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First-Principles Calculation of Electronic Structure and Optical Properties of Sb-Doped ZnO

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2008 Chinese Phys. Lett. 25 3735

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CHIN.PHYS.LETT. Vol. 25, No. 10 (2008) 3735

First-Principles Calculation of Electronic Structure and Optical Properties of


Sb-Doped ZnO
ZHANG Fu-Chun( LS) 1,2
, ZHANG Zhi-Yong( ]
)3 , ZHANG Wei-Hu( %m) 1,2
,
YAN Jun-Feng( A
)3 , YUN Jiang-Ni( V
)3
1
Xian Institute of Optics and Precision Mechanics, Chinese Academy of Sciences, Xian 710068
2
College of Physics and Electronic Information, Yanan University, Yanan 716000
3
Information Science and Technology Institution, Northwest University, Xian 710127

(Received 29 June 2008)


The geometric structure, electronic structure, optical properties and the formation energy of Sb-doped ZnO with
the wurtzite structure are investigated using the first-principles ultra-soft pseudo-potential approach of plane
wave based upon the density functional theory. The calculated results indicate that the volume of ZnO doped
with Sb becomes larger, and the doping system yields the lowest formation energy of Sb on the interstitial site
and the oxygen site. Furthermore, Sb dopant first occupies the octahedral oxygen sites of the wurtzite structure.
It is found that Sb substituting on oxygen site behaves as a deep acceptor and shows the p-type degenerate
semiconductor character. After doping, the electron density difference demonstrates the considerable electron
charge density redistribution, which induces the effect of Sb-doped ZnO to increase the charge overlap between
atoms. The density of states move towards lower energy and the optical band gap is broadened. Our calculated
results are in agreement with other experimental results and could make more precise monitoring and controlling
possible during the growth of ZnO p-type materials.

PACS: 71. 15. Mb, 78. 20. e, 78. 45. +h

Zinc oxide (ZnO) is a typical wide band gap ZnO:N.[6] Joseph et al.[7] experimentally reported that
(3.37 eV) IIVI compound semiconductor with a large they have observed resistivity of 2cm at room tem-
exciton binding energy (60 meV) at room tempera- perature and a hole concentration of 4 1019 cm3 ,
ture. It has attracted much attention because of po- and the effect of dopant on the electronic properties
tential applications in fields of optoelectronic devices has been studied by Yamamoto[8] using the ab ini-
such as blue-light emitting, short wavelength laser tio pseudo-potential density function theory. On the
diodes with low thresholds in the UV light-emitting other hand, a few reports of p-type ZnO have been pre-
diodes, solar cells, transparent and conducting elec- sented for other elements such as P, As or Sb.[9] How-
trode in solar cells surface acoustic wave devices, ever, Sb-doped ZnO is quite puzzling due to large size
and chemical and biological sensors.[13] It is well mismatching and deeper acceptor levels. The studies
known that undoped ZnO exhibits n-type semiconduc- of p-type ZnO are a little made both experimentally
tor characters. Generally speaking, the electronic, op- and theoretically. So it is necessary for us to use the
tical, and magnetic properties of ZnO can be adjusted first principle method to study the effect of Sb-doped
by using suitable dopants. Fabrication of high-quality ZnO.
p-type ZnO is rather difficult due to the problems such ZnO has a hexagonal wurtzite structure belong
as deep acceptor level, low solubility of the acceptor to P 63mc space group, a C6v4 symmetry system.
dopants and a strong self-compensating effect forming The unit cell contains two Zn cations and two O an-
native defects containing zinc interstitials (Zni ), oxy- ions. The ZnO crystal thus can be viewed as a se-
gen vacancies (VO ) and hydrogen incorporation.[4,5] quence of O-Zn double layers stacked along the c-axis
Although experimental and theoretical investigations or the (0001) direction. The lattice parameters are
have been reported that p-type ZnO can be fabricated the second nearest neighbour distances a = 0.3253 nm,
by substituting O by group V elements (such as N, c = 0.521 nm, = = 90 , = 120 , the bond length
P, As and Sb). To our knowledge, the work on p- of Zn-O along the c axis is 0.199 nm, the other axis is
type doped ZnO is still very difficult to obtain low- 0.197 nm and the ratio c/a = 1.602. In order to study
resistivity p-type ZnO in experimental investigations. the fractional Sb substitution, we consider a cell larger
Now the behaviour of p-type ZnO has been widely than the basic unit. Thus we construct a 2 2 2 su-
investigated in an attempt to understand how to percell consisting of 32 atoms, as displayed in Fig. 1.
successfully fabricate p-type ZnO materials. Some In our study, the electronic structure, band struc-
groups have reported to successfully fabricate p-type ture, density of states (DOS) and electronic den-

Supportedby the National Natural Science Foundation of Shaanxi Province under Grant Nos 2005F39 and 08jk487.
Email:
zhangfuchun72@163.com

c 2008 Chinese Physical Society and IOP Publishing Ltd
3736 ZHANG Fu-Chun et al. Vol. 25

sity difference of Sb-doped ZnO are performed using The total DOS of pure ZnO is displayed in Fig. 2(a)
the CASTEP program.[10] The PW91 parametriza- for comparison. Figure 2(a) shows that valence bands
tion is taken as the exchange-correlation potential in of ZnO can be divided into two main groups, the low-
the generalized gradient approximation (GGA). The est valence bands from 6.0 eV to 4.0 eV are mostly
cut-off energy of plane wave is set to be 420 eV. derived from the Zn 3d states. The upper valence
The maximum rms convergent tolerance is less than bands above 4.0 eV originate mostly from the O 2p
2 105 eV/atom. That is, the force imposed on each states. In addition, the O 2s states around -18eV are
atom is not greater than 0.1 eV and 0.1 GPa for stress. weakly interaction with other valence bands and are
The Brillouin zone integration are approximated using omitted in this study. For the conduction bands, the
the special k-points sampling scheme of Monkhorst- lowest conduction bands show a strong Zn 4s contri-
Pack and 13 13 7 k-points grid are used. All the bution, Zn 4s states play an important role in the con-
calculations are performed in reciprocal space. ductive properties and show the charge transfer from
the Zn 4s levels to O 2p levels, which leads to the
centre of gravity for the local density of states at the
oxygen sites shifting towards the lower-energy levels.
Those indicate that ZnO is a kind of mixed bond metal
oxide semiconductor material with ionic bond greatly
stronger than covalent bond. The band gap is found
to be 1.12 eV in our work, much smaller than the ex-
perimental value of 3.37 eV.[11] The reason for such
a disagreement is the well-known shortcoming of the
theory frame of DFT-LDA. The underestimate of the
band gap is 2.25 eV, compared with the experimental
data of band gap of 3.37 eV. When the scissor ap-
proximation (SA) makes the conductive bands rigidly
shift towards higher energy by 2.25 eV, the band gap
becomes 3.37 eV, in excellent agreement with the ex-
perimental results.
The formation energy of the interstitial site, the
oxygen site and the zinc site are calculated. The for-
mation energy Ef may be expressed as

Ef = EZnO:Sb + EZnO + nESb + mEZn + 0 , (1)


Fig. 1. Supercell of ZnO. White atoms are oxygen and
black atoms are zinc. where EZnO:Sb is the total energy of ZnO doped with
Sb, EZnO is the total energy of the perfect supercell,
All the present works are performed by employing ESb and EZn are the total energy of Sb and Zn, and
the method of the first principles calculation on the 0 is the chemical potential of an oxygen molecule.
electronic structure of Zn1x Sbx O for the cases of Sb The formation energies Ef of Sb on the interstitial
on the interstitial site, the oxygen site and the zinc site site, the oxygen site and the zinc site are 3.625, 7.843,
by the CASTEP software package based on density 3.014 eV, respectively. It is obvious that the formation
function theory (DFT) using the supercell approach. energies of Sb on the interstitial site and the oxygen
In the cases of Sb-doped ZnO, the electronic structure site are smaller than those on the zinc site. Thus,
and conductive properties are theoretically calculated, in the case of Sb-doped ZnO, the Sb ion will occupy
the relationship between the distribution of electronic the interstitial site and the oxygen site firstly, which
state and electronic structure is studied. Addition- is in agreement well with the experimental results,[12]
ally, since the supercell approach is time-consuming, the formation energies of Sb on the zinc site is much
we construct a supercell of eight unit cells consisting higher, which can not form this structure and are not
of 32 atoms at most. investigated in the study.
In order to show the Sb doping effect on the elec- We show the total DOS of Sb-doped ZnO in
tronic structure and optical properties of ZnO, the Figs. 2(b)2(c), respectively. There is excess holes at
band structure, total DOS, partial density of states the top of the valence bands, which results in the p-
(PDOS) and the electron density difference of pure type nature of Sb-doped ZnO. The Fermi level moves
ZnO are calculated firstly for comparison. The com- into the valence bands (VBs). For Sb on the oxygen
putational results are shown in Figs. 2(a), 3(a), 4(a), site, Fig. 2(b) show a narrow Sb-impurity band with
respectively. the introduction of Sb impurity in the band gap. Holes
No. 10 ZHANG Fu-Chun et al. 3737

in the band are localized by repulsion due to a narrow


Sb impurity and form a acceptor level in the middle Eg = Ego + EgBM EgW , (2)
of the band gap. For the case of Sb on the intersti-
where Ego is the band gap of undoped ZnO, EgBM
is
tial site, we can see that additional peaks appear near
the BursteinMoss moving and EgW is the change of
the Fermi energy level. One with the bandwidth about
conduction band resulting from the many-body effect
2.0 eV locates at the bottom of the lower VBs, another
among electrons.
with the bandwidth about 1.2 eV lies above 15 eV.
In order to further probe the effect of p-type dop-
The acceptor level due to the Sb dopant on the inter-
ing with Sb in the valence band, the PDOS of dopant-
stitial site appears near the Fermi energy level, which
site are shown in Figs. 3(b) and 3(c). It is found that
gives rise to a strong self-compensation effect. It is the
some additional peaks appear in the bottom of the
main difficulty in fabricating high quality p-type ZnO
upper VBs and another large peak emerges above the
materials for the case of Sb on the interstitial site.
lower VBs because of the overlap of the Sb-acceptor
In addition, the DOS moves greatly towards lower
orbitals. From the PDOS, we can see that the Sb
energy, and optical band gap is broadened. The rea-
2p state contributes to the additional peak near the
sons are as follows: on the one hand, the Burstein
Fermi energy. For the large one, Sb 2s state makes
Moss shift due to the high concentration of carriers
great contribution. At the same time, a number of
makes the optical absorption edge moving towards low
holes are produced around the top of the VBs. For
energy and the optical band gap is broadened.[13] On
the case of Sb on the oxygen site, this shows greatly
the other hand, interactions among electric charges
localization characteristics than Sb on the interstitial
result in many-body effect, which causes the optical
site due to the strong repulsive potential. For Sb on
band gap becomes narrow.[14] However, the Burstein
the interstitial site, we find that the wide Sb-impurity
Moss effect on the band gap is more larger than that of
bands are formed and broadened near the top of va-
many-body effect, so the band gap is broadened with
lence band. We can clearly observe that bandwidth
Sb doping.
about 3.1 eV including three additional peaks locates
It can be expressed by the following equation:
at the bottom of the lower VBs.

Fig. 2. Total density of states (a) undoped ZnO, (b) Sb on the oxygen site, (c) Sb on the interstitial site.

Fig. 3. Site-decomposed density of states: (a) undoped ZnO, (b) Sb on the oxygen site, (c) Sb on the interstitial site.
3738 ZHANG Fu-Chun et al. Vol. 25

Fig. 4. Plot of electron density difference: (a) undoped ZnO, (b) Sb on the oxygen site, (c) Sb on the interstitial
site. Grey atoms are oxygen, white atoms are zinc, and black atoms are antimony.

In addition, the DOSs move greatly towards lower density of Sb-doped ZnO. Due to the hole doping, the
energy and the VBs are broadened. From the above Fermi level moves into lower energy and the system
results of Sb-doped ZnO, we can notice that although shows the p-type degenerate semiconductor charac-
the Fermi level moves downwards into the original ter. In addition, for the case of Sb on the oxygen site,
VBs, there is significant change in the bottom of VBs. a narrow Sb-impurity band appears near the Fermi
It is predicted that those impurity levels in the band level, and holes are localized by repulsion due to a
gap are acceptor level. narrow Sb-impurity band. For Sb on the interstitial
The plot of difference charge density of undoped site, Sb-impurity band is broadened and the donor
ZnO, Sb on the oxygen site and Sb on the inter- level appears at the bottom conductive bands. This
stitial site are shown in Figs. 4(b) and 4(c), respec- leads to a strong self-compensation effect. Hence, it
tively. The difference charge density is plotted along is adaptive to fabricate ZnO as highly conductive p-
the x z plane containing Zn, O and Sb in the super- type materials, further experimental works are needed
cell. For undoped ZnO in a 222 supercell, Fig. 4(a) to compare with our calculated results.
shows that ZnO looks like strongly ionic character
and presents the O 2p and Zn 3d hybridization phe-
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