Opt Quant Electron

DOI 10.1007/s11082-014-0052-7

First principles study on the electronic and optical

properties of Al- and Si-doped ZnO with GGA and mBJ
approximations

A. Abbassi H. Ez-Zahraouy A. Benyoussef

Received: 26 May 2014 / Accepted: 14 October 2014

Springer Science+Business Media New York 2014

Abstract Optical properties of ZnO doped with Silicon and Aluminum were studied by
first principle calculations using the density functional theory. The optical absorption, trans-
mittance and optical constants are investigated using the full potential-linearized augmented
plane wave method with the generalized gradient approximation and mBJ approximation,
implemented in Wien2k package. With the mBJ approximation the direct optical gap of a pure
ZnO is about 3.34 eV, which is in good agreement with experimental results. The behavior
of the transmittance and the absorption of the Al-doped ZnO are higher and better than those
of the Si-doped ZnO. The transmittance of Al-doped ZnO is stable and high in the visible
light range and can reach 96 % at 400 nm. This confirms the physical characteristics that can
present Al to be used as suitable transparent material electrodes in solar cells.

Keywords DFT Optical properties Dielectric functions Wien2k Transmittance

Refractive index

1 Introduction

The zinc oxide is a transparent semiconductor of type IIVI with a normal type n conductivity.
Among the significant properties of ZnO are the direct wide band gap (3.4 eV) at ambient
temperature, the high energy binding of exciton (60 meV), which is higher than some materials
usually used such as ZnSe (20 meV) and GaN (25 meV) (Mihailovic et al. 2009; Peng et al.
2012). The no toxicity and the abundance on the ground make ZnO an ideal candidate
for transparent electrical contact for the solar cells in thin layers. This material is of great

A. Abbassi (B) H. Ez-Zahraouy A. Benyoussef

Laboratoire de Magnetisme et de Physique des Hautes Energies (URAC 12), Faculte des Sciences,
Universite Mohammed V Agdal, B.P. 1014, Rabat, Morocco
e-mail: abbassi.abder@gmail.com

A. Benyoussef
Institute for Nanomaterials and Nanotechnology, MAScIR (Moroccan for Advanced Science, Innovation
and Research), Rabat, Morocco

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 A. Abbassi et al.

importance in the field of optoelectronics and of photovoltaics. It can be used in several

applications in various scientific and industrial fields such as the piezoelectric transducers
(zgr et al. 2005), wave guides, gas detectors (Kim et al. 2010), and conducting transparent
electrodes (Lucas et al. 2007).
Semiconductors IIVI crystallize in different structures; whether, zinc sphalerite or
wurtzite. The structure studied here is wurtzite. It is the most stable structure in an ambient
temperature, and it belongs to the P63mc group space.
The electronic structures of Oxygen and Zinc band are: O: 1s 2 2s 2 2 p 4 , Zn: 1s 2 2s 2 2 p 6 3s 2
3 p 3d 10 4s 2 . The states 2 p of oxygen form the valence band and the states 4s of zinc constitute
6

the conduction band in ZnO semiconductor. The effect of doping by aluminum and indium
on ZnO properties have been studied extensively (Phillips et al. 1995; Zuo and Erbe 2010;
Ginley and Bright 2000; Gabas et al. 2005; Sharma et al. 2003; Ma and Feng 1996; Zafar et
al. 1995; Chopra et al. 1983). Chopra et al. showed that conductivity becomes higher with
doping Al and In, conductivity is then about (>5 103 1 cm1 ).
In this work we studied the aluminum and silicon doped ZnO. In the first step we substituted
aluminum in the oxygen site and continued to substitute it in Zinc site for the second step.
For silicon we substituted it in Zinc site. Finally, we will study the effect of this doping on
the electronic and optical properties of Zinc oxide (Band structure,absorption transmittance,
refractive index).
This study was realized in the 2 2 1 model which corresponds to 12.5 % with two
approximation GGA and mBJ (Tran and Blaha 2009). We will demonstrate that substituting
the Aluminum in Zinc produces more effective results when compared to the substitution
in oxygen sites. It is also very important to use this substitution as a transparent instead of
silicon. We will also show that the approximation mBJ is more effective than the GGA.
The doping of ZnO by various appropriate elements can improve its electrical and optical
characteristics and can also be a basis for others practical applications. In particular, the
doping of ZnO by the Al and Si, modifies considerably its optical properties, and it is the
subject of this work.

2 Calculation method

Electrical and optical properties of ZnO doped with Silicon and Aluminum were calculated
within a self-consistent scheme by solving the KohenSham equation based on first principles
using DFT with the generalized gradient approximation GGA method (Perdew et al. 1992;
Peterson et al. 2000) and the exchange-correlation function realized by PerdewBurke
Ernzerhof (PBE) (Perdew et al. 1996) and with mBJ approximation in Wien2k package
(Blaha and Schwarz 2006). The complex dielectric tensor was calculated in this code using
the following well known relations (Wooten 1972):

4e2    
Im () = dk ck |P |Vk Vk |P |ck (C K VK ) (1)
m
2 2 c,v
 
2 Im ( ) 
Re () = + P d (2)
0 2 2

The optical conductivity is given by:

Re () = Im () (3)
4

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First principles study on the electronic and optical properties

In the Eq. (1), C K and Vk are the crystal wave functions corresponding to the conduction
and the valence bands with crystal wave vector k. In Eq. (3), is the conductivity depends
on the current density J between the CB and VB in the direction of which flows on the
application of an electric field E in the direction in which the sum in Eq. (1) is over all
conduction and valence band states C and V. Moreover, the complex dielectric constant of a
material is given by:
() = 1 () + i2 () (4)
with

2 =   2 (5)
0 p 0 2 + 2
2 2

Using the relation of the complex refractive index and dielectric function (Lifei et al. 2012):
() = 1 () + i2 () = N 2 (6)
with
N () = n() + ik() (7)
we can then write:
1 = n 2 k 2 (8)
2 = 2nk (9)
Equation (5) is a simple formula for calculating the imaginary part where presents the
frequency of the light, 0 is the average frequency of the wavelength in the crystal, and 0 is
the dielectric constant in a vacuum. The increase of leads to the increasing of 2 (), which
may explain the high intensity of new peaks which will appear with the doping of Silicon.
The locations of new peaks are determined by:
h 0 = E i E j
where h is the Plancks constant, E i and E j are respectively the initial and final energies of
transition electrons.

3 Results and discussion

3.1 Band structures and density of states (DOS)

Figure 1ad shows the calculated band structure and total electronic density of states (TDOS)
of pure ZnO. We can see that the bottom of the conduction band and the top of the valence band
are at the same point (sigma ). It represents a characteristic of direct gap semiconductor. The
calculating of the energy gap in the first principles based on the local density functional theory
is lower than that in the experiment. A study realized with CASTEP code found that the energy
gap is 0.73 eV (Hsuan-Chung et al. 2012) using GGA approximation. In the present work
the calculation of the band structure shows that it is 1 eV with GGA approximation, which
is lower than the experimental value (3.3 eV). In some studies this gap can be placed in the
range 3.13.37 eV (Thomas 1960; Hengehold et al. 1970; Liang and Yoffe 1968; Gupta 1990;
Landolt-Bornstein 1982; Freeouf 1972; Pankove 1971; Liu et al. 1992; Kossanyi et al. 1990;
Srikant and Clarke 1997; Natsume et al. 1995; Roth et al. 1981; Srikant and Clarke 1997).
Therefore with mBJ approximation the value is 2.6 eV and becomes close to the exper-
imental value (Table 1). The Total DOS shows that the valence band above 6 eV of ZnO

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 A. Abbassi et al.

(a) (b)

(c) (d)
Fig. 1 Band structure (a, c) and total DOS (b, d) of pure ZnO with GGA and mBJ calculation

Table 1 Gap values of ZnO

GGA calculation mBJ calculation Experimental value

Gap 1.0 eV [present work] 2.6 eV [present work] 3.3 ev [2234]

can present the two following regions in the mBJ approach: the lower part from 6 to 4 eV
and the upper part from 4 to 0 eV, of which the lower valence band can be explicated by a
mixture of 3d states of Zn and 2 p of O, while the upper part comes from 2 p states of O. The
conduction band of ZnO is mainly composed of the 4s of Zn and 2 p of O.
Figures 2a, b and 3 (band structure of 2 2 1 of Al and Si) presents 2 2 1 supercell
model of doping ZnO with Aluminum and Silicon. The model of Aluminum was realized
for two cases. With the following two situations of Aluminum, the substitution of Aluminum
in the oxygen site, and for that of Zinc, we show that the band gap approaches to the metal,
zero gap semiconductor is seen. For the substitution of Al in the oxygen site we note that an
intense band around the Fermi level appears in the DOS (Fig. 4). It is mainly due to aluminum
3 p layers as shown in Fig. 4a.
ZnO doped with Si shows that several levels of energy appear and are placed very close to
the Fermi level, which almost makes ZnO a metal. TDOS calculations performed confirms
the results found in the structure of the band. In addition, for lower doping concentration
(6.25 %) the conductivity is enhanced. The energy levels (Fig. 5) approach the Fermi level
and exceed it in the case of using Aluminum and the conduction and valence bands are
overlapped.

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First principles study on the electronic and optical properties

mbj 2x2x1 model mbj

(a) (b)
Fig. 2 Band structure of: a Al substituted in Zinc site, b Si doped ZnO

Fig. 3 Band structure of Al

substituted in Oxygen site with 8
mBJ calculation
6

-2

-4

-6

3.2 Optical properties

The optical absorption study is very useful as a technique to understand the basic analysis of
optical behavior. Indeed, the optical band gap can be found in the following equation (Wang
and Guangming 2013):
( h v)m = A(h v Eg) (10)

A is a constant depending on the transition probability and m is equal to 2 for a direct gap
and 1/2 for an indirect gap. To calculate the band gap energies, we plot ( h v)m versus the
incident radiation energy (hv). By extrapolating the values of the coefficient of absorption
to zero we can find the band gap values. Figure 6 is a typical plot of ( h v)m versus incident
energy (hv). As represented in the Fig. 6, we found for mBJ calculation that the gap of pure

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 A. Abbassi et al.

-8 -6 -4 -2 0 2 4 6 8
0,3
PDOS
3p-Al

0,2

0,1

02,0
TDOS
20

15

10

0
-8 -6 -4 -2 0 2 4 6 8

Fig. 4 a PDOS of 3 p-Al in Oxygen site. b Total DOS of ZnO substituted in Oxygen site

Fig. 5 Band structure of Al substituted in Zinc site and Si doped ZnO

ZnO is direct and equal to 3.34 eV, which is in agreement with experimental values. We noted
that for GGA calculation the gap is still lower and equal to 1.87 eV.

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First principles study on the electronic and optical properties

Fig. 6 Plot of ( h v)m versus (hv) for the estimation of the band gap energy, direct gap of pure ZnO

200 pure ZnO -GGA

0
200 400 600 800
200 pure ZnO -mbj

0
200 400 600 800
200 Al in O site-GGA
Absorption

0
200 400 600 800
200
Al in O site-mbj
0
200 400 600 800
200 Al in Zn site-GGA
0
200 400 600 800
200 Al in Zn site-mbj

0
200 400 600 800
Wavelength(nm)
Fig. 7 Absorption spectra versus wavelength for pure ZnO and Al doped ZnO in 2 2 1 supercell

The optical properties of intrinsic ZnO and Zinc oxide doped with Silicon and Aluminum
were investigated on the basis of electronic structure. The intensity of absorption depends
directly on the number of light-absorbing particles, and the absorbance is proportional to the
specific absorption coefficient.
In our studies we deduced the results in Figs. 7 and 8. According to Fig. 7, the behaviors of
absorption are shown for Aluminum substituted in oxygen site, Zinc site, and for pure ZnO
versus wavelength. Using the GGA and mBJ approximation, good results were found for
mBJ. The absorption displays excellent physical behavior in the range of visible light (400
800 nm) for the Aluminum substitute in Zinc sites in the 2 2 1 structure. This substitution

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 A. Abbassi et al.

100 pur

50

0
200 400 600 800 1000 1200 1400 1600 1800
Al
Absorption

100

50

0
200 400 600 800 1000 1200 1400 1600 1800

100 Si

50

0
200 400 600 800 1000 1200 1400 1600 1800
Wavelength (nm)
Fig. 8 Absorption spectra versus wavelength for pure ZnO and Si and Al doped ZnO in 2 2 1 supercell

100 100

80 80
ZnO-GGA ZnO-mbj
60 60
40 40
Transmittance %

200 400 600 800 1000 0 200 400 600 800 1000
100 100
80 80
Al in Zn site-GGA Al in O site-GGA
60 60
40 40
0 200 400 600 800 1000 0 200 400 600 800 1000
100 100
80 Al in Zn site-mbj 80
Al in O site-mbj
60 60
40 40
0 200 400 600 800 1000 0 200 400 600 800 1000
Wavelength (nm)
Fig. 9 Transmittance spectra versus wavelength for pure ZnO and Al doped ZnO in 2 2 1 supercell

is more crucial than a pure ZnO from the 300 nm wavelength because the absorption becomes
very low. In this range the material does not absorb, however the substitution of Al at the
site of oxygen shows a high absorption which will influence the transparency of ZnO. The
introduction of Al atoms in the oxygen site is not vital for the optical properties.
Figure 8 shows that the absorption of Al doped ZnO in 2 2 1 supercell, is lower than
that of pure ZnO and that of Si doped ZnO in the range of visible light.
Figure 9 shows that in pure ZnO the average transmittance is 86 % in the visible light
region; that is to say, the Zinc oxide has a transmittance at normal incidence in 350800 nm.
It could be noted that at longer wavelengths ( > 400 nm), ZnO becomes transparent and no
light is scattered or absorbed. It was shown in several experimental results that thin film Al

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First principles study on the electronic and optical properties

100 100
80 80
Pure ZnOmbj
60 60
40 40
200 400 600 800 1000 200 400 600 800 1000
Transmittance %

100
90
80
60 60 si-mbj
Si
40
30
200 400 600 800 1000 200 400 600 800 1000
100 100
80 80 Al-mbj
Al
60 60
40 40
200 400 600 800 1000 200 400 600 800 1000
Wavelength (nm)
Fig. 10 Transmittance spectra versus wavelength for pure ZnO and Si, Al doped ZnO in 2 2 1 supercell

doped ZnO has a higher transmittance above 80 % (Wang et al. 2007; Kuo et al. 2006). In the
present work its noted also that the substitution of Aluminum in oxygen sites in 2 2 1
supercell with two approximation mBJ and GGA, have a low transparency. The transmittance
is low in the region of visible light, while for Aluminum in Zinc sites, the material presents a
high transparency and can reach 96 % at 400 nm. With incorporation of Si the transmittance
increases in significant value, but it remains unstable in the visible light. We can also see that
the mBJ calculation shows a favorable result.
According to the Figs. 9 and 10, the substitution of Al in Zinc sites in the 2 2 1 model
is more important than that of oxygen sites and that of doping Silicon. It shows that the
transmittance is high and stable in the visible light. Therefore the Al in Zinc sites can be used
to improve this property and can be used in several PV applications. According to the curves
in Fig. 11, small doping concentrations (6.25 %) present a relatively stable transmission in
the range of visible light. This stability is clearly seen in the case of Silicon, with the absence
of the attenuation observed for 25 and 12.5 % above 500 nm.
The static dielectric constant 1 (0) extracted at the equilibrium lattice constant is about
3.92. The electronic part of the static dielectric constant can be related to the refractive index;
n(0) = 1 (0) (Poelman and Smet 2003), the values are in Table 2.
For ZnO doped Si, Al substitute in Oxygen site and Al substitute in Zinc site, the static
refractive index value is respectively 2.72, 4.18, 1.78. According to Fig. 12, the refractive
index of ZnO doped Si varies according to energy. n = 3.80 is the maximum value cor-
responding to energy 1.24 eV. This value shows a weak transparence and a considerable
absorbance. For the substitution of Aluminum in the oxygen site in the range 300500 nm,
the refractive index reached respectively these two peaks 2.92 and 2.55. They correspond
to a very weak transmittance of 65 %. The substitution of Al in the site of oxygen does not
produce transparency. This result is consistent with Fig. 7 where the absorption is important
in the same range.
In Fig. 12 the Aluminum substituted in the Zinc sites present good transparency and a
stability in the range of the visible light. The refractive index varies slightly according to

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 A. Abbassi et al.

100 100

80 80
Al-25%
60 60
Si-25%
40 40

0 300 600 0 300 600

Transmittance %

100
90 Si-12,5%
80
Al-12,5%
60 60
40
30
0 300 600 0 300 600
100 100

80 80
Al-6,25%
60 Si-6,25% 60

40 40

0 300 600 0 300 600

Energy (ev) Energy (ev)
Fig. 11 Transmittance spectra versus wavelength for different percentages of Al and Si

Table 2 Static refractive index

n(0) = 1 (0) 1 (0)
and static dielectric constant of
pure ZnO and doped with Si and
Pure ZnO 1.98 3.92
Al in 2 2 1 supercell
Al doped ZnO (Al at Oxygen site) 4.18 17.44
Al doped ZnO (Al at Zinc site) 1.78 3.16
Si doped ZnO 2.72 7.43

energy. At 800 nm corresponding to energy 1.55 eV, the refractive index of Al doped ZnO is
1.7 which is in agreement with the refractive index for indium oxide at the same wavelength
(Rahnamaye Aliabad et al. 2009). This analysis confirms the results found for the calculation
of transmittance and absorption.

4 Conclusion

We have calculated the electronic and optical properties of undoped ZnO and doped with
Aluminum and Silicon in the 2 2 1 supercell model with different approximations;
the generalized gradient approximation (GGA) and mBJ using the FP-LAPW method. The
calculations show a refractive index which increases with increasing Silicon doping and
becomes suitable for Aluminum compared to pure ZnO.
The decrease of absorption coefficient, a stable and high transmittance in the visible light
range were gained with the incorporation of Al in ZnO. We showed effective results between
calculations and the existing experimental data. These studies based on first-principles calcu-
lations investigate that the substitution of Al in the sites of oxygen is not optimal for optical
properties of ZnO. However, substituting it in the Zinc sites produced agreeable results.
Therefore when comparing Si with Al in the 2 2 1 structure, Silicon does not present

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First principles study on the electronic and optical properties

4 pure 4 Al in Zn site

3 3

2 2

1 1
Refractive Index

0 0
0 2 4 6 8 10 12 14 0 3 6 9 12 15

4 4
Al in O site Si
3 3

Si
2 2

1 1

0 0
0 3 6 9 12 15 0 3 6 9 12 15
Energy (ev) Energy (ev)
Fig. 12 Refractive index spectra of pure ZnO, and doped with Si, Al

a stability of transmittance to the length of visible light. This confirms the performance that
can present Al to be used as suitable transparent material electrodes in solar cells.

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