Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 118 (2014) 11351143

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Spectrochimica Acta Part A: Molecular and

Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Preparation and characterizations of SnO2 nanopowder and

spectroscopic (FT-IR, FT-Raman, UVVisible and NMR)
analysis using HF and DFT calculations
A. Ayeshamariam a, S. Ramalingam b,, M. Bououdina c,d, M. Jayachandran e
a

Department of Physics, Khadir Mohideen College, Adirampattinam, Tamilnadu, India

Department of Physics, A.V.C. College, Mayiladuthurai, Tamilnadu, India
Nanotechnology Centre, University of Bahrain, Bahrain
d
Department of Physics, College of Science, University of Bahrain, Bahrain
e
Central Electrochemical Research Institute, ECMS Division, Karaikudi, Tamilnadu, India
b
c

h i g h l i g h t s

g r a p h i c a l a b s t r a c t

 The pure and singe phase SnO2 Nano

powder is prepared by solgel

combustion route.
 The vibrational pattern in nano phase
gets realigned and are shifted up
compared with bulk phase.
 The HOMOLUMO band gap (Kubo
gap) of compound is reduced to
3.04 eV at 800 C.
 The Photoluminescence spectra
showed a peak shift with the change
of Kubo gap to 3.22 eV.

a r t i c l e

i n f o

Article history:
Received 24 July 2013
Received in revised form 18 August 2013
Accepted 1 September 2013
Available online 13 September 2013
Keywords:
SnO2
Bulk phase of SnO2
NMR and UVVisible spectra
Photoluminescence
Kubo gap

a b s t r a c t
In this work, pure and singe phase SnO2 Nano powder is successfully prepared by simple solgel combustion route. The photo luminescence and XRD measurements are made and compared the geometrical
parameters with calculated values. The FT-IR and FT-Raman spectra are recorded and the fundamental
frequencies are assigned. The optimized parameters and the frequencies are calculated using HF and
DFT (LSDA, B3LYP and B3PW91) theory in bulk phase of SnO2 and are compared with its Nano phase.
The vibrational frequency pattern in nano phase gets realigned and the frequencies are shifted up to
higher region of spectra when compared with bulk phase. The NMR and UVVisible spectra are simulated
and analyzed. Transmittance studies showed that the HOMOLUMO band gap (Kubo gap) is reduced from
3.47 eV to 3.04 eV while it is heated up to 800 C. The Photoluminescence spectra of SnO2 powder showed
a peak shift towards lower energy side with the change of Kubo gap from 3.73 eV to 3.229 eV for as-prepared and heated up to 800 C.
Crown Copyright 2013 Published by Elsevier B.V. All rights reserved.

Introduction
Rapid developments in todays electronic devices including at
panel displays and touch panels are asking for highly sophisticated
Corresponding author. Tel./fax: +91 4364 222264.
E-mail address: ramalingam.physics@gmail.com (S. Ramalingam).

components, with an ever increasing performance. The development of transparent conducting coatings as electrodes with
customized characteristics like high electron work function, high
electron mobility and high transparency, hence, is becoming more
and more relevant [1]. To meet these forthcoming requirements,
however, novel materials or improved coating techniques have to
be developed. One of these approaches is focusing on a combination

1386-1425/$ - see front matter Crown Copyright 2013 Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.saa.2013.09.030

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A. Ayeshamariam et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 118 (2014) 11351143

of several coating methods, as for example, magnetron sputtering

and solgel dip coating, to benet from the advantages of both
techniques [2]. The properties of such materials are fascinating
and have formed the subject of intense research in recent years
[3,4]. These materials behave differently from bulk semiconductors.
With decreasing particle size the band structure of the semiconductor changes; the band gap increases and the edges of the bands
splits into discrete energy levels. These so-called quantum size effects occur [5,6]. These quantum size effects have stimulated great
interest in both basic and applied research.
Tin oxide, SnO2, is a well-known n-type semiconductor with a
wide band gap (Eg = 3.8 eV) and for its potential applications in
gas sensors [7], dye-based solar cells, transparent conducting electrodes [8], and catalyst supports [9].
Research in the area of nano scale materials is motivated by the
possibility of processing and designing nano structured materials
with unique properties and important applications. Due to their
nite small size and the high surface-to volume ratio, nano structured materials often exhibit novel, and sometimes unusual properties [10]. The optical, electrical, magnetic, thermal, and chemical
properties depend to a large extent on the particle size and shape
of these materials [11]. Meanwhile the large number of surface and
edge atoms provides active sites for catalyzing surface reactions. In
the areas of optoelectronic devices such as transparent semiconductor electrodes in liquid crystal displays, light emitting transport
conductors and solarelectrical energy converters and chemical
and gas sensitive semiconductor devices and nano electronics,
the SnO2 and their composites are nding great interest and attention in recent years [12].
Beltran et al. reported the structural and electronic properties of
the TiO2/SnO2/TiO2 and SnO2/TiO2/SnO2 composite systems. Periodic quantum mechanical method with density functional theory
at the B3LYP level has been carried out. Relaxed surface energies,
structural characteristics and electronic properties of the (1 1 0),
(0 1 0), (1 0 1) and (0 0) low-index rutile surfaces for TiO2/SnO2/
TiO2 and SnO2/TiO2/SnO2 models are studied [13]. Yoichi Yamaguchi et al., reported that density functional theory calculations within the generalized gradient approximation have been performed
for the interaction of oxygen with reduced M/SnO2(1 1 0) (M = Pd,
Pt) surfaces [14].
However, so far, no work has been reported on the study (comparison of Bulk and Nano phase) of preparation and characterization of pure and singe phase SnO2 Nano powder with HF and DFT
computational calculation. In this work, the SnO2 nano powder is
successfully prepared by solgel combustion method and is investigated by FTIR, Laser Raman spectroscopy UVVis, and Photoluminescence measurements. Moreover, FT-IR and FT-Raman, NMR, UV
and Visible spectra are recorded for bulk SnO2 for the comparison.
The geometrical parameters and vibrational frequencies are calculated using HF and DFT theory and their results are compared with
the experimental values.

Experimental methods
Synthesis of SnO2
Nanocrystalline SnO2 powders were prepared by solgel combustion process. Nitric acid was used in order to introduce oxidizing ions, while urea was chosen as the fuel. Aqueous solutions of
pure metallic Sn (Malinckrodt), was dissolved in nitric acid (70%,
Merck), and stoichiometric ratio of fuel urea (Merck) and deionised
water were prepared. The solutions were heated under constant
stirring at a temperature of about 90100 C in a Pyrex vessel
and concentrated slowly without producing any precipitation until
it turned into a white, viscous gel. The portions of the gels were

heated at temperatures of about 350 C, which suffered a strong

self propagating combustion reaction with the evolution of a large
volume of gases. The entire combustion process was over after few
seconds. The resulting yellow ashes were then calcined at
100800 C for an hr in order to eliminate the carbonaceous residues as shown in owchart Fig. 6[15].
During the process of combustion using a fuel, carbon and
hydrogen atoms combine with oxygen with simultaneous liberation of heat at a rapid rate. This energy is liberated due to the rearrangement of valency electrons in these atoms, resulting in the
formation of new compounds.

Fuel O2 ! Products heat

According to Cooper et al. we can dene the oxygen balance (OB) of

the reaction, as dened in the eld of propellants and explosives, as
follows:

OB% 100 

AWoxygen
2cO2
FWmixture

where AW and FW are respectively the atomic weight of oxygen

and the formula weight of the mixture, cO2 is the molar number
of oxygen.
Three modes of Combustion [16] can be classied depending on
the value of OB:
 Smoldering Combustion Synthesis (SCS) when OB > 0 (fuel
lean regime): an excess amount of oxygen in the reactant mixture is present and stied the reaction. Thats why this mode is
characterized by a slow and ameless reaction.
 Volume Combustion Synthesis: (VCS) when OB = 0 (stoichiometry regime), a thermal explosion takes place and the reaction
occurred in the solution volume, resulting in the formation of
a homogeneous solid. The whole oxygen content of the metal
nitrates can react completely in oxidizing the fuel.
 Self propagating high-temperature Synthesis (SHS) when
OB < 0 (fuel rich regime), the reaction is locally ignited and
propagate as a combustion wave in a self-sustained manner
through the reaction volume. In this regime, oxygen atmosphere is required for a complete combustion between fuel
and metal nitrates.
These three modes depend on the fuels/oxidizer ratio and determine the reactivity of the reaction (explosive or moderate reaction). It is worth noting that the fuel to oxidizers ratio affects
also the surface area of the resulting powder and then the particle
size of the nal products.
Spectral information
Bulk SnO2 is purchased from SigmaAldrich Chemicals, which is
of spectroscopic grade and hence used for recording the spectra as
such without any further purication. SnO2 Nano powder is prepared by above said method. The FT-IR spectra of the compound
in both phases are recorded in Bruker IFS 66V spectrometer in
the range of 4000400 cm1. The spectral resolution is 2 cm1.
FT-Raman spectra of same compound is also recorded in the same
instrument with FRA 106 Raman module equipped with Nd:YAG
laser source operating at 1.064 lm line widths with 200 mW
power. The spectra are recorded in the range of 4000100 cm1
with scanning speed of 30 cm1 min1 of spectral width 2 cm1.
The frequencies of all sharp bands are accurate, i.e., 1 cm1.
Characterization techniques
As-prepared nano powder and bulk SnO2 were characterized by
different techniques. The structure and phase purity of the

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1137

Table 1
Optimized geometrical parameters for Tin oxide computed at HF and DFT [LSDA, B3LYP and B3PW91] methods with 3-21G(d,p) basis sets.
Geometrical Parameters

Methods Bulk phase

Experimental value
Nano phase

HF/3-21G(d,p)

LSDA/3-21G(d,p)

B3LYP/3-21G(d,p)

B3PW91/3-21G(d,p)

Bond length ()
Sn1O2
Sn1O3

1.841
1.841

1.852
1.852

1.865
1.865

1.858
1.858

2.0585
2.0472

Bond angle ()
O2Sn1O3

179.94

173.34

172.53

173.72

180.0

powders are examined by powder X-ray diffraction (XRD) technique using PAN alytical XPert diffractometer equipped with Cu
Ka radiation of wavelength 1.5406 . UVVis absorption spectrometer Infrared spectra of the nano particles were recorded using
Fourier transform infrared (FTIR) spectrometer (Shiraz) in the
range of 4000400 cm1 with a resolution of 1 cm1. Laser Raman
Spectroscopy was carried out by Renishaw invia Laser Raman Spectrometer. UVVis absorption measurements were carried out at
room temperature using (Shimadzu-2450). Varian Cary Eclipse
Spectrophotometer employing 15W Xe ash lamp was used for
the photoluminescence studies.

Computational methods
In the present work, HF and some of the hybrid methods; LSDA,
B3LYP and B3PW91 are carried out using the basis set 3-21G(d,p).
All these calculations are performed using GAUSSIAN 09W [17]
program package on Pentium IV processor in personal computer.
In DFT methods; Beckes three parameter hybrids function combined with the LeeYangParr correlation function (B3LYP)
[18,19], Beckes three parameter exact exchange-function (B3)
[20] combined with gradient-corrected correlational functional of
Lee, Yang and Parr (LYP) [21,22] and Perdew and Wang (PW91)
[23,24] predict the best results for molecular geometry and vibrational frequencies for moderately larger molecules. The calculated

frequencies are scaled down by suitable scaling factors to yield the

coherent with the observed frequencies.
The optimized molecular structure of the molecule is obtained
from Gaussian 09 and Gaussview program and is shown in Fig. 1.
The comparative optimized structural parameters such as bond
length, bond angle and dihedral angle are presented in Table 1.
The observed (FT-IR and FT-Raman) and calculated at HF and DFT
(LSDA, B3LYP and B3PW91) with 3-21 basis set vibrational frequencies, vibrational assignments and the total energy distribution
(TED) for B3PW91 of Tin Oxide are presented in Table 2. Experimental and simulated spectra of IR and Raman in both phases
are presented in the Figs. 2 and 3 respectively (see Table 3).
The total energy distribution (TED) calculations show the relative contributions of the redundant internal coordinates to each
normal vibrational mode of the molecule which enable numerically to describe the character of each mode and are carried out
by SQM method [25,26] using the output les created at the end
of the frequency calculations. The TED calculations are performed
by using PQS program [26].
Results and discussion
Molecular geometry
SnO2 posses a symmetry top molecular structure and belong to
C2V point group symmetry. The optimized structure of the molecule is obtained from Gaussian 09 and Gaussview program and is
shown in Fig. 1 with electrostatic potential surface map. The structure optimization and zero point vibrational energy of the compound in HF, LSDA, B3LYP and B3PW91/3-21G(d,p) are 2.37, 2.49,
2.41 and 2.44 kCal/mol, respectively. The present molecule has
two symmetrical SnO bonds. The bond length of SnO in bulk is
1.865 whereas the bond length of SnO in Nano phase is 2.058
and 2.047 respectively. From these results of the two phases, it
is observed that the SnO bond length of is 0.193 and 0.182
greater in Nano phase than the bulk. Due to this bond length increment, the property of present molecule is changed in Nano phase.
The calculated bond angle of OSnO is 172.53 in bulk and the
molecular structure is rather symmetry top. But the angle OSn
O in ano phase is 180 precisely which means that the molecule
is linear tri atomic. The shape of the molecular structure is changed
in Nano phase from bulk. So the present molecule SnO2 has attained a higher coordination and satised bonds in Nano phase.
Vibrational assignments

Fig. 1. Molecular structure and MEP of SnO2.

The molecule SnO2 belongs to C2V point group symmetry which

consists of 3 atoms, so it has 4 normal vibrational modes. Out of 4
fundamental vibrations of the molecule only three are observed
due to the suppression of vibration along bond axis and it can be
distributed as two stretching B2- asymmetric and A1 symmetric
and one in plane bending A1 vibrations, i.e., Cvib = 2A1 + 1B2. The
harmonic vibrational frequencies (un-scaled and scaled) calculated

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Table 2
Observed and calculated vibrational frequencies at HF & DFT (LSDA/B3LYP/B3PW91) with 3-21G (d,p) basis set of Tin oxide.
S. No.

FT-IR

Observed frequency(cm1) bulk

1
610vs
2
520vs
3

Unscaled values
1
2
3

FT-Raman

phase

120w

Observed frequency(cm1) nano phase

1
630vs
630m
2
570vs
570m
3

230w

Calculated frequency (cm1) [scaled]

Vibrational assignments

Species

B3LYP 3-21G (d,p) TED

HF

LSDA

B3LYP

B3PW91

3-21G (d,p)

3-21G (d,p)

3-21G (d,p)

3-21G (d,p)

627
576
120

624
582
104

625
574
119

617
574
119

(SnO)t Asym
(SnO)t Sym
(SnO)d

B2
A1
A1

(SnO)t 98%
(SnO)t 95%
(SnO)d 95%

794
778
92

879
786
80

845
765
79

864
779
68

627
576
120

624
582
104

625
574
119

617
574
119

(SnO)t Asym
(SnO)t Sym
(SnO)d

B2
A1
A1

(SnO)t 98%
(SnO)t 95%
(SnO)d 95%

vs; very strong, s; strong, m; medium, w; weak, vw; very weak. t; stretching, d; in plane bending.

Fig. 2. Experimental and calculated FT-IR spectra of SnO2.

Fig. 3. Experimental and calculated FTRaman spectra of SnO2.

at HF, LSDA, B3LYP and B3PW91 levels using the double split
valence basis set along with the diffuse and polarization functions,
3-21G(d,p) and observed FT-IR and FT-Raman frequencies for
various modes of vibrations have been presented in Table 2.

Electronic properties (HOMOLUMO analysis)

The calculations of the electronic structure of SnO2 are optimized in singlet state. The low energy electronic excited states of
molecule are calculated at the B3LYP/3-21G(d,p) level using the
TD-DFT approach on the previously optimized ground-state geometry of the molecule. The calculations are performed with gas
phase, DMSO and chloroform solvent effect. The calculated excitation energies, oscillator strength (f) and wavelength (k) and
spectral assignments are given in Table 5. The major contributions
of the transitions are designated with the aid of SWizard program
[34]. TD-DFT calculations predict three transitions in the near
ultraviolet region for SnO2 molecule. The strong transitions at
850.92 nm with an oscillator strength f = 0.0054 in gas phase, the
843.08 nm with an oscillator strength f = 0.0054 in chloroform
and the 833.14 nm with an oscillator strength f = 0.064 in DMSO
are calculated and assigned to an r ? r* transition. As can be seen,
the calculations performed at DMSO, gas phase and chloroform are
very close to each other. In view of calculated absorption spectra,
the maximum absorption wavelength corresponds to the

SnO vibrations
Many simple metal oxides with more than one oxygen atom
bound to a single metal atom usually absorb in the region 1020
970 cm1 [27]. Owing to the Nano size effect, the SnO stretching
vibrations are found in the region 800300 cm1 [2830]. The
SnO stretching is usually observed around 670 and 560 cm1
[31,32]. In this present case, the SnO asymmetric and symmetric
stretching vibrations appeared with very strong intensity at 610
and 520 cm1 respectively in bulk phase whereas the same are
observed at 630 and 530 cm1 respectively in Nano phase. The
deformation is identied at 120 cm1 in bulk and 230 cm1 in
Nano phase. When compared with bulk, all the SnO vibrations
are shifted up to higher region of the spectra which is purely due
to the change of bulk SnO to pseudo (super atoms) SnO [33].

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A. Ayeshamariam et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 118 (2014) 11351143
Table 3
Calculated IR intensity and Raman activity by HF/DFT (LSDA, B3LYP & B3PW91) with 3-21G(d,p) basis set.
S. No.

1
2
3

Observed frequency cm1

630
570
120

Methods
HF/3-21G (d,p)

LSDA/3-21G(d,p)

B3LYP/3-21G(d,p)

IR intensity

Raman activity

IR Intensity

Raman activity

IR intensity

Raman activity

B3PW91/3-21G(d,p)
IR intensity

Raman activity

0.00
0.66
46.87

74.82
0.00
0.00

13.27
0.030
12.40

0.148
27.15
0.088

12.83
0.028
16.74

0.256
29.13
0.138

15.50
0.0248
18.61

0.189
30.17
0.103

Fig. 4. The atomic orbital compositions of the frontier molecular orbital for SnO2.

Fig. 6. Preparation owchart of SnO2.

Fig. 5. Electrostatic potential surface map.

electronic transition from the HOMO to LUMO with 75% and from
the HOMO to LUMO+1 with 22% contribution. The other wavelength, excitation energies, oscillator strength and calculated counterparts with major contributions can be seen in Table 5. In nano
phase, the strong transitions at 303.94 nm with an oscillator
strength f = 0.121 in gas phase. In nano phase the transition is
shifted down with high oscillator strength which is due to the large
Kubo gap d(band gap).

The frontier molecular orbitals play an important role in the

electric and optical properties. The HOMO represents the ability
to donate an electron, LUMO as an electron acceptor. The 3D plots
of the frontier orbitals, HOMO and LUMO for molecule are in gas,
shown in Fig. 4. According to Fig. 4, LUMO is mainly localized over
the entire molecule and however HOMO is characterized by a
charge distribution on all atoms except Sn atom. The HOMO?LUMO transition implies an electron density transfer from Sn atom.
The HOMO and LUMO energy is 3.7907 eV in gas phase. Energy
difference between HOMO and LUMO orbital is called as Kubo
gap d that is an important stability for structures. The calculated
energy gaps 3.7907 eV, but in nano phase Kubo gap is 4.079 eV.
The increment of Kubo gap ensures the enhanced semiconductor
property of the molecule. The Fig. 5 showed that the electrostatic
potential map of the present compound.
NMR analysis
NMR spectroscopy is currently used for structure of organic
molecules as well as metal. The combined use of experimental
and computer simulation methods offer a powerful way to interpret and predict the structure of large molecules. The optimized
structure of SnO2 is used to calculate the NMR spectra at the HF
and DFT (B3LYP andB3PW91) methods with 3-21G(d,p) level using

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Table 4
Experimental and calculated 1H and

13

C NMR chemical shifts (ppm) of SnO2.

Atom position

Degeneracy

HF

B3LYP

B3PW91

Sn
O

1
2

3139.25
6669.66

1772.58
6373.11

1949.45
6082.52

Nano phase
Sn
O

1
2

2205.89
1756.37

the GIAO method. The theoretical 1H and 13C NMR chemical shifts
of SnO2 have been compared with the experimental data as shown
in Table 4. Chemical shifts are reported in ppm relative to TMS for
1H and 13C NMR spectra. Taking into account that the range of 13C
NMR chemical shifts for analogous organic molecules usually is
>1000 ppm. The accuracy ensures reliable interpretation of spectroscopic parameters. In the present work, 13C NMR chemical
shifts in the SnO2 are >1000 ppm, as they would be expected (in
Table 4).
Sn atom has the most electronegative property than oxygen
atom. The Sn atom which bonded to both the oxygen atom shows
too high chemical shifts. The values of the chemical shift of the
B3LYP and B3PW91 are nearly equal and lower than HF value.
The calculated chemical shift of the molecule in bulk phase is
1772.58 ppm whereas in Nano phase 2205.89 ppm. From this
observation it is clear that the diamagnetic shielding of SnO2 is also
increased in nano phase which results change in magnetic property
of the compound.
Fig. 7. XRD analysis of SnO2 nano powder.

XRD analysis
XRD patterns for as-prepared and after annealing a temperatures from 100 to 800 C for 2 h, are shown in Fig. 7. All the diffraction peaks are assigned to the tetragonal crystalline phase of SnO2.
The characteristics peaks positions are associated with (hkl) planes
(1 1 0), (1 0 1), (2 0 0), (2 1 1), (2 2 0) (0 0 2) (3 1 0) and (3 0 1) respectively. The peak positions of as-prepared SnO2 phase agree well
with the bulk and standard (SnO2) according to the JCPDS card
No. 88-0287), as shown in Fig. 7. The crystallite size (D) was calculated from line broadening analysis of the diffraction peaks using
the Scherer equation. The estimated average crystallite size is in
the nanometer scale, about 10 nm for as-prepared and increases
up to 32 nm after annealing at 800 C, which is the smallest crystallite size obtained so far through this route. The lattice constant
values a increases from 4.7461 to 4.7591 whereas c decreases
from 3.2027 to 3.1763 . The results agree well with oxides nanoparticles; usually they exhibit a lattice expansion with the reduction of strain and dislocation density.
In addition to the fundamental Raman peaks of rutile SnO2, two
weak Raman peaks located at about 632 and 679 cm1 are also
observed, whereas these two Raman peaks are not detected in
the rutile bulk SnO2 shown in Fig. 9. According to Granqvist and
Hultaker [35], these two weak Raman bands seem to correspond
to IR-active Eu(3) TO and A2uLO (TO is the mode of the transverse
optical phonons, LO is the mode of the longitudinal optical phonons) modes, respectively. Generally, the relaxation of the k 1=4 0

selection rule is progressive when the rate of disorder increases

or the size decreases, and infrared (IR) modes can become weakly
active when the structural changes induced by disorder and size
effects take place is shown in Fig. 8. And also, it is well known that
in an innite perfect crystal only the phonons near the center of
the Brillouin zone (BZ) contribute to the scattering of incident radiation due to the momentum conservation rule between phonons
and incident light. As the crystallite is reduced to Nano scale, the
phonon scattering will not be limited to the center of the Brillouin
zone, and phonon dispersion near the center of Brillouin zone must
also be considered. As a result, the symmetry-forbidden modes will
be observed, in addition to the shift and broadening of the rst-order optical phonon.
UVVisNIR analysis
The relationship between the absorption coefcient and optical
band gap can be expressed as,

aht A htEg 1=n

where a is the absorption coefcient corresponding to frequency t

and Eg is the band gap energy. The constant n depends on the nature
of electronic transition. SnO2 possess direct allowed transition and
hence n is equal to 2. The optical band gaps of SnO2 were determined by extrapolating the linear portion of the curve from the plot
of (aht)2 versus ht to aht = 0. For allowed transition (a)2 is plotted

Table 5
Theoretical electronic absorption spectra of SnO2 (absorption wavelength k (nm), excitation energies E (eV) and oscillator strengths (f) using TD-DFT/B3LYP/3-21G(d,p) method in
DMSO, chloroform and gas phase.
DMSO

Chloroform

Gas

Assignment
a

k (nm)

E (eV)

(f)

k (nm)

E (eV)

(f)

k (nm)

E (eV)

(f)

Major contribution

833.14

1.4881

0.064

843.08

1.0746

0.0063

850.92

1.4571

0.0054

H ? L (75%), H ? L+1 (22%)

r ? r*

r ? r*

Nano phase [solid]

303.94
1.716
a

Gas

H: HOMO; L: LUMO.

0.121

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1141

Fig. 10a. UVVisNIR reectance spectra of SnO2 as-prepared and annealed up to

800oC.

Fig. 8. FTIR Spectrum of SnO2 nano powder.

Fig. 10b. UVVisNIR direct allowed region of SnO2 as-prepared and annealed up
to 800 C.

Fig. 9. FTRaman spectrum of SnO2 nano powder.

against energy (E = ht) to yield a straight line for direct transitions

as shown in Fig. 10a from which the band gap was found. In this
study, the obtained optical band gap values show a small variation
between 3.476 and 3.048 eV, for as-prepared and samples heated
up to 800 C, as shown in Table 6.
When annealing temperature is increased from 100 to 800 C,
the band gap decreases due to mainly two factors: (i) decrease of
carrier concentration and (ii) un-lling (empty state) of the electronic states near the bottom of conduction band of SnO2 lattice.
When annealing temperature increases, the grain sizes are larger
thereby the density of grain boundary decreases and consequently
the number of trapped carriers is less which makes the availability
of higher amount of carriers for conduction. Such a variation in

Fig. 11. Photoluminescence spectra of SnO2 annealed up to 800 C.

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Table 6
UVVis band gap values and (PL) band gap values of SnO2 as-prepared and annealed up to800 C.
SnO2

ASP

100 C

200 C

300 C

400 C

500 C

600 C

700 C

800 C

UVVisNIR Eg (eV)
(PL) Eg (eV)

3.476
3.735

3.444
3.69

3.345
3.679

3.311
3.625

3.245
3.615

3.179
3.298

3.098
3.289

3.080
3.255

3.048
3.229

carrier concentration leads to a modication in the optical band

gap of degenerate semiconducting material which is related to
the Burstein-Moss effect [36] and represented as:

Eg  Ego DEgBM

h
2=3
3p2 ne
2m

where Ego is the intrinsic (un-doped) band gap, m is the electron

effective mass, ne number of carrier concentration.
The decrease of band gap for the SnO2 nanoparticles after
annealing at temperatures in the range 100800 C may be attributed to some oxygen deciency which is also based on BursteinMoss shift. This can be due to the fact that the carrier concentration
of these SnO2 nanoparticles gets reduced because of the creation of
acceptor type non-stoichiometric defects produced with increasing
temperature which may act as compensation centers. Information
concerning optical reectance is important in evaluating the optical performance of conducting oxide particles. An optical reection
spectrum of pure SnO2 particles is shown in Figs. 10a and 10b and
gap values of SnO2 powders annealed at different annealing
temperature are shown in Fig. 10b. It can be noticed that the
optical reection decreases may be due to subsurface scattering,
particularly true for reections from surroundings and broadened
decrease in reection of nano particles may be due to the roughness of the surface of the nano particles.
The ripples observed in these spectra results from the interference light, since they show waveform that are characteristic of the
interference light [37]. Higher annealing temperature led to a
steeper optical reection curve, which indicates a better larger
crystallinity of the particles and lower carrier density near the
band edge. Furthermore, there was a shift in the absorption edge
to shorter wavelength with increasing annealing temperature,
which was due to the Burstein Moss shift [38].
Photoluminescence analysis
Photoluminescence spectrum is convenient to investigate the
structure and defect or impurity levels [39]. Fig. 11, shows the
room temperature PL spectrum for the SnO2 as-prepared and
annealed up to 800 C samples. The excitation wavelength used
for the PL measurements is 210 nm. PL spectra show a strong UV
emission peak for all SnO2 samples and their corresponding band
gap values are given in Table 6. In polycrystalline and nano-crystalline oxides, oxygen vacancies are the most common defects, which
act as radiative centers in photoluminescence emission processes.
These peaks might have risen from the luminescence center of Sn
interstitials present in SnO2 nano particles [40].
Conclusion
The size of SnO2 particles can be tuned from 10 to 32 nm by
heating at different temperatures. The UV absorption of SnO2 nano
crystals occurs at 350 nm, indicating the existence of a weak quantum connement effect. PL emissions of as-prepared SnO2 nano
crystals centered in the range of 330370 nm and were originated
from various oxygen vacancies. It is interesting to note here that
the amount of reduction of thermal conductivity in nano sized
SnO2 from bulk SnO2 can be associated with the reduction of oxygen vacancy within nano phase. The optimized parameters of SnO2

are calculated at the HF and DFT (LSDA, B3LYP andB3PW91) methods with 3-21G(d,p) level and NMR spectra simulated using the
GIAO method. From the molecular geometry, it is found that
SnO2 is symmetry top molecule and belong to C2V point group
symmetry. From the molecular vibrations it is clear that, when
compared with bulk, all the SnO vibrations are shifted up to higher region of the spectra which is purely due to the change of bulk
SnO to pseudo (super atoms) SnO.

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