and As at (1/4,
1/4, 1/4). Then the unit cell is divided into interstitial and
non-overlapping atomic spheres. Inside atomic spheres (radius
R muffin-tin spheres) denoted by RMT around each atom,
spherical harmonic expansion is used to treat Kohn–Sham
Semicond. Sci. Technol. 28 (2013) 105015
(KS) wave functions, charge density as well as potential. Plane-
wave basis set, in the interstitial space, is used. RMT values
of 1.7 a.u and 2.1 a.u are used for B and As to simulate BAs
structure, and for GaAs 2.09 a.u and 2.1 a.u are used, whereas
in the case of AlAs and InAs, 2.0, 2.1 and 2.4 a.u for Al,
As and In atoms, respectively. Inside MT sphere, spherically
symmetric potential is assumed and outside it is taken constant.
To get good energy convergence in the irreducible wedge of
the Brillouin zone, we used 35 k-points, RMT × Kmax = 8, and
Gmax = 14.
To perform CASTEP computations [21], we employed the
hybrid functional (sX-LDA) because sX-LDA is also reported
in literature to reproduce acceptable values of bandgap energy
especially for III–V semiconductor materials with comparable
computational cost of standard LDA. In the screened
exchange (sX) local density approximation (sX-LDA), to
overcome the LDA shortcoming of self-interaction, non-local
exchange potential of electron interaction is included by
adding statically screened exact Hartree–Fock exchange to
some extent into LDA formulism without compromising the
advantages of LDA. In fact, sX-LDA scheme was ‘developed
in the context of the generalized KS procedure’ [22]. In our
CASTEP calculations the same basis sets for valence electron
are used as in WIEN2k calculations, but the core electrons
are described by employing an ultrasoft pseudo-potential
(UPP). The pseudo-atomic calculations performed for our
elements are: As 4s24p3, In 5s25p1, Ga 3d10 4s2 4p1, B 2s2 2p1,
Al 3s2 3p1. The following plane-wave basis set cut-off energy
was considered: 250 eV for AlAs and InAs, 440 eV for
BAs and 590 eV for GaAs. For geometry optimization,
Broyden–Fletcher–Goldfarb–Shanno (BFGS) scheme was
used for k-point sampling.
Siesta code [23, 24] also solves the standard KS equations
self-consistently. To perform our calculations with this code,
we employed LDA, GGA-PBE and meta-GGA [25] functional
approximations to incorporate the XC term. Meta-GGA
has the upper hand over standard GGA-PBE because it
involves an additional second-order derivative term of kinetic
energy density that results in marginal improvement in
comparison with experiments. In this approach of calculations,
valence electrons were described using ‘norm-conserving
Troullier–Martins pseudo-potentials scheme’ [26]. Non-local
components and atomic core were expressed using Kleiman
and Bylander fully factorized form [27, 28]. Sankey and
Niklewsky proposed ‘finite-range pseudo-atomic orbitals’
[29], which are exploited as the ‘split-valence double zeta basis
set with polarization’ (DZP) for valence electrons. Similar
values of energy cut-off were used as mentioned in CASTEP
code. Brillouin zone integration was also sampled using a
similar approach to that adopted for WIEN2k and CASTEP
runs.
3. Results and discussions
3.1. Structural properties
At ambient conditions of temperature and pressure XAs
compounds exist in stable ZB structure with space group
3
N N Anua et al
F-43 m (No-216). In our present DFT study, optimization
of each structure over a range ±10% around equilibrium
volume is performed and obtained data is fitted to Murnaghan’s
equation of state [30] to find out equilibrium lattice constants,
bulk modulus and its pressure derivative, and total energy
for each compound of XAs. These calculations of structural
properties were performed at the level of LDA (WIEN2k,
SIESTA), GGA-PBE (WIEN2k, SIESTA) and GGA-WC
(WIEN2k), sX-LDA (CASTEP) and meta-GGA (SIESTA).
Our calculated lattice constants, bulk modulus and its pressure
derivative, and total energy of unit cell with different exchange
and correlation energy functionals are listed in table 1. For
the sake of comparison, the experimental measurements as
well as the data from previously theoretical works are also
shown. Although the results of all XC-potentials are in good
agreement with the experimental and other theoretical data,
the calculated value of lattice constant ‘a’ with GGA-WC is
significantly closer to experimental value, indicating it as a
more suitable approach for calculating structural properties.
The calculated value of ‘a’ with GGA-PBE is slightly higher
(for all the three codes) while with LDA is slightly smaller in
comparison with experiment. The observed discrepancy in the
value of ‘a’ with LDA and GGA-PBE in our work to that of
experimental values is a well established fact [31]. For bulk
modulus, even though the calculated value is not as accurate
as the experimental value, it is in good agreement with other
computational data. However, our calculated results at the
level of LDA are closer to reported experimental values than
GGA-PBE and GGA-WC.
3.2. Electronic structure and the bandgap calculations
For the investigations of electronic properties of XAs we
calculated the electronic band structure and density of states
(DOS). Calculations of electronic band structure have been
performed using some important (local and non-local) XC
functional to investigate their impact comprehensively. For
efficient and reliable results we used the experimental lattice
parameters in our calculations. The calculated electronic
band structures with different XC-potentials are shown in
figures 1–3 for WIEN2k, CASTEP and SIESTA codes,
respectively. Moreover, we report the band gap values as
extracted from these calculations in table 2. To check
authenticity of our work, we compared the obtained results
with the former theoretical calculation and the experimental
results extracted from the literature.
From the electronic band structures of GaAs and InAs
it can be seen clearly that the conduction band minima
and valence band maxima are lying at the same high
symmetry -point in Brillouin zone, thus endorsing direct
band gap semiconductors. On the other hand, BAs, and
AlAs band structures reveal their indirect band gap nature
because their V.B maxima and C.B minima are lying at
different symmetry points in Brillion zone. From WIEN2k
calculation, it is evident that mBJ functional calculates
the band gap value wider and close to experimental value
followed by GGA-PBE, GGA-WC and LDA. For the
case of GaAs, from SIESTA code calculation, we see
Semicond. Sci. Technol. 28 (2013) 105015 N N Anua et al

Table 1. The calculated data is compared to the experimental and other theoretical data available in the literature.
Lattice Volume Bulk Modulus B0 Pressure
Compounds Method parameter a(A0) V0 (a.u)3 (GPa) derivative B Total energy (eV)
BAs
Our work GGA-PBE 4.815 188.518 131.9 4.199 −62 203.8613
WIEN2k GGA-WC 4.778 184.095 140.8 4.278 −62 115.4178
LDA 4.741 179.788 148.8 4.741 −62 188.9545
CASTEP sX-LDA 4.776 179.768 140.7 4.277 −62 115.3980
SIESTA GGA-PBE 4.823 186.768 143.5 4.125 −63 125.3760
Meta-GGA 4.775 178.965 143.8 4.237 −62 188.3459
LDA 4.739 178.685 151.2 4.098 −62 289.4622
Experiment 4.777 [37] 3.984 [42]
Others calculations FP-LDA 4.741 [11] 79.795 [11] 147.5 [11] 4.216 [11]
FP-GGA 4.817 [11] 188.563 [11] 131.2 [11] 4.179 [11]
FP-LDA 4.743 [38] 152 [38] 3.65 [38]
FP-GGA 4.812 [38] 153 [38] 3.75 [38]
FP-GGA 4.784 [39] 137 [39] 3.49 [38]
HF 4.828 [40] 162 [40]
HF 4.83 [41] 149 [41]
AlAs
Our work GGA-PBE 5.725 317.525 66.63 4.331 −68 136.1056
WIEN2k GGA-WC 5.673 308.623 72.08 4.162 −68 117.3111
LDA 5.630 301.312 75.06 4.309 −68 029.1549
CASTEP sX-LDA 5.645 324.124 79.9 4.277 −68 112.3050
SIESTA GGA-PBE 5.739 307.117 76.3 4.125 −67 928.3580
Meta-GGA 5.679 301.678 66.1 4.237 −67 985.2969
LDA 5.633 301.243 79.2 4.098 −68 286.5012
Experiment 5.620 [37] 82.0 [42] 4.182 [42]
5.661 [43] 77.3 [48]
Others calculations FP-LDA 5.633 [11] 301.526 [11] 75.1 [11] 4.512 [11]
FP-GGA 5.734 [11] 317.988 [11] 66.5 [11] 4.184 [11]
PP-LDA 5.614 [44] 74.7 [44] 4.182 [45]
PP-GGA 5.690 [45] 71.0 [45]
FP-LDA 5.664 [46] 71.0 [46]
FP-LDA 5.644 [47] 75.4 [47] 4.4 [47]
HF 5.741 [40] 90.0 [40]
HF 5.76 [41] 79.0 [41]
GaAs
Our work GGA-PBE 5.749 320.652 60.84 4.256 −114 430.5449
GGA-WC 5.665 306.749 68.10 4.394 −114 404.7767
WIEN2k LDA 5.607 297.380 72.40 4.539 −14 272.1906
sX-LDA 5.645 318.120 57.39 4.469 −114 427.2342
CASTEP GGA-PBE 5.748 322.513 66.12 4.241 −112 336.7767
SIESTA Meta-GGA 5.679 288.260 69.91 4.298 −113 211.2736
LDA 5.601 289.432 86.95 4.621 −116 598.3451
5.654 [37] 77.0 [42] 4.487 [42]
Experiment 5.65 [44] 76.0 [51]
FP-LDA 5.608 [11] 297.606 [11] 75.2 [11] 4.814 [11]
Other calculations FP-GGA 5.748 [11] 320.309 [11] 60.8 [11] 4.800 [11]
PP-GGA 5.530 [44] 75.7 [44] 4.487 [44]
PP-GGA 5.700 [45] 65.0 [45]
FP-LDA 5.651 [46] 63.0 [46]
FP-LDA 5.508 [49] 77.1 [49]
FP-LDA 5.649 [47] 74.2 [47]
FP-LDA 5.592 [50] 81.1 [50] 4.800 [50]
FP-GGA 5.726 [50] 68.0 [50] 4.460 [40]
HF 5.755 [40] 87.0 [40] 4.450 [40]
HF 5.760 [41] 77.0 [41]
InAs
Our work GGA-PBE 6.192 400.659 50.10 4.191 −221 620.9974
WIEN2k GGA-WC 6.096 382.4398 56.20 4.525 −221 588.1455
LDA 6.035 370.858 56.93 4.58 −221 397.9506
CASTEP sX-LDA 6.089 388.234 49.23 4.178 −221 910.3345
SIESTA GGA-PBE 6.096 400.1245 62.18 4.439 −221 898.2390

4
Semicond. Sci. Technol. 28 (2013) 105015
Table 1. (Continued.)
Lattice Volume
Compounds Method parameter a(A0) V0 (a.u)3
Meta-GGA 6.289 359.772
LDA 5.956 388.353
Experiment 6.036 [37]
Other calculations FP-LDA 6.030 [11]
FP-GGA 6.195 [11]
PP-LDA 5.921 [44]
PP-LDA 5.902 [52] 370.879 [11]
FP-LDA 6.015 [47] 401.104 [11]
HF 6.152 [40]
HF 6.150 [41]
that GGA-PBE and LDA are underestimating the band
gap compared to the meta-GGA value. On the other
hand, for InAs, we can observe that both LDA and
meta-GGA are failing compared to GGA-PBE, whereas
GGA-PBE results are somewhat closer to the experiment.
For the hybrid functional, as calculations performed using
CASTEP code, though sX is approaching the experimental
band gap, results with mBJ approach are more systematic and
closest to experiments.
From the calculated electronic structures of XAs, we
calculated the valence band width by considering all the states
in the valence band as a single group. The mBJ calculates a
slightly narrower valence band width compared to the LDA and
GGA-PBE (table 3). This shows that although, mBJ improved
the energy gap value compare to LDA and GGA-PBE, its
response to the band width is not very significant. On the
other hand, sX significantly overestimates the bandwidth
as calculated with common LDA and GGA-PBE. However,
following the recent work on band widths and gaps calculation
from the Tran–Blaha functional and with a comparison with
many-body perturbation theory, performed on some oxides
and semiconductors [32], Martin Schlipf, et al [33] have
implemented HSE hybrid functional within the FLAPW
method. It was revealed that Tran–Blaha functional leads
to band gaps in much better agreement with experiments
than LDA but it globally underestimates, often strongly, the
valence (and conduction) band widths (more than LDA). If we
compare the InAs band gap as found with HSE03 approach
[34], we notice that for InAs, they found a zero band gap,
consequently our approach mBJ-LDA is leading to correction
of the calculation from LDA.
More recently Lucero et al [35] have reported an
improved middle-range screened hybrid exchange functional
in order to determine the lattice parameters and band gap for
semiconductors. In this work, a comparison between HSE06
and functional hybrid, developed a few years ago, called Tao,
Perdew, Staroverov and Scuseria [25] have been presented.
The presented approach developed by Henderson, Izmaylov,
Scuseria and Savin (HISS) was able to perform extremely
well for elemental and binary semiconductors with narrow or
visible spectrum band gaps as well as some wider gap or more
ionic systems used in devices. HISS was proven to be more
efficient than HSE06 for some III–V compounds such as BAs,
but they proved that HISS may be a useful adjunct to HSE in
the modelling of geometry-sensitive semiconductors.
5
N N Anua et al
Bulk Modulus B0 Pressure
(GPa) derivative B Total energy (eV)
46.94 4.67 −221 403.1245
53.32 4.68 −221 603.2373
58.0 [42] 4.79 [53]
60.9 [11] 4.691 [11]
48.1 [11] 4.683 [11]
61.7 [44] 4.545 [44]
61.9 [52] 4.488 [52]
60.3 [47] 4.9 [47]
74.0 [40]
64.0 [41]
In order to complete our description of the electronic
structure with mBJ approach, we calculate the DOS of XAs
with mBJ-XC-potential as displayed in figure 4. The DOS
profiles of all the four compounds are highly analogous in
arrangement of electronic states. There are three significant
structures in DOS of each compound separated by a gap. The
first structure that appears below −10 eV is mainly attributed
to the s orbital of As. The comparatively dispersed second
structure in DOS is mainly composed of highly hybridized s
and p states of X and p states of As. This structure appears in
energy regime ∼−8 to 0 eV in BAs, ∼−6 to 0 eV in AlAs,
∼−6.7 to 0 eV in InAs, and ∼−5.6 to 0 in GaAs. The bottom
of the conduction band is mainly originated from the mixture
of s and p states of X and As elements.
3.3. Optical properties
In the presence of an external electromagnetic field,
the linear response of a system is usually described
by the frequency dependent dielectric function ε(ω) =
ε1 (ω) + iε2 (ω) , which is directly associated with electronic
structure. ε1 (ω) and ε2 (ω) are real (dispersive) and
imaginary(absorptive) parts of the complex dielectric function.
The structures appearing in spectra of ε(ω) mainly describe
the transitions of electrons, which may be either inter band
or intra band. However in semiconductors, where there are
no intra band transitions, structures in ε(ω) are thus caused
by transitions of electrons between the occupied states in V.B
and unoccupied C.B states along high symmetry points in
BZ. Moreover a single peak in ε2 (ω) may not correspond
to a single transition as there might occur many transitions
simultaneously at an energy corresponding to a single peak.
ε2 (ω) is evaluated from momentum matrix elements and is
given by the relation
2e2 π   C 2  
ε2 = K |û.r|kC  δ EkC − EkV − E .
ε0 k,V,C
The real part of the dielectric function can be derived from
ε2 (ω) using Kramers–Kronig transformations. Once the
values of ε1 (ω) and ε2 (ω) are evaluated, the other energy-
dependent optical parameters can be determined using these
obtained values of ε1 (ω) and ε2 (ω).
Our evaluated optical parameters in the present work
with mBJ are shown in figures 5–7. These parameters are
investigated in the energy range 0–30 eV. XAs’ real and
Semicond. Sci. Technol. 28 (2013) 105015 N N Anua et al

Figure 1. The electronic structure of III–V arsenides with various XC potential have been shown calculated with LDA, PBE-GGA,
WC-GGA, and LDA-mBJ (obtained from WIEN2k code).

Figure 2. The electronic structure of III–V arsenides with sX-LDA (obtained from CASTEP code).

6
Semicond. Sci. Technol. 28 (2013) 105015
Figure 3. The electronic structure of III–V arsenides with SIESTA code (LDA, GGA-PBE and meta-GGA).
imaginary components of ε(ω) have been shown in figure 5
and corresponding calculated static dielectric function values
have been listed in table 4.
Table 4, shows a good agreement in our calculated static
dielectric function values to the experimental measurements
and other theoretical results. Figure 5 shows that a major peak
in imaginary part spectra arises at 6.05 eV and 6.02 eV for
Bas and AlAs, respectively. In the case of InAs and GaAs the
major curve appears between two humps. In InAs and GaAs
curves, the major structures are located at energies 4.55 eV
7
N N Anua et al
and 4.17 eV, which are in good agreement with those reported
in [12, 14].
The absorption spectra α(ω) of XAs, calculated in the
present study, have been shown in figure 6. The figure shows
a very small absorption at lower energies (below the band gap
energy) for all XAs compounds. This absorption is mainly due
to free carrier absorption, and is said to be Urbach’s absorption.
Dominant absorption starts at 3.41 eV, 1.01 eV, 2.52 eV and
0.57 eV for BAs, AlAs, InAs and GaAs, respectively. The
absorption spectra for all compounds show a fast increase at
Semicond. Sci. Technol. 28 (2013) 105015 N N Anua et al

Table 2. The energy bandgap (Eg) properties of Bas, AlAs, GaAs and InAs.
Compounds Methods XC Eg(eV) Type of band gap

BAs
Present work FP-LAPW (WIEN2k) GGA-PBE 1.235 Indirect(-
min )
GGA-WC 1.142 Indirect(-
min )
LDA 1.176 Indirect(-
min )
LDA-mBJ 1.730 Indirect(-
min )
UPP (CASTEP) LDA-sX 1.933 Indirect(-
min )
NCP (SIESTA) GGA-PBE 2.52 318 Indirect(-
min )
LDA 1.48 901 Indirect(-
min )
Meta-GGA 1.4347 Indirect(-
min )
Experiment 0.67 [54, 55]
1.46 ± 0.025
Other Calculations LDA 1.13 [11] Indirect(-
min )
GGA 1.18 [11] Indirect(-
min )
GGA-EV 1.79 [11] Indirect(-
min )
LDA 1.12 [38] Indirect(-
min )
GGA 1.21 [38] Indirect(-
min )
GGA 1.23 [39] Indirect(-
min )
GGA 1.25 [56] Indirect(-
min )
AlAs FP-LAPW GGA-PBE 1.478 Indirect(-
min )
Our work GGA-WC 1.365 Indirect(-
min )
LDA 1.385 Indirect(-
min )
LDA-mBJ 2.21 Indirect(-
min )
UPP (CASTEP) LDA-sX 1.944 Indirect(-
min )
GGA-PBE 1.35 496 Indirect(-
min )
LDA 1.4279 Indirect(-
min )
NCP (SIESTA) Meta-GGA 2.5433 Indirect(-
min )
Experiment 2.24 [48]
Other calculations LDA 1.31 [11] Indirect(-
min )
GGA 1.40 [11] Indirect(-
min )
GG-EV 2.25 [11] Indirect(-
min )
LDA 1.37 [46] Indirect(-
min )
LDA 1.25 [47] Indirect(-
min )
LDA 1.32 [45] Indirect(-
min )
GGA 1.39 [45] Indirect(-
min )
LDA 1.35 [57] Indirect(-
min )
LDA 1.31 [58] Indirect(-
min )
GaAs
Our work FP-LAPW GGA-PBE 0.329 Direct (-)
UPP (CASTEP) GGA-WC 0.206 Direct (-)
LDA 1.613 Direct (-)
LDA-mBJ 1.46 Direct (-)
LDA-sX 1.639 Direct (-)
GGA-PBE 0.52 317 Direct (-)
NCP (SIESTA) LDA 0.54 755 Direct (-)
Meta-GGA 1.27 637 Direct (-)
Experiment 1.42 [59]
Other Calculations PP-PW LDA 0.28 [11] Direct (-)
GGA 0.51 [11] Direct (-)
GGA-EV 1.03 [11] Direct (-)
LDA 0.23 [42, 46] Direct (-)
LDA 0.18 [56, 60] Direct (-)
LDA 0.09 [43, 47] Direct (
GGA-EV 0.97 [57, 61] Direct (
LDA 0.32 [41, 45] Direct (
GGA 0.49 [41, 45] Direct (-)
InAs
Our work FP-LAPW GGA-PBE 0.118 Direct (-)
GGA-WC 0.024 Direct (-)
LDA 0 Direct (-)
LDA-mBJ 0.760 Direct (-)

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Semicond. Sci. Technol. 28 (2013) 105015 N N Anua et al

Table 2. (Continued.)
Compounds Methods XC Eg(eV) Type of band gap

UPP (CASTEP) LDA-sX 1.598 Direct (-)

NCP (SIESTA) GGA-PBE 0.523 Direct (-)
LDA 0.0 Direct (-)
Meta-GGA 0.0 Direct (-)
Experiment 0.42 [54]
Other Calculations FP-LAPW LDA 0.00 [11] Direct (-)
PP-LAPW GGA 0.00 [11] Direct (-)
GGA-EV 0.40 [11] Direct (-)
LDA −0.64 [47] Direct (-)
LDA 0.00 [58] Direct (-)

(a) (b)

(c) (d)

Figure 4. Density of states of XAs (a) BAs, (b) AlAs, (c) GaAs, (d) InAs) calculated with mBJ potential.

energies close to their band gap values. This is because of the
fact that photons of energies higher than the band gap values
cause transition from V.B to C.B. All compounds show a broad
spectrum of absorption for higher energies. We analyzed from
our calculations that all the materials have highly absorptive
nature in UV region mainly corresponding to the region
3.43–24 eV for BAs, 1.04–20.50 for AlAs, 2.53–27.83
for GaAs and for InAs 0.59–21.97eV. The maximum
absorption takes place at 7.93, 6.65, 6.51 and 5.78 eV
corresponding to BAs, AlAs, GaAs and InAs. However α(ω)
experiences a gradual decrease for energies higher than these
energies.
The energy lost by an electron while it is traversing
through a medium is described by the energy loss function
L(ω) and mathematically can be written as 1/ε(ω). XAs spectra
of L(ω) against photon energy have been schematically shown
in figure 6. The structures appearing in L(ω) spectrum are
associated with plasma frequency. The structures appearing
below 10 eV are assigned to π -electrons, whereas those
occurring at higher energies are attributed to π + σ plasmons
[36]. Moreover, these structures appear at that energy where
the dispersive component of dielectric function transforms
from metallic to dielectric nature, that is, from negative value
to positive value. From figure 5, it is evident that all the

9
Semicond. Sci. Technol. 28 (2013) 105015 N N Anua et al

Figure 5. The calculated real and imaginary parts of dielectric functions of XAs calculated with mBJ potential.

Figure 6. The calculated absorption coefficient α (ω), energy loss function L(ω) and reflectivity spectra of XAs calculated with mB potential.

four compounds exhibit a single metallic region in ε1 (ω). XAs reflectivity spectra R(ω), calculated in the present
In accordance, L(ω) of XAs shows a single peak at energies work, have been shown in figure 6. R(ω) is generally described
21.91, 17.34, 14.46 and 16.09 eV, a remarkably negative ε1 (ω) as the ratio between incident and reflected beam of light
transforms to positive at about the same energies. through a medium. Our investigations show that the reflectivity

10
Semicond. Sci. Technol. 28 (2013) 105015 N N Anua et al

Figure 7. The calculated refractive index n(ω) and extinction coefficient k(ω) spectra of XAs calculated with XAs.

Table 3. The valence band width of XAs calculated with different Table 4. The static dielectric function of XAs calculated with mBJ
XC functionals. potential in WIEN2k package.
V.B Bandwidth BAs AlAs GaAs InAs ε1(0) Experimental Other theoretical
WIEN2k BAs 8.17 790 9.9 [7], 9.38 [14], 9.9 [9]
LDA 15.40 12.04 12.60 12.00 AlAs 7.32 084 8.20 [62] 9.775 [12]
GGA-PBE 15.44 11.99 12.56 11.97 InAs 9.48 144 14.5 [63] 16.8 [7]
GGA-WC 15.43 12.08 12.67 11.96 GaAs 14.3007 12.9 [64] 14.8 [65], 15.2 [7]
mBJ 15.17 11.60 12.41 11.59
SIESTA
LDA 15.26 11.97 12.65 11.85 Table 5. Refractive index for XAs calculated with mBJ potential in
GGA-PBE 15.30 11.96 12.69 10.97 WIEN2k package.
Meta-GGA 15.34 11.97 12.71 11.79
CASTEP n(0)
sX 17.81 13.67 14.80 13.50
BAs 2.85 972
AlAs 2.70 573 2.864 [62] 3.126 [12]
InAs 3.07 925
index is less than 24% for BAs in energy range 0–1.31 eV GaAs 3.78 179
and above 31.11eV, less than 22% for AlAs in energy range
0–1.18 eV and above 17.53 eV, less than 26% for InAs in
energy range 0–0.72 eV and above 14.51 eV and less than The spectra of refractive index n(ω) and extinction
33% for energy 0–0.17 eV and above 15 eV for GaAs. This coefficient k(ω) have been shown in figure 7. Both parameters,
shows the transparent nature of XAs materials for UV light n(ω) and k(ω) have their origin in ε2 (ω). The static refractive
at these energies. All XAs show a broader structure in energy index n(0) values for XAs have been listed in table 5. Our
regime 3.9–21.7, 3.74–15.57, 1.10–14.95, 2.6259–12.66 eV calculated values successfully satisfy the condition n(0)2 =
for BAs, AlAs, GaAs and InAs, respectively. ε1(0) , indicating the high level reliability of our calculations

11
Semicond. Sci. Technol. 28 (2013) 105015
with mBJ potential. Refraction spectra show that n(ω)
increases with increase in photon energy in the lower energy
regime for ultra violet region. For BAs, AlAs, GaAs and
InAs, n(ω) attain maximum values of 4.31, 4.71, 4.05 and
3.69 at energies 5.07, 4.53, 3.95 and 4.39 eV, respectively.
Extinction coefficients reveal the absorption of light. k(ω)
have distinct peaks at maximum intensity 3.34, 3.26, 3.41 and
3.78 corresponding to energies 6.24 eV, 4.99 eV, 4.36 eV and
2.70 eV, respectively.
4. Conclusion
We employed three different computational approaches, based
on density functional theory, in order to observe the most
reliable approach, able to extract the correct electronic band
gap. We presented at first a discussion of the geometry
optimization and extracted the relaxed lattice parameters as
well as the bulk modulus, its derivative and total energy
for all the employed functionals. It was found that almost
all employed approaches and functionals have succeeded
in determining lattice parameters closer to experimental
measurements. The main goal was to see the dependence of
the band gap on the employed approximations, especially non-
local exchange-correlation functionals. It is observed, in this
study, that some approaches were successful in one compound
but were found to have failed in another. However, calculated
band structure and obtained results of bandgap, at the level of
mBJ-LDA approximation of Vxc incorporated in FP-LAPW
scheme of calculation, were systematic and reliable. It is
also found that mBJ-LDA is not only suitable for electronic
properties; it gives reliable results for optical parameters. Thus,
our study endorses mBJ-LDA approach as one of the best Vxc
approximations for DFT investigations related to electronic
and optical properties.
Acknowledgments
Authors would like to thank the Ministry of Higher
Education (MOHE) Malaysia/Universiti Teknologi Malaysia
(UTM) for financial support for this research work through
grant nos R.J130000.7726.4D034; Q.J130000.2526.02H89;
R.J130000.7826.4F113. Moreover, SGS wish to thank the
research computing service (KAUST-IT) for access to
CASTEP code.
References
[1] Ghebouli M A, Choutri H, Bouarissa N and Ghebouli B 2012
First-principles study on stability, energy gaps, optical
phonon and related parameters of In1−x−yAlxGay As alloys
J. Solid State Chem. 192 161–7
[2] Zaoui A and Hassan F E H 2000 Full potential linearized
augmented plane wave calculations of structural and
electronic properties of BN, BP, BAs and BSb J. Phys.:
Condens. Matter 13 253
[3] Ferhat M, Bouhafs B, Zaoui A and Aourag H 1999
First-principles study of structural and electronic properties
of BSb J. Phys.: Condens. Matter 10 7995
[4] Hart G L W and Zunger A 2000 Electronic structure of BAs
and boride III–V alloys Phys. Rev. B 62 13522
12
N N Anua et al
[5] Wang S, Swingle S F, Ye H, Fan F R F, Cowley A H
and Bard A J 2012 Synthesis and characterization of a
p-type boron arsenide photoelectrode J. Am. Chem. Soc.
134 11056–9
[6] Mujica A, Rubio A, Munoz A and Needs R 2003
High-pressure phases of group-IV, III–V, and II–VI
compounds Rev. Mod. Phys. 75 863
[7] Chimot N, Even J, Folliot H and Loualiche S 2005 Structural
and electronic properties of BAs and BxGa1− xAs,
Bx In1−x As alloys Physica B 364 263–72
[8] Zaoui A, Kacimi S, Yakoubi A, Abbar B and Bouhafs B 2005
Optical properties of BP, BAs and BSb compounds under
hydrostatic pressure Physica B 367 195–204
[9] Boudjemline A, Islam M M, Louail L and Diawara B 2011
Electronic and optical properties of BAs under pressure
Physica B 406 4272–7
[10] Arabi H, Pourghazi A, Ahmadian F and Nourbakhsh Z 2006
First-principles study of structural and electronic properties
of different phases of GaAs Physica B 373 16–22
[11] Ahmed R, Javad Hashemifar S, Akbarzadeh H and Ahmed M
2007 Ab initio study of structural and electronic properties
of III-arsenide binary compounds Comput. Mater. Sci.
39 580–6
[12] Amrani B 2006 First-principles investigation of AlAs at high
pressure Superlatt. Microstruct. 40 65–76
[13] Wang H Y, Li X S, Li C Y and Wang K F 2009
First-principles study of phase transition and structural
properties of AlAs Mater. Chem. Phys. 117 373–6
[14] Guemou M, Bouhafs B, Abdiche A, Khenata R, Al Douri Y
and Bin Omran S 2012 First-principles calculations of the
structural, electronic and optical properties of cubic Bx
Ga1-x As alloys Physica B 407 1292–300
[15] Kohn W and Sham L J 1965 Self-consistent equations
including exchange and correlation effects Phys. Rev.
140 A1133–8
[16] Blaha P, Schwarz K, Madsen G K H, Kvasnicka D and Luitz J
2001 WIEN2k An augmented plane wave+ local orbitals
program for calculating crystal properties (Vienna: Techn.
Universität Wien) (available at www.wien2k.at/index.html)
[17] Wu Z and Cohen R E 2006 More accurate generalized gradient
approximation for solids Phys. Rev. B 73 235116
[18] Perdew J P, Burke K and Ernzerhof M 1996 Generalized
gradient approximation made simple Phys. Rev. Lett.
77 3865–8
[19] Perdew J P and Wang Y 1992 Pair-distribution function and its
coupling-constant average for the spin-polarized electron
gas Phys. Rev. B 46 12947
[20] Tran F and Blaha P 2009 Accurate band gaps of
semiconductors and insulators with a semilocal
exchange-correlation potential Phys. Rev. Lett. 102 226401
[21] Segall M et al 2002 First-principles simulation: ideas,
illustrations and the CASTEP code J. Phys.: Condens.
Matter 14 2717
[22] Seidl A, Görling A, Vogl P, Majewski J and Levy M 1996
Generalized Kohn–Sham schemes and the band-gap
problem Phys. Rev. B 53 3764
[23] Ordejón P, Artacho E and Soler J M 1996 Self-consistent
order-N density-functional calculations for very large
systems Phys. Rev. B 53 10441–4
[24] Soler J M et al 2002 The SIESTA method for ab initio
order-N materials simulation J. Phys.: Condens. Matter
14 2745
[25] Tao J, Perdew J P, Staroverov V N and Scuseria G E
2003 Climbing the density functional ladder:
nonempirical meta–generalized gradient approximation
designed for molecules and solids Phys. Rev. Lett.
91 146401
[26] Troullier N and Martins J L 1991 Efficient pseudopotentials
for plane-wave calculations Phys. Rev. B 43 1993
Semicond. Sci. Technol. 28 (2013) 105015
[27] Kleinman L and Bylander D 1982 Efficacious form for model
pseudopotentials Phys. Rev. Lett. 48 1425–8
[28] Bylander D and Kleinman L 1990 4f resonances with
norm-conserving pseudopotentials Phys. Rev. B 41 907
[29] Sankey O F, Niklewski D J, Drabold D and Dow J D 1990
Molecular-dynamics determination of electronic and
vibrational spectra, and equilibrium structures of small Si
clusters Phys. Rev. B 41 12750
[30] Murnaghan F 1944 Proc. Natl Acad. Sci. USA 30 244
[31] Kanouin M, Merad A, Merad G, Cibert J and Aourag H 2004
Prediction study of elastic properties under pressure effect
for zincblende BN, AlN, GaN and InN Solid-State Electron.
48 1601–6
[32] Waroquiers D et al 2013 Band widths and gaps from the
Tran-Blaha functional: Comparison with many-body
perturbation theory Phys. Rev. B 87 075121
[33] Schlipf M, Betzinger M, Friedrich C, Ležaić M and
Blügel S 2011 HSE hybrid functional within the FLAPW
method and its application to GdN Phys. Rev. B 84 125142
[34] Heyd J, Scuseria G E and Ernzerhof M 2003 Hybrid
functionals based on a screened Coulomb potential J. Chem.
Phys. 118 8207–16
[35] Lucero M, Henderson T M and Scuseria G 2012 Improved
semiconductor lattice parameters and band gaps from a
middle-range screened hybrid exchange functional J. Phys.:
Condens. Matter 24 145504
[36] Jain S K and Srivastava P 2011 Electronic and optical
properties of ultrathin single walled boron nanotubes—an
ab initio study Comput. Mater. Sci. 50 3038–42
[37] Wyckoff R W G and Wyckoff R 1986 Crystal Structures
2nd edn (Malabar: Krieger)
[38] Meradji H, Drablia S, Ghemid S, Belkhir H, Bouhafs B
and Tadjer A 2004 First-principles elastic constants and
electronic structure of BP, BAs, and BSb Phys. Status Solidi
b 241 2881–5
[39] Pickett W E 1989 Pseudopotential methods in condensed
matter applications Comput. Phys. Rep. 9 115–97
[40] Kalvoda S, Paulus B, Fulde P and Stoll H 1997 Influence of
electron correlations on ground-state properties of III–V
semiconductors Phys. Rev. B 55 4027
[41] Causa M, Dovesi R and Roetti C 1991 Pseudopotential
Hartree–Fock study of seventeen III–V and IV–IV
semiconductors Phys. Rev. B 43 11937
[42] Hellwege K and Madelung O 1982 Physics of Group IV
Elements and III–V Compounds (Landolt–Börnstein New
Series vol 17a) (New York: Springer)
[43] Adachi S 2005 Properties of Group-IV, III–V and II-VI
Semiconductors vol 1 (New York: Wiley-VCH) p 406
[44] Wang S and Ye H 2002 A plane-wave pseudopotential study
on III–V zinc-blende and wurtzite semiconductors under
pressure J. Phys.: Condens. Matter 14 9579
[45] Rushton P P, Clark S J and Tozer D J 2001 Density-functional
calculations of semiconductor properties using a
semiempirical exchange-correlation functional Phys. Rev. B
63 115206
[46] Min B, Massidda S and Freeman A 1988 Structural and
electronic properties of bulk GaAs, bulk AlAs, and the
(GaAs)1(AlAs)1 superlattice Phys. Rev. B 38 1970
13
N N Anua et al
[47] Wei S H and Zunger A 1999 Predicted band-gap pressure
coefficients of all diamond and zinc-blende semiconductors:
chemical trends Phys. Rev. B 60 5404
[48] Vurgaftman I, Meyer J and Ram-Mohan L 2001 Band
parameters for III–V compound semiconductors and their
alloys J. Appl. Phys. 89 5815–75
[49] Agrawal B K, Yadav P, Kumar S and Agrawal S 1995
First-principles calculation of Ga-based semiconductors
Phys. Rev. B 52 4896
[50] Staroverov V N, Scuseria G E, Tao J and Perdew J P 2004
Tests of a ladder of density functionals for bulk solids and
surfaces Phys. Rev. B 69 075102
[51] Filippi C, Singh D J and Umrigar C J 1994 All-electron
local-density and generalized-gradient calculations of the
structural properties of semiconductors Phys. Rev. B
50 14947
[52] Van Camp P, Van Doren V and Devreese J 1990 Pressure
dependence of the electronic properties of cubic III–V In
compounds Phys. Rev. B 41 1598
[53] Vukcevich M 1972 On the stability of the alkali halide
lattices under hydrostatic pressure Phys. Status Solidi b
54 219
[54] Bross H and Bader R 1995 Calculation of the ground state
properties of diamond and cubic boron nitride Phys. Status
Solidi b 191 369–85
[55] Martienssen W and Warlimont H 2005 Springer Handbook of
Condensed Matter and Materials Data (New York:
Springer)
[56] Wentzcovitch R M, Cardona M, Cohen M L
and Christensen N E 1988 X1 and X3 states of electrons and
phonons in zincblende type semiconductors Solid State
Commun. 67 927–30
[57] Stroppa A and Peressi M 2005 Composition and strain
dependence of band offsets at metamorphic Inx
Ga1–xAs/InyAl1–y As heterostructures Phys. Rev. B
71 205303
[58] Karazhanov S Z and Lew Yan Voon L 2005 Ab initio studies of
the band parameters of III–V and II–VI zinc-blende
semiconductors Semiconductors 39 161–73
[59] Adachi S 1982 Material parameters of InGaAsP and related
binaries J. Appl. Phys. 53 8775
[60] Dufek P, Blaha P and Schwarz K 1994 Applications of Engel
and Vosko’s generalized gradient approximation in solids
Phys. Rev. B 50 7279
[61] Mokhtari A and Akbarzadeh H 2002 Electronic and structural
properties of β-Be3N2 Physica B: Condens. Matter
324 305–11
[62] Pavesi L and Guzzi M 1994 Photoluminescence of
AlxGa1− x As alloys Appl. Phys. Rev. 75 4779
[63] Madelung O, Schulz M and Weiss H 1982 Crystal and Solid
State Physics: Semiconductors subvol. b: Physics of II–IV
and I–VII Compounds, Semimagnetic Semiconductors
(Berlin: Springer)
[64] Moore W and Holm R 1996 Infrared dielectric constant of
gallium arsenide J. Appl. Phys. 80 6939–42
[65] Yan Y et al 2012 First-principle study of the electronic and
optical properties of BInGaAs quaternary alloy
lattice-matched to GaAs Physica B 407 4570–3