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First Principles LDA plus U Calculations for ZnO Materials

Article  in  Integrated Ferroelectrics · July 2014

DOI: 10.1080/10584587.2014.905086

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 Integrated Ferroelectrics, 155:15–22, 2014
Copyright © Taylor & Francis Group, LLC
ISSN: 1058-4587 print / 1607-8489 online
DOI: 10.1080/10584587.2014.905086

First Principles LDA+U Calculations

for ZnO Materials

M. K. YAAKOB,1,2 N. H. HUSSIN,1,2 M. F. M. TAIB,1,2

T. I. T. KUDIN,1,2 O. H. HASSAN,2,3,∗ A. M. M. ALI,1,2
Downloaded by [Universiti Teknologi Mara], [Oskar Hassan] at 20:58 27 May 2014

AND M. Z. A. YAHYA4
1
Faculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam,
Malaysia
2
Ionics Materials & Devices Research Laboratory (iMADE), Institute of Science,
Universiti Teknologi MARA, 40450 Shah Alam, Malaysia
3
Faculty of Art & Design, Universiti Teknologi MARA, 40450 Shah Alam,
Malaysia
4
Faculty of Defence Science and Technology, Universiti Pertahanan Nasional
Malaysia, 57000 Kuala Lumpur, Malaysia

The electronic, structural, elastic, and optical properties of zinc oxide (ZnO) with
wurtzite-type structure were investigated using first-principles calculation based on
density functional theory (DFT) with local density approximation (LDA) plus Hubbard
U (DFT–LDA+U)method. Hubbard U improved the calculated results, allowing it to
exhibit good agreement with experimental data. The DFT–LDA+U method successfully
predicted the electronic properties of ZnO with better described the localization of
transition metal Zn 3d electron. The calculated optical dielectric function of ZnO and
its relation with electronic properties were further discussed.

Keywords ZnO; electronic properties; density functional theory (DFT)

Introduction
Zinc oxide (ZnO) is among the most popular materials that have received considerable at-
tention because of its wide energy gap semiconductivity, piezoelectricity, room-temperature
ferromagnetism, high photoactivity, and chemical sensing effects [1–5]. Hence, ZnO is a
promising material for a wide range of applications, such as in sensors, optoelectronics,
spintronics, photocatalysts, light-emitting diodes, and solar cells [3, 6–8]. ZnO exhibits a
stable wurtzite crystal structure under ambient conditions. Meanwhile, a rock-salt crystal
structure is observed at a relatively high pressure, and ZnO is stabilized with a zinc-blende
crystal structure growing from the cubic substrate [3].
Recently, p-type doping of ZnO has attracted considerable theoretical and experimental
studies because of its in-demand applications in optoelectronic devices [9]. In addition,
impurities such as oxygen vacancies (VO ), interstitial zinc atoms (Zni ), and hydrogen

Received July 23, 2013; in final form January 12, 2014.

∗
Corresponding author. E-mail: oskar@salam.uitm.edu.my
Color versions of one or more of the figures in the article can be found online at
www.tandfonline.com/ginf.

15
 16 M. K. Yaakob et al.

impurities introduced during crystal growth are responsible for the n-type behavior of
ZnO. This essential behavior makes ZnO attractive fundamentally and this behavior can
be exploited in a wide range of electronic applications [10, 11]. In addition, ZnO contains
transition metal of Zn 3d electrons, which provide interesting phenomena in condensed
matter physics [12, 13]. Thus, ZnO has tremendous potential in novel electronic devices.
The first-principles method based on density functional theory (DFT) within local density
approximation (LDA) has been successfully applied to study material systems in molecular,
surface, interface, and solid states. This first principles approach can accurately predict
the ground state properties of perovskite-type ABO3 materials [14–16]. However, this
conventional DFT–LDA approach is collapsible for strongly correlated transition material
cases that cannot efficiently describe the localization of strongly correlated d and f electrons
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[17, 18]. The hybrid DFT–HF functional (such as BH&HLYP, B3LYP, and B3PW91)
[19], dynamic mean field theory (DMFT) [20], and DFT–LDA+U functional [17] can
significantly improve the calculation of strong electron–electron correlation transition metal
localization.
In the present study, the first-principles method based on DFT–LDA with semiempirical
Hubbard U was applied to calculate the structural, elastic, electronic, and optical properties
of ZnO materials with wurtzite structure. The calculated results were compared with various
experimental data from literature. The performance and accuracy of the Kohn–Sham plane-
wave DFT method with semiempirical LDA+U functional, as implemented in CASTEP
computer code for transition oxide materials of ZnO, were further discussed.

Computational Methods
First-principles calculations of structural, elastic, electronic, and optical properties of ZnO
materials with wurtzite structure were performed using DFT as implemented in CASTEP
code [21]. CASTEP uses a plane wave basis set and a pseudopotential within the frame-
work of Kohn–Sham DFT. LDA [22, 23] was used to describe the exchange–correlation
functional. An ultrasoft pseudopotential [24] was also introduced to allow the present cal-
culation to be performed with a 380 eV kinetic cutoff energy. The 5 × 5 × 4 k-point grid
with 0.07 Å−1 k-point separations was used in all calculations. We employed the semiem-
pirical LDA+U approach with effective Hubbard U values of 0, 2, 4, and 6 eV to treat the
transition metal of Zn 3d electron. Geometric optimization calculation was performed with
less than 5×10−6 eV per atom convergence threshold of energy change, 0.01 eV per Å, and
0.02 GPa maximum force and stress, respectively, and not more than 5.0 × 10−4 Å dis-
placement.

Results and Discussion

The ZnO crystal with wurtzite-type structure and hexagonal phase (P 63mc space group)
is shown in Fig. 1. The initial lattice parameter and atomic positions of Zn and O atoms
were set based on experimental data collected from reference [25]. The calculated lattice
parameter, electronic energy gap, bulk modulus, and elastic tensor of ZnO crystal with
wurtzite-type structure are presented in Table 1. Experimental data and other calculations
obtained from literature are also provided for comparison. The calculated results exhibit
good agreement with other calculation methods using DFT–LDA and the experimental
data. The calculation based on the Kohn–Sham DFT–LDA approach is an underestimation
of experimental data, with 1% to 3% and 50% difference for lattice parameter and energy
 First Principles LDA+U Calculations for ZnO Materials 17
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Figure 1. Crystal structure of ZnO with hexagonal phase (P 63mc space group).

band gap, respectively. As expected, the LDA (U = 0 eV) calculation as implemented in

CASTEP code show underestimates lattice constants up to −2%. The increase of effective U
from 2 eV to 6 eV in LDA+U calculation tends to improve the calculated lattice parameter
with better agreement to the experimental data [26]. This is believe to be associated with
the improved electronic localization of Zn 3d shells in LDA+U calculation. In addition, the
calculation with Hubbard U also can significantly enhanced the calculated electronic energy
gap of 1.154 eV (U = 6 eV) rather than using conventional LDA (U = 0 eV) with smaller

Table 1
Lattice parameter, crystal volume, electronic energy gap, bulk modulus and elastic
stiffness tensor of ZnO calculated using DFT−LDA+U methods. Other calculation [26]
and experimental data [25, 27] also given for comparison

Present work (LDA+U) Calculationa Experimental

U = 0 eV U = 2 eV U = 4 eV U = 6 eV LDA -

a (Å) 3.186 3.190 3.193 3.197 3.210 3.253b

c (Å) 5.150 5.151 5.154 5.154 5.136 5.205b
! (Å3) 45.27 45.40 45.51 45.62 45.83 47.70
c/c 1.62 1.62 1.61 1.61 1.60 1.60
Eg (eV) 0.794 0.945 1.062 1.154 0.764 3.2b
B (GPa) 176.9 156.2 147.7 159.8 162 142.4c
C11 (GPa) 240 223 211 222 227 209d
C12 (GPa) 161 132 128 140 133 120d
C13 (GPa) 135 115 107 118 118 104d
C33 (GPa) 253 234 225 241 232 216d
C44 (GPa) 37 41 41 40 40 44d
C66 (GPa) 39.5 45.5 41.5 41 47 44.5d
 18 M. K. Yaakob et al.

electronic energy gap of 0.794 eV. However, the relative error between the calculated
electronic band gap of 1.154 eV (U = 6 eV) and the experimental optical energy gap of
3.2 eV is as high as 60%. For better comparison, the measurement of electronic energy gap
using core-level spectroscopic methods, such as X-ray photoelectron spectroscopy, X-ray
emission spectroscopy and electron energy loss spectroscopy, could be suggested to be
carried out.
We also calculated the elasticity of ZnO crystal with wurtzite-type structure. Elastic
modulus and elastic tensor provide important information regarding microelectronic de-
vices. To the best our knowledge, the present study is the first to determine the effect of
Hubbard U on the elastic properties of ZnO. In this work, the inclusion of Hubbard U in
DFT–LDA significantly improved the calculation of the bulk modulus and elastic stiffness
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tensor (Table 1). This result is consistent with previous studies on elastic constants for
BiFeO3 materials using first-principles DFT–GGA+U calculation [27]. Our calculated re-
sults with a Hubbard U value of 4 eV yields a bulk modulus of 147.7 GPa, which is in good
agreement with the experimental bulk modulus of 142.4 GPa [28]. Moreover, the elastic
stiffness tensors C11 , C12 , C13 , C33 , C44 , and C66 were calculated to be 211, 128, 107, 225,
41, and 42 GPa, respectively, which are in agreement with the other calculation [29] and
experimental data [30].
The first-principles DFT–LDA+U method has been extensively applied in calculating
electronic properties because, unlike the conventional DFT–LDA approach, the former
successfully defines the strongly correlated materials of d and f electron localization. The
calculated electronic band structure of ZnO is shown in Fig. 2. It can be obtained that
the effective Hubbard U (U = 2, 4, and 6 eV) in LDA+U calculation tends to upper

Figure 2. Calculated electronic band structure of ZnO with wurtzite-type structure using
DFT−LDA+U (U = 0 eV, 2 eV, 4 eV and 6 eV) methods.
 First Principles LDA+U Calculations for ZnO Materials 19
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Figure 3. Calculated electronic total and partial density of states (DOS) for ZnO with wurtzite-type
structure using DFT−LDA+U (U = 0 eV, 2 eV, 4 eV and 6 eV) methods. The experimental observed
spectra [28] (black dotted circle) for Zn 3d states also given for comparison.

shifted the minimum conduction band, to give larger gap between lowest conduction band
and highest valence band. Figure 3 shows the comparison among the calculated electronic
density of state of ZnO with different Hubbard U values of 0, 2, 4, and 6 eV. The calculation
with Hubbard U values successfully improved our calculated DOS of ZnO with a better
description of the localization of transition metal of Zn 3d electron. The calculated total
DOS of ZnO with DFT–LDA+U (U = 6 eV) (green solid lines) is in agreement with the
experimental data [31] (black dotted circles) compared with a smaller Hubbard U (U = 0,
2, 4 eV). The calculated partial DOS of Zn 3d states on the valence band was significantly
shifted to the experimental spectra at approximately −8 eV when Hubbard U was applied
in the calculation. A similar but smaller shift could be observed for O 2p states. This shift
is attributed to the Coulomb energy U treatment of the electron–electron interaction in Zn
3d orbital. The high accuracy of first-principles DFT–LDA+U method presented in the
 20 M. K. Yaakob et al.
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Figure 4. Calculated optical real and imaginary part of dielectric function of ZnO with wurtzite-type
structure using DFT−LDA+U (U = 6 eV) methods. The calculated imaginary part of dielectric
function is in good agreement with experimental observed spectra [29] (black dotted circle).

current study is important for future work in materials systems with transition metal Zn 3d
atom.
We extended our first-principles prediction to the optical properties of ZnO. Optical
properties are crucial in optical, optoelectronic, and photonic devices. These properties are
also important in first-principles DFT because they are related to electronic properties. The
optical dielectric functions of ZnO for real (ε1 ) and imaginary (ε2 ) parts are shown in Fig. 4.
The calculated dielectric function for the imaginary part exhibits good agreement with the
experimental observed spectra [32]. The three major peaks of A, B, and C are located at
approximately 4, 8, and 14 eV photon energy, respectively. These peaks are consistent with
the peaks observed in the experimental spectra. According to the calculated DOS, we found
that the first A peak at 4 eV photon energy is associated with the excitation electron of O
2p states from the occupied valence band to the unoccupied conduction band. The second
B peak at 8 eV probably results from the excitation electron of small O 2p states from the
lower energy of the occupied valence band to the unoccupied conduction band. The third
highest C peak at 14 eV photon energy is attributed to the excitation electron of the largest
Zn 3d states from the occupied valence band to the unoccupied conduction band.

Conclusion
The first-principles DFT–LDA+U study was successfully performed on the structural,
elastic, electronic, and optical properties of ZnO with wurtzite-type structure. The calculated
lattice parameter and elastic properties of ZnO were closer to the experimental data when
Hubbard U was applied in the calculation. This study is the first to reveal that the application
 First Principles LDA+U Calculations for ZnO Materials 21

of Hubbard U can significantly improve the calculation of the elastic properties of ZnO. A
Hubbard U of 4 eV exhibited the best calculated elastic constant of ZnO compared with
the experimental data. For calculated electronic DOS, Hubbard U enhanced the calculation
of the localization of Zn 3d electron. As a result, the calculated data exhibited significantly
good agreement with the experimental data. The calculated optical dielectric function of
ZnO using the DFT–LDA+U method was consistent with the experimentally observed
spectra.

Acknowledgments
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The authors would like to acknowledge the Ministry of Education (MOE), Malaysia and the
Institute of Science (IOS), Universiti Teknologi MARA (UiTM), Malaysia for the facilities
and support provided.

Funding
The authors would like to acknowledge the Ministry of Education (MOE), Malaysia for
FRGS funding and Universiti Teknologi MARA (UiTM) for PSI and CIFI funding.

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