Rare Metal Materials and Engineering

Volume 44, Issue 10, October 2015

Online English edition of the Chinese language journal

Cite this article as: Rare Metal Materials and Engineering, 2015, 44(10): 2409-2414. ARTICLE

Density Functional Theory Study on the Electronic Struc-

ture and Optical Properties of SnO2
Shao Tingting, Zhang Fuchun, Zhang Weihu

Yan’an University, Yan’an 716000, China

Abstract: The structure electronic and optical properties of rutile-type SnO2 were studied based on plane-wave pseudopotential
density functional theory (DFT) adopting GGA, LDA, B3LYP and PBE0, respectively. The computing results show that the
properties calculated by GGA and LDA are very close, which correspond to those by ultra-soft pseudopotential and norm
conserving pseudopotential, respectively, and the properties calculated by B3LYP are near to those by PBE0. The band gap
obtained from B3LYP and PBE0 is much more consistent with the available experimental data than that fr om GGA and LDA,
whose band gap calculated by norm conserving pseudopotential is bigger than that by ultra-soft pseudopotential. However, the
density of state and optical properties calculated from every type are basically similar in qualitative analysis, and the numerical
values have a little difference. From the whole results calculated by the six methods, we can see that the structure, electronic and
optical properties of rutile-type SnO2 calculated by B3LYP and PBEO are more near to the available experimental data than
those by other methods.

Key words: SnO2; density functional theory; electronic structure; electronic property; optical property

Stannic oxide SnO 2, an n-type wide band gap semicon-
ductor, with band gap of 3.6 eV in experiment which is
wider than that of ZnO (3.36 eV), has high exciton binding
energy (130 meV in experiment) [1], so SnO 2 has attracted
increasing interests and presents potential applications such
as catalytic support materials, transparent electrodes for liq-
uid crystal displays (LCDs), solar cells, chemical gas sen-
sors, varistors and optoelectronic devices[2,3]. The behaviors
of SnO2, such as electronic properties, lattice dynamics and
optical properties have attracted sustained investigations
both in experiments and theories[4,5]. However, those studies
seem just to use one or two methods to calculate the proper-
ties of SnO2 that is inadequate to illustrate the different re-
sults calculated by different methods and which method is
better for SnO2. The more methods to calculate the same
SnO2 structure the better to understanding the behavior of
the SnO 2. Thus in the present paper, we will investigate the
structure, electronic, and optical properties of rutile-type
SnO2 via different types of functional forms and compare
the results.
1 Method for calculation
In the present letter, we used four types of functional forms
to calculate the electronic and optical properties of SnO2. The
four types of functional forms were used through the Vienna
Ab-initio Simulation Package (VASP) program[6,7], including
the generalized gradient approximation (GGA)[8], the local
density approximation (LDA)[9], Becke’s Three Parameter
Hybrid Functional Using the LYP Correlation Functional
(B3LYP), and Perdew-Burke-Ernzerh of based hybrid func-
tional(PBE0). The oxygen 2s2, 2p4 electrons and the stannum
5s2, 5p2 electrons were treated as part of the valence states.
The energy cut-off of plane wave, Monkhorst–Pack mesh of
Brillouin-zone sampling, and the self-consistent convergence
of the total energy for GGA (Ultra-soft), GGA (Norm con-
serving), LDA (Ultra-soft), LDA (Norm conserving), B3LYP

Received date: April 15, 2015

Foundation item: Scientific Research Program of the Educational Committee of Shanxi Province, China (2013JK0917); Scientific Research Program of Yan’an, Chi-
na (2013-KG03)
Corresponding author: Zhang Fuchun, Ph. D., Associate Professor, College of Physics and Electronic Information, Yan’an University, Yan’an 716000, P. R. China,
Tel: 0086-911-2332045, E-mail: yadxzfc@yau.edu.cn
Copyright © 2015, Northwest Institute for Nonferrous Metal Research. Published by Elsevier BV. All rights reserved.

2409
 Shao Tingting et al. / Rare Metal Materials and Engineering, 2015, 44(10): 2409-2414

and PBE0 are listed in Table 1. Table 2 Values of optimized structure and experimental structure

2 Results and Discussion Structure a=b/nm c/nm c/a

Optimized structure 0.4924 0.3295 0.669
2.1 Structural properties
Experimental structure 0.4738 0.3189 0.673
The rutile-type SnO2 belongs to the tetragonal system,
which contains two Sn atoms and four O atoms in a primitive
20 20
cell[10]. Two Sn atoms occupy body heart position [0, 0, 0] and 15
GGA Ultra-soft
15
GGA(Norm conserving)

vertex position [1/2, 1/2, 1/2] of the tetrahedron, and two O 10 10

atoms [u, u, 0], [1/2+u, 1/2-u, 1/2] are coplanar with Sn atoms, 5 5

Energy/eV
0.015 eV 0.602 eV
0 0
whose plane is perpendicular to that of the other two O atoms
-5 -5
[-u, -u, 0], [1/2-u, 1/2+u, 1/2][11]. The structure of the primitive -10 -10
cell of SnO2 is shown in Fig.1. To minimize the total energy of -15 -15
SnO2 primitive cell, geometry optimization is processed by -20
Z A M G Z R X G
-20
Z A M G Z R X G
GGA (PW91), and the values of SnO2 optimized and experi- 20 20
LDA(Norm conserving)
LDA(Ultra-soft)
mental structure[12] are shown in Table 2. All of the calcula- 15 15
10 10
tions are done to the optimized structure of SnO2.
5 5

Energy/eV
2.2 Electronic properties 0
0.015 eV
0
0.619 eV

The energy band structures of SnO2 for GGA (Ultra-soft), -5 -5

GGA (Norm conserving), LDA (Ultra-soft), LDA (Norm con- -10 -10
serving), B3LYP and PBE0 are show in Fig.2. -15 -15
-20 -20
From Fig.2, we can see that rutile-type SnO2 is direct Z A M G Z R X G Z A M G Z R X G
20 20
band-gap semiconductor. The Fermi level is chosen to be zero B3LYP PBE0
15 15
of the energy scale, and the occupied state below the Fermi 10 10
5 5
Energy/eV

2.581 eV 2.724 eV
Table 1 Parameters of energy cut-off, k-point and SCF for GGA 0 0
-5 -5
(Ultra-soft), GGA (Norm conserving), LDA (Ultra-soft), -10 -10
LDA (Norm conserving), B3LYP and PBE0 -15 -15
-20
Pseudo po- Energy SCF toler- Z A M G Z R X G -20Z A M G Z R X G
Method k-point set Position Position
tential cut-off/eV ance/eV·atom-1
GGA Ultra-soft 340 5×5×8 1×10-6 Fig.2 Calculated band structure of SnO2 for GGA (Ultra-soft), GGA
(Norm conserving), LDA (Ultra-soft), LDA (Norm conserv-
Norm con-
GGA 750 5×5×8 1×10-6 ing), B3LYP and PBE0
serving
LDA Ultra-soft 340 5×5×8 1×10-6 energy is valence band, whereas the unoccupied state lying
Norm con- above the Fermi energy is conduction band. The position of
LDA 750 5×5×8 1×10-6
serving bottom of conduction band and top of valence band is G-point
Norm con- of Brillouin zone. The band gaps are 0.015, 0.602, 0.015,
B3LYP 750 3×3×4 1×10-6 0.619, 2.581, 2.724 eV, respectively, when calculation is done
serving
by ultra-soft, norm conserving pseudopotential of GGA and
Norm con-
PBE0 750 3×3×4 1×10-6 LDA, B3LYP and PBE0. The band gaps calculated by B3LYP
serving and PBE0 are more close to the available experimental data
than that by GGA and LDA, which is because GGA and LDA
are ground state theory, and the energy-gap belongs to prop-
erty of excited state[13] .
The total density of state (TDOS) and partial density of
states (PDOS) of SnO2 calculated for GGA (Ultra-soft), GGA
(Norm conserving), LDA (Ultra-soft), LDA (Norm conserv-
ing), B3LYP and PBE0 are shown in Fig.3.
From Fig.3, we can see that while the energy-gaps of SnO2
calculated by different functional forms are very different
from each other, the total density of state (TDOS) and partial
Fig.1 Unit cell of SnO2 (black ball is Sn atom and grey ball is O atom) density of states (PDOS) have little difference, especially the

2410
 Shao Tingting et al. / Rare Metal Materials and Engineering, 2015, 44(10): 2409-2414
positions of peak values are mainly identical except the re-
sults calculated by B3LYP and PBE0 that have some transla-
tion motion. From the figure of density of state calculated by
GGA and LDA, we can find that the valence band includes
two parts: (1) the low valence band, –15.5~–18.5 eV region,
which are dominated by O 2s2 states, with a minor-presence
of Sn 5s2 and Sn 5p2 states, can be ignored because it is far
from Fermi level that has little influence on it; (2) the high
valence band, –8.5 ~ 0 eV region, which is dominated by O
2p4 states, with a few contributions of Sn 5s2 and Sn 5p2
states to the valence band, is close to Fermi level, and illus-
trates that O atom can absorb electrons strongly and O 2p4
orbits are almost filled. The conduction band is mainly
dominated by Sn 5p2 and Sn 5s2, and O 2p4 have a few con-
tributions. There are some hybridizations of atomic orbits,
such as hybridization between Sn 5s2 and Sn 5p2 ranging
from –15.5 eV to –18.5 eV, hybridizations between Sn 5s2
and Sn 5p2 as well as between Sn 5s2 and O 2p4 ranging from
–8.5 eV to Fermi energy, and hybridizations between O 2p4
and Sn 5s2 as well as between Sn 5s 2 and Sn 2p2 in conduc-
tion band. From the TDOS and PDOS, we can see that the
electronic state contributions of Sn and O atoms are obvious,
and there is a strong interaction between them. The densities
of states calculated by B3LYP and PBE0 are similar, but the
low valence bands shift left a little, and the conduction bands
shift right a little, which is consistent with the result of en-
PDOS/electron·eV-1 TDOS/electron·eV-1
PDOS/electron·eV-1 TDOS/electron·eV-1
Energy/eV
Fig.3 Calculated TDOS and PDOS of SnO2 for GGA (Ultra-soft), GGA (Norm conserving), LDA (Ultra-soft),
LDA (Norm conserving), B3LYP and PBE0
ergy gap calculated above.
2.3 Optical properties
The complex dielectric function ε(ω)= ε1(ω)+iε2(ω), which
can reflect band structure and other spectrum information, is
usually used to describe the optical properties of solidity
macroscopically[14]. The complex dielectric functions of ru-
tile-type SnO2 from the polarization vectors [0 0 1] calculated
for GGA (Ultra-soft), GGA (Norm conserving), LDA (Ul-
tra-soft), LDA (Norm conserving), B3LYP and PBE0 are
shown in Fig.4.
From Fig.4, we can see that there are some differences in
the positions of the peaks in the six conditions, but the
curve trend seems to be similar. The real part ε1(ω) is de-
scended as a whole as the energy increases, and the inten-
sity reaches maximum at 2.0, 2.7, 9.0, 9.3 eV, respectively,
for GGA/LDA (Utra-soft), GGA/LDA (Norm conserving),
B3LYP and PBE0. The probability of photon absorption is
directly related to the imaginary part of complex dielectric
function ε2(ω). For ε2(ω), the points of curves beginning to
rise are very consistent with the calculated energy gaps. In
addition, there are three clear peaks, but the positions of the
peaks and the peak values are different for GGA (Ul-
tra-soft), GGA (Norm conserving), LDA (Ultra-soft), LDA
(Norm conserving), B3LYP and PBE0, and those are listed
in Table 3.
2411
 Shao Tingting et al. / Rare Metal Materials and Engineering, 2015, 44(10): 2409-2414

The peaks appear because of the electrons transition from
valence band to conduction band. The first peak arises from
Complex Dielectric Function
the electron transition from the top of valence band to the
bottom of conduction band, and the second peak results from
the electron transition from O 2p4 orbits to Sn 5s2 orbits. The
highest peak appears because of electrons transition from O

2p4 orbits to Sn 5p2 orbits.

The codex refractive index is an important optical con-
stant of absorbing medium. The real part n is refractive in-
dex, and imaginary part k is extinction coefficient. The re-
fractive index and extinction coefficient of rutile-type SnO2
from the polarization vectors [001] calculated for GGA
(Ultra-soft), GGA (Norm conserving), LDA (Ultra-soft),
LDA (Norm conserving), B3LYP and PBE0 are shown in
Fig.5.
Complex Dielectric Function

From Fig.5, we can see that the curves tends seem to be

similar calculated by different functional forms but there
are also some differences. The n and k calculated for
GGA/LDA (Ultra-soft), GGA/LDA (Norm conserving),
respectively, are very close, and the results calculated by
Complex Dielectric Function

Refractive Index

Photon Energy/eV
Refractive Index

Fig.4 Calculated complex dielectric function of SnO2 for GGA (Ul-

tra-soft), GGA (Norm conserving), LDA (Ultra-soft), LDA
(Norm conserving), B3LYP and PBE0 (Note: Re and Im de-
note real part and imaginary part, respectively)

Table 3 Peak positions and values of ε2(ω) for GGA (Ultra-soft),

GGA (Norm conserving), LDA (Ultra-soft), LDA (Norm
conserving), B3LYP and PBE0
Refractive Index

Pseudo
Method Position of peaks/eV Peak values/unit
potential
GGA Ultra-soft 2.71 4.96 8.08 2.37 3.41 7.16
Norm con-
GGA 3.32 5.34 7.98 1.81 3.02 7.25
serving
LDA Ultra-soft 2.75 4.94 7.96 2.52 3.57 7.43
Norm con-
LDA 3.44 5.43 7.90 1.88 3.16 7.31
serving Energy/eV
Norm con-
B3LYP 5.03 7.44 10.05 0.70 1.61 4.18
serving Fig.5 Calculated codex refractive index of SnO2 for GGA (Ul-
Norm con- tra-soft), GGA (Norm conserving), LDA (Ultra-soft), LDA
PBE0 5.15 7.69 10.27 0.62 1.48 3.86
serving (Norm conserving), B3LYP and PBE0

2412
 Shao Tingting et al. / Rare Metal Materials and Engineering, 2015, 44(10): 2409-2414

B3LYP and PBE0 are very similar but different from the Table 4 Peak position and value of loss function for GGA (Ul-
former. The values of refractive indexes in low energy are tra-soft), GGA (Norm conserving), LDA (Ultra-soft),
2.29, 2.11, 2.34, 2.12, 1.63, 1.59 for GGA/LDA (Ultra-soft), LDA (Norm conserving), B3LYP and PBE0
GGA/LDA (Norm conserving), B3LYP and PBE0, respec- Peak The Peak values
tively. Comparing 1.997 and 2 for the bulk and the values Method Pseudo potential
positions/eV /unit
1.8~1.9 for MLD (molecular layer deposition) films [15], the
values calculated by norm conserving pseudopotential of GGA Ultra-soft 20.57 16.78
GGA and LDA are close. GGA Norm conserving 20.11 25.74
The absorption and loss function of SnO 2 from the
LDA Ultra-soft 20.45 18.25
polarization vectors [001] calculated for GGA (Ul-
tra-soft), GGA (Norm conserving), LDA (Ultra-soft), LDA Norm conserving 19.98 32.11
LDA (Norm conserving), B3LYP and PBE0 are shown in B3LYP Norm conserving 20.76 5.22
Fig.6.
PBE0 Norm conserving 20.97 4.83
From Fig.6a, we can see that the absorption edge ener-
gies are 1.20, 1.81, 1.13, 1.83, 3.38, 3.52 eV, calculated for
GGA (Ultra-soft), GGA (Norm conserving), LDA (Ul-
tra-soft), LDA (Norm conserving), B3LYP and PBE0, re-
3 Conclusions
spectively which are bigger than the corresponding calcu- 1) The band gaps getting from PBE0 and B3LYP are much
lated energy gaps, because of the need of electron transition more consistent with the available experimental data, while
between occupied state to unoccupied state. The strongest those getting from GGA and LDA are much smaller.
absorption peak is at about 16.0 eV calculated by the six 2) The density of state, dielectric function, codex re-
methods, which is formed by direct transition of electrons fractive index, absorption and loss function calculating
from valence band to conduction band. Loss function indi- from every type basically have the same trend in qualita-
cates the energy loss when electrons rush through solid tive analysis but different from each other. The results
materials. From Fig.6b, we can see that the loss peak posi- calculated by ultra-soft pseudopotential of GGA and LDA
tions and the peaks values are different for GGA (Ul- are very close, and those getting from norm conserving
tra-soft), GGA (Norm conserving), LDA (Ultra-soft), LDA pseudopotential of GGA and LDA are very consistent,
(Norm conserving), B3LYP and PBE0, and they those are while the results calculated by B3LYP fit well with those
listed in Table 4. acquire from PBE0.
3) Although there are differences in calculating behaviors of
30 rutile-type SnO2 using different methods, the results calculated
a
25 by every method are very consistent. The structural electronic
Absorption/×104

GGA(Ultra-soft)

20
GGA(Norm) and optical properties of SnO2 calculated by B3LYP and
LDA(Ultra-soft)
LDA(Norm) PBED are more near to the available experimental data than
15 B3LYP
PBE0 those by other methods.
10
5 References
0 1 Batzill M, Katsiev K, James M et al. Phys Rev B[J], 2005, 72:
0 5 10 15 20 25 30
165414
30 GGA(Ultra-soft) b 2 Bataill M, Diebold U. Prog Surf Sci[J], 2005, 79: 47
GGA(Norm)
25 LDA(Ultra-soft) 3 Liu Chunmei, Chen Xiangrong, Ji Guangfu. Comp Mater Sci [J],
Loss Function

LDA(Norm)
20 B3LYP 2011, 50: 1571
PBE0
15 4 He Y, Liu J F, Chen W et al. Phys Rev B[J], 2005, 72: 212
10 102
5 5 Shieh S R, Kubo A, Duffy T S et al. Phys Rev B[J], 2006, 73:
0 014 105
0 5 10 15 20 25 30
6 Milman V, Winkler B, White J A et al. Quantum Chem[J], 2000,
77: 895
Energy/eV
7 Kresse G, Furthmüller J. Phys Rev B[J], 1996, 54, 011 169
8 Perdew J P, Burke K, Ernzerhof M. Phys Rev[J], 1996, 77:
Fig.6 Calculated absorption (a) and loss function (b) of SnO 2 for 3865
GGA (Ultra-soft), GGA (Norm conserving), LDA (Ultra-soft), 9 Vosko S H, Wilk L, Nusair M et al. Phys[J], 1980, 58: 1200
LDA (Norm conserving), B3LYP and PBE0 10 Hassan F El Haj, Moussawi S, Noun W et al. Comp Mater Sci [J],

2413
 Shao Tingting et al. / Rare Metal Materials and Engineering, 2015, 44(10): 2409-2414

2013, 72: 86
11 Bouhemadou A. Braz J Phys[J], 2010, 40: 52
12 Hadia N M A, Ryabtsev S V, Domashevskaya E P et al. Eur
Phys J AP[J], 2009, 48: 10 603
13 Rahman G, Victor M, Garcia S. APPL [J], 2010, 96: 052 508
14 Yu Feng, Wang Peiji, Zhang Changwen. Acta Physica Sinica[J],
2010, 59: 7285
15 Chatelon J P, Terrier C, Roger J A. Semiconduct Sci[J], 1999, 14:
642

2414