Columbia International Publishing

Advances in Alloys and Compounds

(2015) Vol. 2 No. 1 pp. 30-36
doi:10.7726/aac.2015.1003
Short Communication

DFT Investigations of the Structural and Electronic

Properties of XN (Al, Ga, In) Compounds

M.M. Alsardia1, M A Saeed1*, Tariq Mahmood2, S Islam1, and Ahmad Radzi Mat Isa1

Received 23 July 2015; Published online 12 December 2015

© Columbia International Publishing 2015. Published at www.uscip.us

Abstract
In this study, density functional theory investigation for structural and electronic properties of XN (Al, Ga, In)
compounds have been investigated by using full-potential linearized augmented plane wave plus local
orbitals (FP-L (APW+lo)) method. To investigate and compare the electronic structures a new approach;
modified Becke-Johnson (mBJ) exchange potential plus local-density approximation (mBJ-LDA) has been
implemented. Our comparative calculations for band gap energy show that, mBJ-LDA results are in very good
agreement to the experimental results than the local density approximation (LDA) and generalized gradient
approximation (PBE-GGA).

Keywords: DFT; Electronic properties; Structural properties; Modified Becke-Johnson potential

1. Introduction
Recently, III–nitride semiconductors XN (Al, Ga, In) are used in the fabrication of the electronic and
optoelectronic devices (from blue to near ultraviolet region) (Christensen, I. Gorczyca, 1994) such
as laser diodes, light emitting diodes, solar blind photo detectors (Hove et al., 1997; Nagahama et
al., 2001; Morkoc, 1999). This nitride has a high thermal conductivity, high melting point, a high
ionicity and low compressibility (Christensen, I. Gorczyca, 1994). These outstanding properties and
a wide band gaps (except InN) (Inushima et al., 2001; Davydov et.al., 2002; Wu et. al., 2002b;
Carrier and Wei, 2005; Ahmed et.al., 2005) are related to the large electronegativity difference
between group III and V elements (Sharma et.al., 2008; Mokhtari and Akbarzadeh, 2003; 2002). Due
to incomparable physical properties, these materials also viewed as promising candidates in the
future optoelectronic device applications like “high-density data devices and undersea optical
communication systems” (Usman et. al., 2011). Normally, these compounds appear in the wurtzite
structure with direct energy band gap. In this research work, we carry out an all- electron full-

______________________________________________________________________________________________________________________________
*Corresponding e-mail: saeed@utm.my
1 Department of Physics, Faculty of Science, Universiti Teknologi Malaysia, Skudai -81310, Johor, Malaysia
2 Centre for Excellence of Solid State Physics, University of the Punjab, Lahore, Pakistan

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/ Advances in Alloys and compounds (2015) Vol. 2 No. 1 pp. 30-36

potential linearized augmented plane wave plus local orbitals FP-(L (APW+lo) method to determine
the structural and electronic properties of XN (Al, Ga, B, In) compounds in the wurtzite structure
within the framework of DFT (Adetunji et.al., 2012).

2. Computational Details
Total energy calculations are performed using WIEN2k package (Blaha, et. al., 2001) based on FP-(L
(APW+lo). In this method, the unit cell is split into non-overlapping muffin-tin spheres of radius
(RMT) around the atomic sites and an interstitial region. Different basis sets are used for these
regions. The Kohn–Sham energy function, which is based on the DFT (Hohenberg et. al., 1964; Kohn
et.al., 1965) is solved in a self-consistent scheme. We performed the calculations using the LDA
(Perdew and Wang, 1992), GGA (Perdew et. al., 1996) and LDA-mBJ (Tran and Blaha, 2009). In the
computation, we differentiate between the core-shell electrons of Al (1s2 2s2 2p6), Ga (1s2 2s2 2p6
3s2 3p6 3d10), In (1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10) & N (1s2); and the valence electrons
of Al (3s2 3p1), Ga (4s2 4p1), In (5s2 5p1) & N (2s2 2p3). The muffin–tin sphere radii Rmt adopted
were 1.6 a.u. (Al and N), 1.8 a.u. (Ga and N) and 2.1 a.u. (In and N).

3. Results and Discussion

3.1 Structural properties

Fig.1. Band structures of XN (Al, Ga, In) compounds calculated by the LDA, GGA and mBJ-LDA,
respectively

For the wurtzite phase, there are four atoms per hexagonal unit cell, where AlN, GaN and InN are in
(2b) positions as R (Al, Ga, In): (0, 0, 0), (1/3, 2/3, 1/2); X (N): (0, 0, u), (1/3, 1/2, 1/2 +‫‏‬u). Where u
is the dimensionless internal parameter that represents the relative displacement between the R
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/ Advances in Alloys and compounds (2015) Vol. 2 No. 1 pp. 30-36

(Al, Ga, In) plane and its nearest-neighbor N plane along the c direction. We use experimental lattice
parameters for AlN: a =3.111 Å and c = 4.978 Å; GaN: a =3.180 Å and c = 5.166Å; InN: a = 3.533 Å
and c = 5.693Å .

Our calculations for structural properties by using Murnaghan equation of state (Murnaghan, 1944)
are summarized in Table 1 along with other computational and experimental results for
comparison. From the table, it can be seen that, the LDA underestimates while GGA overestimates
the lattice parameters. For Bulk modulus, we have an underestimation (GGA) and an
overestimation (LDA).

Table 1 Calculated structural parameters, Lattice constants (a), volume (V), bulk modulus (B), its
pressure derivative (B0) along with experimental data and other theoretical calculations
available in the literature.

Compounds Method 𝐚(Å) 𝐜(Å) 𝐜⁄𝐚 𝐕(𝐚. 𝐮. )𝟑 𝐁(𝐆𝐏𝐚) 𝐁𝐨

AlN(WZ)
Our Work FP-LDA 3.089 4.942 1.60 275.8393 201.0785 3.7274
FP-GGA 3.132 5.127 1.60 287.5456 193.2606 3.6775

Experiment 3.111* 4.978* 1.601 ̶ 208+ 6.3+

Other FP-LDA** 3.097 4.956 ̶ 214.21 4.01 13.21

calculation
FP-GGA** 3.139 5.236 ̶ 193.31 4.17 11.47

GaN(WZ)
Our Work FP-LDA 3.156 5.128 1.625 298.8426 203.3062 4.4161
FP-GGA 3.220 5.232 1.625 317.2775 174.2009 4.1765
Experiment 3.180++ 5.166++ 1.624 195+ 4.3+++

Other FP-LDA** 3.166 5.143 ̶ ̶ 205.71 4.56

calculation
FP-GGA** 3.229 5.247 ̶ ̶ 172.15 4.32

InN(WZ)
Our Work FP-LDA 3.510 5.652 1.611 406.6196 146.3152 4.5989
FP-GGA 3.585 5.777 1.611 434.3476 121.0833 4.4075

Experiment 3.533* 5.693* 1.613 ̶ 125*** 12.7***

Other FP-LDA** 3.529 5.687 ̶ ̶ 151.58 4.94
calculation
FP-GGA** 3.600 5.802 ̶ ̶ 123.37 5.36
*(Wyckoff, 1986), ** (Ahmed et.al., 2009), ***( Kim et.al., 1996), +(Ueno et.al., 1992), ++( Madelung
and Bornstein, 1982), +++( Paulus et.al., 1997)

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3.2 Electronic properties

Table 2 The calculated band gaps (eV) of XN (Al, Ga, In) compounds by the LDA, GGA and mBJ-LDA
in comparison with the experimental results and other calculations, respectively
Compounds Methods XC Eg (eV) Band gap
AlN
Present work FP-LAPW LDA 4.178 Direct (Γ-Γ)
GGA 4.165 Direct (Γ-Γ)
mBJ-LDA 5.555 Direct (Γ-Γ)
Experiment ‫ـــــــ‬ ‫ـــــــ‬ 6.231 Direct (Γ-Γ)*
Other calculations
Calculations FP-LAPW LDA 4.200 Direct (Γ-Γ)**
FP-LAPW GGA 4.210 Direct (Γ-Γ)***
FP-LAPW GGA-EV 5.034 Direct (Γ-Γ) ***
GaN
Present work FP-LAPW LDA 1.976 Direct (Γ-Γ)
GGA 1.975 Direct (Γ-Γ)
mBJ-LDA 3.202 Direct (Γ-Γ)
Experiment ‫ـــــــ‬ ‫ـــــــ‬ 3.420 Direct (Γ-Γ)*
Other calculations
FP-LAPW LDA 1.870 Direct (Γ-Γ)+
FP-LAPW GGA 1.992 Direct (Γ-Γ)++ aulus
FP-LAPW GGA-EV 2.577 et.al.,Direct
1997(Γ- Γ)***
InN
Present work FP-LAPW LDA 0 Direct (Γ-Γ)
GGA 0 Direct (Γ-Γ)
mBJ-LDA 1.162 Direct (Γ-Γ)
Experiment ‫ـــــــ‬ ‫ـــــــ‬ 0.780 Direct (Γ-Γ)+++
1.890 Direct (Γ-Γ)*
0.800 Direct (Γ-Γ)$
Other calculations
FP-LAPW LDA - 0.340 Direct (Γ-Γ)+
FP-LAPW GGA 0.192 Direct (Γ-Γ)***
FP-LAPW GGA-EV 0.355 Direct (Γ-Γ)***
*(Adachi, 2005), ** (Litimein et.al., 2002), ***(Ahmed et.al., 2005), +(Wei et.al., 2003), ++(Persson
et.al,, 2001), +++( Carrier and Wei,2005), $( Wu et.al., 2002a)

In Figure 1, we show the electronic band structure of XN (Al, Ga, In) compounds in the wurtzite
structure investigated by the LDA, GGA and mBJ-LDA methods along the high-symmetry directions
of the Brillion zone. The results show that, the XN (Al, Ga, In) compounds are direct (Γ-Γ) band gap.
Overall, the shapes of band structures investigated by the three functionals are rather similar for all
the XN (Al, Ga, In) compounds and the main differences is in the numerical value of the energy band
gap. Table 2, shows calculated band gap values along with other computations and experimental
results as a comparison. It can be seen clearly (Table 2) that, our computed gap values within LDA
and GGA are substantially smaller than the experimental results, but are in agreement with the

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/ Advances in Alloys and compounds (2015) Vol. 2 No. 1 pp. 30-36

previous calculations. Whereas, the mBJ-LDA apparently enhances them to become closer to the
experimental values. In the case of InN, this underestimation leads to a wrong metallic behavior
within LDA and GGA.

4. Conclusion
In summary, we’ve carried out the structural and electronic properties of XN (Al, Ga, IN)
compounds within the DFT investigation using the LDA, GGA and mBJ-LDA methods. Our calculated
results of structural properties with LDA and GGA nicely agree to experimental values. In the case
of the electronic properties, the energy gaps are remarkably improved by mBJ-LDA over LDA and
GGA and make them closer to the experimental results.

Acknowledgements
The authors would like to thank for the financial support (Research University Grant) of Universiti
Teknologi Malaysia (UTM) Skudai, Johor, Malaysia for the grant No. 06H14/10H78 for this research
work.

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