Structural and optical properties of Cu doped SnO2 nanoparticles: An experimental and

density functional study

Pawan Chetri, Bhamyarswa Saikia, and Amarjyoti Choudhury
Citation: Journal of Applied Physics 113, 233514 (2013); doi: 10.1063/1.4811374
View online: http://dx.doi.org/10.1063/1.4811374
View Table of Contents: http://scitation.aip.org/content/aip/journal/jap/113/23?ver=pdfcov
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JOURNAL OF APPLIED PHYSICS 113, 233514 (2013)

Structural and optical properties of Cu doped SnO2 nanoparticles:

An experimental and density functional study
Pawan Chetri, Bhamyarswa Saikia, and Amarjyoti Choudhurya)
Department of Physics, Tezpur University, Napaam-784028, Tezpur, India

(Received 29 March 2013; accepted 3 June 2013; published online 21 June 2013)
The paper investigates, both theoretically and experimentally, the structural and optical changes in
SnO2 system brought about by introduction of Cu in a SnO2 system. On the experimental front, a
cost effective sol-gel technique is used to prepare hexagonal shaped Cu doped SnO2 nanoparticles.
The prepared pristine SnO2 nanoparticle is found to be of random shape by transmission electron
microscope (TEM) studies. A structural and morphological study is carried out using X-ray
diffraction and TEM techniques. The different phonon interaction in the system is observed by
Raman spectroscopy while electron paramagnetic resonance and UV-Visible spectroscopy
confirms the presence of Cu in 2 state. First principle calculations have been performed using
density functional theory-based MedeA Vienna Ab Initio Simulation package on a SnO2 system
where Cu is introduced. The introduction of Cu in the SnO2 system brings distortion which is
corroborated by the variation in the corresponding bond lengths. The Density of State calculation
of Sn16O32 and CuSn15O32 is also performed. Finally, a correlation is established between the
C 2013 AIP Publishing LLC. [http://dx.doi.org/10.1063/1.4811374]
experiment and the theory. V
I. INTRODUCTION

Tin oxide (SnO2) has a tetragonal structure with point

group D144h and space group P42/mnm. The undistorted system has regular octahedron co-ordination in which one tin
(Sn) atom is surrounded by six oxygen (O) atoms. At room
temperature it has a band gap of 3.6 eV. The unique magnetic, optical, and electrical properties of SnO2 system have
generated an enormous interest for its use. Transition metal
(Co, Fe, Mn) doped SnO2 nanoparticles have also been studied for its magnetic and optical properties.1 In nanostructured
SnO2 a large fraction of atoms exist on the surface and thus
the electronic property is completely different from that of
the bulk. Researchers are actively trying to achieve different
morphology of tin oxide because with the change in surface
morphology, the surface reactivity changes which ultimately
affect the properties like electrical, optical, and magnetic
properties. For example, Shi et al.2 has discussed the formation mechanism of SnO2 nanotubes and their application.
Yang et al.3 prepared hexagonal nanosheet of SnO2 using
hydrothermal method. Many authors48 have used density
functional theory (DFT) calculation to account for the
changes in the structure and its magnetic properties.
Recently, Y. Li et al.9 reveal the relation between the donoracceptor complex and the ferromagnetic order in Cu doped
SnO2 thin films while L. Li et al.10 found room temperature
ferromagnetism in Cu doped SnO2 nanowires. But very little
work has been done to correlate the changes in structural
property with the changes in optical property using DFT calculation. Wen et al.11 has obtained photocatalytic activity of
Fe3 doped TiO2 nanoparticles and explained on the basis of
DFT calculation. In our work, we have doped Copper (Cu)
in SnO2 nanosystem and investigated its structural and
a)

Author to whom correspondence should be addressed. Electronic mail:

ajc@tezu.ernet.in. Tel.:913712267120. Fax: 913712267005.

0021-8979/2013/113(23)/233514/8/$30.00

optical properties using experiments and correlated the

observations with DFT results. Random shape pristine SnO2
nanoparticles are prepared via sol-gel synthesis process
while the addition of Cu as dopant leads to the formation of
hexagonal shaped nanosheets. X-ray diffraction (XRD) and
transmission electron microscope (TEM) are the tools used
to investigate structural and morphological properties of
both doped and pristine system. Raman spectroscopy has
been used to check the effect of Cu on the modes of vibration
of SnO2. To know the optical behavior, UV-Visible (UVVis) and photoluminescence (PL) spectroscopy were used.
DFT calculations are used to know the quantum phenomena
occurring in both the system.
II. SYNTHESIS OF SnO2 NANOPARTICLES

The synthesis of pristine SnO2 nanoparticles is started

with the addition of 1 gm of SnCl2.2H2O in a mixture of
11 ml deionized water and 5 ml of ethanol and allow it to
stirrer for 5 min. Later, 1 ml HCl is added drop wise to the
above solution. After stirring it for 15 min, the solution is
fixed at pH 10 by the drop wise addition of aqueous ammonia. This solution is stirred for 23 h at 80  C. A grayish
solution is formed which is washed with deionized water and
ethanol to get an impurity (chlorine) free SnO2 nanoparticles.
The Cu doped SnO2 nanoparticle is achieved by adding drop
wise solution of CuSO4 while stirring in the above solution.
All the prepared nanoparticles are annealed at 600  C.
III. CHARACTERIZATION AND COMPUTATIONAL
DETAILS

Phase structures of the nanoparticles are studied with

Rigaku Miniflex X-ray diffractometer equipped with intense
), at a scanning rate of 1 /min
CuKa radiation (k 1.54 A
and in the scanning range from 10 -70 . High resolution

113, 233514-1

C 2013 AIP Publishing LLC

V

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transmission electron microscope (HRTEM) images of the

prepared nanoparticles are obtained with JEOL JEM 2010
transmission electron microscope operating at a voltage of
200 kV. The Raman spectra of the samples were recorded
using Renishaw In-Via Raman spectrometer (Renishaw,
Wotton-under-Edge, UK) at a resolution of 0.3 cm1. Ar
laser of 514.5 nm wavelength is used for excitation. Electron
paramagnetic resonance (EPR) is performed using JES FA200 ESR Spectrometer in X band, sensitivity 7  109
spins/0.1 mT, and resolution 2.35(micro)T or better. UVVis absorption spectra of all SnO2 nanoparticles are taken in
diffuse reflectance mode (DRS) in Shimadzu 2450 UV Vis
spectrophotometer. PL spectra are monitored in a Perkin
Elmer LS spectrometer.
A 2  2  2 supercell is built with the unit cell of SnO2
in rutile form. The space group of the pure SnO2 is taken as
P42/mnm. The effect of Copper (Cu) on the SnO2 system is
understood by substituting one Centre tin (Sn) atom by Cu
atom and decreasing its symmetry to P1 so that it can obtain
its minimum energy configuration by relaxing all the atoms
in all direction. The space group of optimized CuSn15O32 is
P2/m. The lattice parameters a and c of optimized Sn16O32
, whereas a and c of CuSn15O32 are 4.75
are 4.76 and 3.22 A

and 3.21 A. We performed density functional calculations

using generalized gradient approximation (GGA) functional
with Perdew-Burke-Ernzerhof (PBE) to describe the
electron-electron exchange and correlation effects. The DFT
equations are solved via projector augmented wave (PAW)12
method using plane wave basis set as implemented in
Vienna Ab Initio Simulation Package (VASP) and interfaced
with MedeA technology platform.
The undoped supercell contains 16 atoms of Sn and 32
atoms of oxygen which make it look like Sn16O32. The Cu
doped SnO2 takes the form as CuSn15O32. The minimum
energy state is computed by varying the internal position of
. The doped sysatoms until the residual force is 0.01 eV/A
tem maintained its cubic form with a deviation in angle of
0.009 towards Z-axis. The cutoff kinetic energy is set to
400 eV. A 2  2  2 K-mesh is used which correspond to
in reciprocal space. Methfesselspacing less than 0.5 A
Paxton type of smearing is used with smearing width of
0.2 eV. Real space projection operator is used as the system
contains large number of atoms.
IV. RESULT AND DISCUSSION
A. Structural characterization

Fig. 1(a) represents the XRD pattern of all the prepared

SnO2 nanoparticles. The diffraction peak of the samples corresponds to rutile phase of SnO2 (JCPDS 41-1445). The crystallite size is calculated by Scherrer formula and
Williamson-Hall (W-H) plot as well. The reason behind calculating crystallite size by both the method is to check the
effect of strain on the crystallite size as the former does not
consider strain while the later does. The differences of two
sizes yield the required information. The crystallite size from
Scherrer formula is calculated by using the equation,
d 0:91k=b Cos h;

J. Appl. Phys. 113, 233514 (2013)

FIG. 1. XRD of pristine and Cu doped SnO2.

where d is the crystallite size, k is the wavelength of X-ray

used, and h is the Bragg angle of diffraction peaks. The crystallite size d and lattice strain g are calculated from W-H
plot by plotting the variation of b Cos h/k with Sin h/k. The
results from both the methods show that as doping increases
size decreases. Due to Cu doping system gets distorted and
lattice planes are destroyed so that the crystallite size
decreases. Scherer formula doesnt consider the strain in the
system while W-H calculation does consider the strain. We
can see a clear difference between sizes calculated by both
method and which is due to the lattice strain in the system.
The negative strain implies contraction in the system and
hence doped system has lower W-H calculated crystallite
size values compared to the crystallite sizes calculated by
Scherer equation. The ionic radius of Sn4 and Cu2 in octa and 0.87 A
, respectively. If
hedral co ordination is 0.83 A
Cu2 substitutes Sn4 then the lattice should expand as the
size of Cu2 is larger than that of Sn4 but in our case lattice
has contracted. The contraction in the system due to incorporation of Cu2 can be due to creation of Sn or oxygen vacancies. However, the formation energy of Sn is lower than that
of oxygen.13 Therefore, in this process doping of Cu
increases the Sn vacancies and which ultimately increases
the negative strain listed in Table I. No new phase of Cu is
created as no characteristic peak of Cu or oxides of Cu was
seen. The TEM image of pristine and Cu5% doped SnO2 in
both low resolution and high resolution is shown in Figs.
2(a) and 2(b), respectively. These TEM images confirm that
the prepared pristine and Cu doped SnO2 is in nano regime.
The TEM images are presented at three resolutions 50 (low),
10 (high), and 5 (high) nm. Low resolution shows a little
TABLE I. Sample, crystal size, and lattice strain.
Crystal size
Sample
Pure SnO2
Cu 1% doped
Cu 3% doped
Cu 5% doped

Scherer formula (nm) W-H calculations (nm) Lattice strain

12.76
12.54
10.04
9.31

14
11.77
8.90
5.37

9.05
0.06
0.08
0.31

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J. Appl. Phys. 113, 233514 (2013)

FIG. 2. (a) High and low resolution image of pristine SnO2. (b) High and low resolution image of Cu doped SnO2.

amount of agglomeration of nanoparticles, which is very

much expected as we have not used any kind of surfactant.
The high resolution image of pristine SnO2 shows that the
particles are of random shape having size around 19 nm. The
high resolution image of Cu5% doped SnO2 shows the clear
formation of hexagonal nanosheet. The size of the hexagonal
nanosheet is found to be around 10 nm. This confirms that
doping of Cu in SnO2 has decreased the particle size compared to pristine SnO2. The interplanar spacing in pristine
and Cu5% doped SnO2 nanosystem is found to be 0.37 and
0.41 nm while from XRD it is calculated to be 0.47 and
0.48 nm, respectively.
1. Raman spectroscopy

Raman spectroscopy is an effective tool to investigate

the vibrational mode within the system. A normal mode can
be described by the 3 n (n is the number of atoms in the primitive cell) coordinates giving the displacements of the atoms
from their equilibrium positions.14 Rutile SnO2 having 6
atoms unit cell give out 18 possible vibrations. On the basis
of group theory, the normal lattice vibration at the C point of
the Brillouin zone is as follows:15
C C1 1A1g C2 1A2g C3 1B1g C4 1B2g
C5  1Eg C1  1A2u 2 C4  B1u 4C5 Eu :
Two modes (A2u and triply degenerate Eu) are infrared
(IR) active. A2u has one optic and one acoustic mode while
Eu has two acoustic and one optic mode. Four modes, i.e.,
A1g, B1g, B2g and doubly degenerate Eg are found to be
Raman active and two (A2g, B1u) modes are silent. Chen
et al.16 and Luo et al.17 observed IR active peaks in the
Raman spectra but we have not observed any IR active mode
or any silent mode in the Raman spectrum. The only peaks
observed are clearly belongs to Raman active modes of rutile
SnO2. In bulk SnO2, Raman active modes are expected
at 123, 476, 634, and 778 cm1 for B1g, Eg, A1g, and B2g,

respectively.18 In our case, we have clearly observed A1g

and B2g modes whereas a hump appears in the range of
vibration where Eg can be expected while the presence of
B1g is not clear. It is unclear because bulk SnO also has its
B1g vibration at 112 cm1. A1g and B2g are due to the
expanding and contracting vibration of Sn-O bonds in a
plane perpendicular to c-axis, respectively.19 Eg mode is
accounted for the vibration of two oxygen atoms opposite to
each other but parallel to c-axis. This mode is highly sensitive to oxygen vacancies than the other modes.20 In Table II,
we have listed the position of different modes of vibration
and its shifting with the increase in Cu doping. We can see
in Fig. 3 that the vibrational modes except B1g move to lower
wavenumber as the concentration of Cu increases and this is
due to the decrease in crystallite size. Actually on the basis
of Heisenberg uncertainty principle, we can write that
Dx Dp  h2 =4;
where Dx is the particle size and Dp is the phonon momentum distribution. h is the well known Plancks constant.
With the decrease in particle size, confinement of phonon
within the particle increases. As the confinement of phonon
has increased in small size particle, it leads to the increase in
energy of phonon. These highly energetic phonons interact
with the incident photon such that the scattered photons have
lesser energy and thus the peak shifted to lower wave numbers. Also as the size of the particle decreases broadening of
the peaks observed.21 As we doped 1% Cu in the system,
due to distortion in the system, the intensity of the A1g peak
decreased. But as the Cu doping increased, the intensity
TABLE II. Mode of vibration, pristine SnO2, Cu1%, 3%, and 5% SnO2.
Mode of vibration Pristine SnO2 Cu 1% SnO2 Cu 3% SnO2 Cu 5% SnO2
B1g
A1g
B2g

111.2
631.7
774.32

111.5
631.7
774.32

111.7
631.1
771.79

116.1
629.64
769.26

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J. Appl. Phys. 113, 233514 (2013)

FIG. 3. Raman spectra of pristine and Cu doped SnO2.

started to rise. In Cu 5%, the intensity of A1g is even greater

than that of pristine SnO2. In fact, CuO itself have a vibrational mode at 632 cm1 (bulk)22 so when the amount of Cu
increases then Cu-O vibration becomes prominent and start to
contribute to the vibration of Sn-O (A1g). The intensity and
FWHM of A1g peak is calculated by Gaussian fitting and
listed in Table III. The vibrational mode B1g appears at 111.2
which is a possible mode of vibration for SnO (in XRD
2h 30 approve this fact). As the doping increases, the
Raman mode shifted to higher wave number. In XRD we
have seen that with Cu doping the peak at 2h 30 vanishes
which implies that SnO phase is decreasing from the system.
As the content of SnO decreases, the system begins to acquire
complete stoichiometry of SnO2. The ionic character of the
bond between Sn-O responsible for B1g mode increases as
Sn2 changes to Sn4. It means the bond strength increases
and which may increase the force constant. This increase in
force constant pushes the peak to higher wave number region.
Thus a blue shifting in B1g peak is observed.

The room temperature EPR spectra of pristine and Cu

doped SnO2 is shown in Fig. 4. The pure SnO2 shows a splitting and the calculated g value is 2.007. This splitting is due
to Vo which is the only one possible component that can
produce splitting in pristine SnO2 system. The nuclear magnetic moment for Cu is 3/2 so one peak should be split into
four peaks due to hyperfine interaction. At room temperature
such a splitting cannot be observed as the peak gets broadened though a slight hump can be seen at low field region.
The g value calculated from EPR spectra for Cu doped SnO2
TABLE III. Sample, FWHM of A1g peak (cm1) and intensity of A1g peak
(a.u.).

Pristine SnO2
Cu 1% SnO2
Cu 3% SnO2
Cu 5% SnO2

system is 2.17. This value almost resembles to the mid field g

value obtained by Madhu et al.23 Further, the splitting
observed in Cu doped SnO2 system confirms that Cu is in 2
state otherwise there would have no splitting. The electronic
configuration for Cu in its atomic state (no charge) is 3d10
4s1, so 1 and 2 states give 3d10 4s0 and 3d9 4s0, respectively. Cu1 has no unpair electron so no splitting can occur
in EPR spectra. As the Cu concentration increases, the longrange dipolar interactions between Cu2 ions in Cu doped
SnO2 increases, which cause broadening of spectral lines.
B. Optical properties
1. UV-Vis spectroscopy

To have a better understanding of the effect of Cu doping

on optical properties of SnO2 at different concentration, UVVis spectroscopy is performed. The absorbance is given by
FR 1  R2 =2R:

2. EPR

Sample

FIG. 4. Electron paramagnetic resonance spectra of pristine and Cu doped

SnO2.

FWHM of A1g peak (cm1)

Intensity of A1g peak (a.u.)

17.51
19.70
20.09
23.69

986.22
685.59
905.34
1610.31

The variation of absorbance with wavelength is shown in

Fig. 5(a). The band gap is calculated using Kubelka-Munk
equation, where [F(R) ht]2 is plotted against incident photon
energy ht and the extrapolated line at [F(R) ht]2 0 gives the
value of band gap in eV as shown in Fig. 5(b). The Urbach
energy of each sample is calculated using the equation
a a0 exp E=Eu ;
where a is the absorption coefficient, E is the photon energy,
and Eu is the Urbach energy. The band gap values and Urbach
energy values are listed in Table IV. The prepared pristine
SnO2 has a band gap of 3.93 eV while its band gap increases
with the increase in Cu concentration. In Table I, we have already seen that as the doping concentration of Cu increases
the crystallite size decreases, this increase in band gap with
the Cu concentration is very obvious (quantum confinement
effect). Urbach type absorption is the absorption below band
gap. When defects in the system increase then the below band
absorption occurs. As the concentration of Cu increases the

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J. Appl. Phys. 113, 233514 (2013)

FIG. 5. (a) UV-Visible absorption

spectra of pristine and Cu doped SnO2.
(b) Band gap determination of pristine
and Cu doped SnO2.

Urbach energy also increases which means that the distortion

increases.24 The increase in distortion can be due to two reasons either Cu is creating levels nearby conduction band or
incorporation of Cu in the system producing oxygen vacancies
which are making levels nearby conduction band.
The inset in Fig. 5(a) shows the low absorption in near
infra-red region. This peak is due to d-d transition of electron
in Cu2. The ground state of Cu2 is 2Eg and its excited state
is 2T2g so in exact words the transition is from 2Eg to 2T2g.
This peak further confirms the presence of Cu in 2 state. If
TABLE IV. Sample, band gap (eV), and Urbach energy (eV).
Sample
Pure SnO2
Cu 1%
Cu 3%
Cu 5%

Band gap (eV)

Urbach energy (eV)

3.93
3.96
3.98
4.00

0.49
36.54
36.95
38.61

Cu would have been in 1 state then its outer electronic configuration is 3d10 4s0 so there is no possibility of electron
transition as there is no unpaired electron and we do not get
any peak near infra red region. The intensity of absorption
near infra-red region increases with the increase in concentration of Cu.
2. Photoluminescence spectroscopy

Fig. 6 shows the room temperature photoluminescence

spectra of pristine and Cu doped SnO2 nanoparticles. The
spectra show typical UV emission (394 nm) for pristine
SnO2 during a broad emission in the visible region. The UV
emission in pristine SnO2 is not due to band edge emission
but due to below band edge emission. The absence of band
edge emission may be due to limitation of instrument.25 The
oxygen vacancies can be in three charged states Voo, Vo,
and V0. Voo is the shallowest level while Vo and Vo
are deeper levels within the band gap.26 In our case the peak

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FIG. 6. Photoluminescence spectra of pristine and Cu doped SnO2.

at 394.8 nm could be due to Voo states while the peak ranging from 425 to 485 nm is due to Vo and V0 states. The
presence of Vo is detected in EPR signal of pristine SnO2.
Fang et al.27 observed a slight red shifting of peaks after Co
doping in SnO2 and they attributed the case to defective
energy levels introduced by Co doping. We also found that
as the doping concentration of Cu increases the peaks red
shifted but there can be many possible reasons for it. As the
percentage of Cu doping increases, it brings distortion within
the system and that is why the Urbach energy value also
increases. This distortion is due to levels within the band gap
where nonradiative transition of electron occurs. This level
can be due to defects such as Sn vacancies or oxygen
vacancies or it can be due to levels formed by Cu within
the system. If the vacancies such as Vo increased with Cu
doping then we would have observed its presence in EPR
but there is nothing like that, while the presence of Vo is
possible. Zhang et al.13 showed that in Cu doped SnO2; formation energy of Sn vacancies is lesser than that of oxygen
vacancies so in our case also the red shifting in PL peaks
might be due to Sn vacancies. In Fig. 8, we have observed
levels of Cu within the band gap so; the effect of Cu on the
PL spectra also cannot be ignored. Therefore, the red shifting in the PL spectra with the increase in concentration of
Cu can be due to Sn vacancies or Cu levels or the oxygen
vacancies.
In order to rationalize the relation between structural
disorder and optical changes, we have done a detailed theoretical study of electronic structure of Cu doped and undoped
SnO2 system.

FIG. 7. 2  2  2 Supercell construction of 48 atoms having one Cu (brown),

fifteen Sn (yellow), and thirty two O (red).

Sn16O32 and CuSn15O32 supercells are tested with both

spin polarized and spin unpolarized calculation. The ground
state energy for Sn16O32 is found to be same in both type of
calculation whereas in CuSn15O32 spin polarized structure is
103 meV more stable than the spin unpolarised one.
Therefore, we consider spin polarized structure in both the
cases to calculate its band structure and density of state
(DOS). The upper part of the valence band is mainly made of
O2p states while the lower part of the conduction band is
dominated by Sn5s states. The band gap value obtained from
DFT calculation is not reliable but still we can observe the
pattern of bands and relative positions of different levels from
band structure as shown in Fig. 8. The band diagram shows
that both the systems have direct band gap, i.e., phonon participation is not required. The inclusion of Cu in the system
has produced two levels within the band gap region. The Cu
is in octahedral co-ordination so according to crystal field
theory in ground state its d states split up into eg and t2g states.
Similarly, Gillen et al.28 show the splitting of d level into eg
and t2g states. The eg and t2g states are shown by arrow in Fig.
10. The asymmetric distribution of majority and minority
spins of eg states shows the presence of magnetic centers.29
TABLE V. System, bond length and ground state energy.

C. Electronic structure investigation

System

To calculate the difference between structural and optical properties of SnO2 and Cu substituted SnO2, we have
resorted to DFT calculations.
The substitutions of one Sn atom from 48 atom SnO2
supercell by Cu (as shown in Fig. 7) affect all the bond
length within the system. All the bond lengths, i.e., Sn-Sn,
Sn-O and Sn-Sn, Sn-O and Cu-O in Sn16O32 and CuSn15O32
supercell, respectively, are listed in Table V. We have found
changes in the bond lengths of Cu doped SnO2 system compared to the undoped SnO2.

Sn16O32

CuSn15O32

Bond
)
Length (A

Ground state energy (E0) in eV

Spin polarized

Nonmagnetic

SnSn
3.22
SnO
2.07 and 2.06

301.291

301.291

SnSn
3.21 and 3.18
SnO
2.08, 2.06 and 2.05
CuO
2.00 and 1.99

295.255

295.152

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FIG. 8. Band structure of Sn16O32 and

CuSn15O32.

In the doped system, top of the valence band is found

to be occupied by Cu3d and O2p states. The inclusion of
Cu has influenced the nearby oxygen and splitted their
energy levels as observed in Fig. 9. Few oxygen levels are
found to be occupying levels above Fermi levels. Wen
et al.11 have observed that Fe-d states induce O2p state
such that few oxygen states occur near Fermi level. The
same has happened in our case as well. Here Cu-d states
induced O2p states such that few oxygen are contributing
their 2 p states to occur nearby Fermi level along with the
Cu-d states.
D. Correlating experimental and theoretical results

1. We have found changes in the bond lengths of Cu doped

SnO2 system compared to the undoped SnO2 (obtained
from DFT Calculation). This indicated a change in the
structural property of both the systems. In XRD and
Raman spectroscopy, we have observed change in structural properties as well.

2. If a Cu substitute Sn atom and enter the octahedral coordination, we expected a peak in the near IR region in
UV-Vis Spectra and which we did observe. This observed
peak comes due to the transition of electron from 2Eg to
2
T2g. DFT calculation provides the DOS Sketch of
CuSn15O32 system (where Cu is sitting in the octahedral
coordination shown in Fig. 7). In the DOS sketch, we
have observed the splitting of d state into Eg and T2g levels as shown in Fig. 10.
3. The width of the peak near IR region in Fig. 5(a) increases
with the increasing Cu concentration. This increase in
width with the increasing Cu concentration is due to the
increase in p-d hybridization in the system.30 The existence of p-d hybridization in the Cu doped system is
proved by the DOS of CuSn15O32 (Fig. 9).
4. The asymmetric distribution of majority and minority
spins of eg states (Fig. 10) of the system was suggested by
DFT investigation. It indicated the presence of magnetic
centers in the system. Experimentally, also the splitting of
ESR signal refers to the presence of Paramagnetic centre.

FIG. 9. DOS of Sn16O32 and CuSn15

O32.

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233514-8

Chetri, Saikia, and Choudhury

J. Appl. Phys. 113, 233514 (2013)

Choudhury acknowledges the financial support provided by

Department of Science and Technology (DST), India, to the
project SR/NM/NS-98/2010 (G), We are obliged to SAIF,
NEHU for helping us in carrying out the TEM measurement
and also acknowledged SAIF, IIT Bombay for EPR
measurement.

C. B. Fitzgerald, M. Venkatesan, A. P. Douvalis, S. Huber, J. M. D. Coey,

and T. Bakas, J. Appl. Phys. 95, 7390 (2004).
L. Shi and H. Lin, Langmuir 27, 3977 (2011).
3
X. Yang and L. Wang, Mater. Lett. 61, 3705 (2007).
4
W. Chen and J. Li, J. Appl. Phys. 109, 083930 (2011).
5
H. Wang, Y. Yan, Y. Sh. Mohammed, X. Du, K. Li, and H. Jin, J. Magn.
Magn. Mater. 321, 3114 (2009).
6
W. Z. Xiao, L. L. Wang, L. Xu, X. F. Li, and H. Q. Deng, Phys. Status
Solidi B 248, 1961 (2011).
7
W. Z. Xiao, L. L. Wang, L. Xu, Q. Wan, and B. S. Zou, Solid State
Commun. 149, 1304 (2009).
8
A. F. Lamrani, M. Belaiche, A. Benyoussef, A. E. Kenz, and E. H. Saidi,
J. Magn. Magn. Mater. 323, 2982 (2011).
9
Y. Li, R. Deng, Y. Tian, B. Yao, and T. Wu, Appl. Phys. Lett. 100,
172402 (2012).
10
L. Li, K. Yu, Z. Tang, Z. Zhu, and Q. Wan, J. Appl. Phys. 107, 014303
(2010).
11
L. Wen, B. Liu, X. Zhao, K. Nakata, T. Murakami, and A. Fujishima, Int.
J Photoenergy 2012, 368750 (2012).
12
G. Kresse and J. Joubert, Phys. Rev. B 59, 1758 (1999).
13
K. C. Zhang, Y. Liu, Y. F. Li, and Y. Zhu, J. Appl. Phys. 113, 053713
(2013).
14
R. S. Katiyar, J. Phys. C 3, 1087 (1970).
15
A. Dieguez, A. Romano-Rodrguez, A. Vila, and J. R. Morante, J. Appl.
Phys. 90, 1550 (2001).
16
W. Chen, D. Ghosh, and S. Chen, J. Mater. Sci. 43, 5291 (2008).
17
S. Luo, P. K. Chu, Z. Di, M. Zhang, W. Liu, C. Lin, J. Fan, and X. Wu,
Appl. Phys. Lett. 88, 013109 (2006).
18
K. Mcguine, Z. W. Pan, Z. L. Wang, D. Milkie, J. Menendez, and A. M.
Rao, J. Nanosci. Nanotechnol. 2, 1 (2002).
19
W. Zhou, R. Liu, Q. Wan, Q. Zhang, A. L. Pan, L. Guo, and B. Zou,
J. Phys. Chem. C 113, 1719 (2009).
20
E. Fazio, F. Neri, and S. Savasta, Phy. Rev. B. 85, 195423 (2012).
21
H. C. Choi, Y. M. Jung, and S. B. Kim, Vib. Spectrosc. 37, 33
(2005).
22
J. F. Xu, W. Ji, Z. X. Shen, W. S. Li, S. H. Tang, X. R. Ye, D. Z. Jia, and
X. Q. Xin, J. Raman Spectrosc. 30, 413 (1999).
23
N. Madhu, A. V. Chandrasekhar, B. J. Reddy, Y. P. Reddy, and R. V. S. S.
N. Ravikumar, Indian J. Chem. 38A, 590 (1999).
24
P. Chetri and A. Choudhury, Physica E 47, 257 (2013).
25
Q. Kuang, C. Lao, Z. L. Wang, Z. Xie, and L. Zheng, J. Am. Chem. Soc.
129, 6070 (2007).
26
S. Das, S. Kar, and S. Chaudhuri, J. Appl. Phys. 99, 114303 (2006).
27
L. M. Fang, X. T. Zu, Z. J. Li, S. Zhu, C. M. Liu, L. M. Wang, and F. Gao,
J. Mater Sci.: Mater Electron. 19, 868 (2008).
28
R. Gillen and J. Robertson, arXiv:1208.0786[cond-mat mtrl-sci].
29
W. Z. Xiao, H. Luo, J. Y. Yang, and D. Shuang, Eur. Phys. J. B 80, 337
(2011).
30
W. L. Yu, W. W. Li, J. D. Wu, J. Sun, Z. G. Hu, and J. H. Chu, J. Appl.
Phys. 110, 123502 (2011).
2

FIG. 10. DOS of Cu in CuSn15O32.

In short, we have established fundamental correlations

between experimental observations and finding of theoretical
calculations.
V. CONCLUSION

Random shape pristine SnO2 is converted to hexagonal

SnO2 with the help of Cu doping XRD. XRD and Raman
measurement shows that the doping of Cu removes Sn2
from the system. EPR and UV-Vis spectra prove that the
doped Cu is in 2 state while photoluminescence spectra
show red shifting of peaks in Cu doped SnO2 compared to
pristine SnO2 The increase in Urbach energy with the Cu
doping indicates the distortion in the system. DFT investigation of Sn16O32 and CuSn15O32 is presented in the paper.
Here, Spin polarized calculation is found to be more stable
as compared to spin unpolarized calculation in CuSn15O32
by 106 meV. The DOS sketch suggests that the top of the valence band is made of O2p while the bottom of the conduction band is made of Sn5s in Sn16O32. In Cu doped SnO2,
i.e., in CuSn15O32, DOS sketch further shows that the top of
the valence band is a hybridized state of Cu3d and O2p while
the bottom of Conduction band is still due to Sn5s. The Cu-d
states induced O2p states to split up near the Fermi level.
ACKNOWLEDGMENTS

Pawan Chetri likes to acknowledge DST, Government

of India for providing Inspire Fellowship and Amarjyoti

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