Vol 2 | Issue 6 | Spring Edition | DOI : February 2014 | Pp 707-710 | ISSN 2279 – 0381

Hydrothermally Synthesized Sb and Zn Doped Sno2 Nanoparticles

J. Mayandi *a, M. Marikkannan a, V. Ragavendran a, P. Jayabal b
a
Department of Materials Science, School of Chemistry, Madurai Kamaraj University, Madurai, India.
b.
Department of Laser studies, School of Physics, Madurai Kamaraj University, Madurai, India.
* e-mail id: [email protected]

Keywords: Hydrothermal, Currently various research works were focused

Nanoparticles, Raman spectra, Bandgap, on, to enhance the electrical and optical properties
Photoluminescence.. of different TCOs for the optoelectronic
applications. Among the various TCOs, the SnO 2
Abstract: We have synthesized was an important n type semiconductor with wide
undoped and doped SnO2 nanoparticles with 5% of band gap (3.6 eV at 300K) and considerable
Antimony and Zinc by a simple hydrothermal material for optoelectronic devices [7]. In the
method. The prepared SnO2 nanoparticles show intrinsic semiconductors the presence of oxygen
tetragonal rutile structure with orientation along vacancies enhances the electrical conductivity of
the (101) reflection by XRD spectra. In addition the material. Since the addition of impurity atoms
structural determination was also carried out by in the SnO2 enhances the electrical and optical
Raman measurements. The observed properties of the material [8]. The antimony and
corresponding vibrational modes agree with the zinc were the good choices to enhance both the
reported SnO2 rutile structure. Scanning electron electrical and optical properties of the SnO2
microscope analysis reveals that the observed nanoparticles. Nowadays tin oxide was
particles were spherical in shape and coalesced. synthesized by different methods such as co
The optical properties of the prepared precipitation, combustion, sol gel and
nanoparticles were examined using UV-visible hydrothermal method [9]. In these methods, the
and Photoluminescence. The optical band gap was hydrothermal method is the simple method to
estimated between 3.29 and 3.43eV. In the produce the SnO2 nanoparticles with high yeild.
photoluminescence spectra the emission peaks at In this report we have synthesized pure,
363 and 381 nm (3.3 eV) were seen for all the Sb and Zn doped SnO2 nanoparticles by
samples. It is understood that with the optical hydrothermal method. The prepared materials
studies it may not be possible to probe the dopant, were analyzed by different structural and optical
due to the less concentration doped in the techniques. The structural and optical properties
material. A further investigation is essential to of the nanoparticles were discussed in detail.
probe the doped materialst. Experimental:
Introduction In this present work, we have synthesized
Due to the outstanding electrical and Pure, Sb and Zn doped SnO2 nanoparticles by
optical properties of the transparent conducting simple hydrothermal method. Initially 0.9 ml of
oxide (TCOs) materials, it has been widely used hydrochloric acid was added to a 30 ml of ethanol
for various optoelectronic devices [1]. Normally solution and stirred for 3 minutes at room
the transparent conducting oxides were used in temperature. After the stirring process, the
flat panel displays, liquid crystal displays, organic precursor SnCl2.2H2O (purified from Merck)
light emitting diodes, solar cells and etc [2]. mixed with the hydrochloric acid and ethanol
Among the various TCOs, the Sn doped indium solution. The final solution was stirred for 2 hours
oxide (ITO) has been reported as a favorable at room temperature. Finally the transparent
material for the optoelectronic applications [3]. solution was transferred in to the Teflon lined
But the issues of an indium were the price, stainless steel autoclave (50 ml capacity). Then
availability in earth crust, poor flexibility and the autoclave was kept at 200oC for 4 hours using
strong reflection of light, so the replacement of muffle furnace. The final solution was dried at
ITO is major challenge [4, 5]. Hence we intend to 100oC to get a solid powder. The above mentioned
explore the possibility to find the alternative similar processes are followed to prepare the 5% of
materials for ITO. The Al doped ZnO and F, Sb Sb and Zn doped SnO2 nanoparticles.
doped SnO2 wereS reported as the alternative The prepared nanoparticles were
materials for ITO [6] with similar properties. subjected various structural and optical

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 Journal of NanoScience and NanoTechnology | Vol 2 | Issue 6 | Spring Edition | ISSN 2279 – 0381

measurements. Structural analysis of the samples estimate the grain size and strain of the
carried out by X ray diffraction (XRD) pattern and nanoparticles. In this work we have used the
the vibrational modes of the samples were uniform deformation model (UDM) to the
understood by Raman measurements. The estimated grain sizes such as 5, 4 and 5 nm for
morphology of the as prepared nanoparticles was pure, Sb and Zn doped SnO2 nanoparticles and
characterized by scanning electron microscope tabulated in table 1.
(SEM). The optical properties of the pure and Table 1: Shows the structural parameters of
doped SnO2 nanoparticles were examined by UV- pure and doped SnO2 samples.
visible and photoluminescence spectroscopic
techniques. Grai W-H plot
d Latti
n
Results and Discussions: spaci ce
Size Grain
XRD Analysis: ng cons
Sam in Size
(101) tant Strai
ple [nm] in
[Å] (101) n
[nm]
[Å]
Pure 2.644
3.186 12 5 -0.010
SnO2 3
Sb: 2.643
3.198 11 4 -0.013
SnO2 2
Zn: 2.644
3.187 12 5 -0.013
SnO2 9
Raman Analysis:

Fig1: XRD pattern of pure and doped SnO2

nanoparticles

The XRD spectra of pure, Sb and Zn doped

SnO2 nanoparticles are shown in fig1. In the XRD
results, the observed diffraction peaks can be
indexed to tetragonal rutile structure of SnO 2 and
the observed planes are consistent with the
JCPDS card file no 41-1445. All the samples
possess the polycrystalline nature with (101)
preferred orientation (lattice parameter a = 4.7382
Fig 2: shows the Raman spectra of pure and
Å and c =3.1871Å). The intensity of the
Zn doped SnO2 nanoparticles.
corresponding peak was changed with respect to
The Raman spectra for the
the different impurity additions. There was no
hydrothermally prepared pure and Zn doped SnO 2
other mixed phase appeared in the fig 1.This
nanoparticles were shown in the fig2. According to
indicates that the Sb and Zn impurity additions
group theory, there were 18 modes possible for
did not change the tetragonal structure of SnO 2. It
rutile SnO2 structure. Among the 18 modes only
was a strong evidence for Zn and Sb substituted in
four modes are Raman active. The three modes
the SnO2 host lattice. The grain sizes of the
were non-degenerate (A1g, B1g and B2g) and
nanoparticles were estimated using the scherrer
another one was doubly degenerate (Eg) mode
formula [10]. These observed sizes such as 12, 11
[12].In our Raman results; we have observed
and 12 nm for pure, Sb and Zn doped SnO 2
vibrational modes at 484, 630 and769 cm-1(A1g) for
nanoparticles respectively. The other structural
pure SnO2. Similarly the peak exhibited at 473,
parameters like d spacing and lattice constant of
568, 633 and 778 cm-1 for Zn doped SnO2
the nanoparticles were calculated and shown in
nanoparticles. These peaks agreed with the
the table 1.The observed values agreed with the
reported rutile structure of SnO2 values [12, 13].
standard values. We used to evaluate the grain
K. Srinivas et al observed the similar peaks for
size and strain of the pure, Sb and Zn doped SnO2
tetragonal structure SnO2 nanorods in the Raman
nanoparticles by Williamson Halls (W-H) plot
measurements [13]. These observed modes
analysis. V.D. Mote et al suggested the W-H
confirmed the formation of rutile structure of
analysis was the significant method to estimate
SnO2 nanoparticles. It is also supported with the
the crystallite size and strain values. The
XRD results shown in fig1. We cannot observe the
observed values agreed with TEM results [11].
similar vibrational modes in the Sb doped SnO2
Usually different models have been proposed to
nanoparticles (shown in the insert fig 2).We were
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 Journal of NanoScience and NanoTechnology | Vol 2 | Issue 6 | Spring Edition | ISSN 2279 – 0381

unable to understand the reason for the absence of shows the tauc’s plot for pure SnO2 nanoparticles).
these kinds of modes. The detailed analysis will be Normally the band gap of the materials depends
carried out for the absence of vibrational modes in on the preparation methods and conditions. In
Sb doped SnO2 nanoparticles in future. this work we observed the band gap values 3.43,
SEM analysis: 3.29 and 3.29 eV for pure, Sb and Zn doped SnO2
nanoparticles respectively. Band gap of the Sb and
Zn doped SnO2 nanoparticles were decreased
compared to the pure SnO2. It confirms that the
carrier concentrations of the Zn and Sb doped
SnO2 nanoparticles increased compared to the
pure SnO2 nanoparticles. The new electronic
states created below the conduction band of the
material may reduce the band gap of the Zn and
Sb doped SnO2 nanoparticles. It was also
explained by the BM shifts in the TCOs.
S.Vijyalakshmi et al reported the different mol%
of the Zn doped SnO2 decreased the band gap
value [15]. We can tune the band gap of the
Fig3: SEM image of the pure SnO2 materials through the Zn and Sb when used as an
nanoparticles. impurity. The shifts in the optical band gap value
The morphology of the pure SnO2 indicate the prepared Zn and Sb doped SnO2
nanoparticles is shown in the fig 3. In this SEM nanoparticles move towards the higher
image the Spherical sized SnO2 nano particles wavelength region (visible region). Hence these
with nearly uniform size. From the SEM image we materials were suitable for the optoelectronic
observed that the particles were agglomerated. devices.
The agglomeration effect depends on the size of Another important
the particles. The size of the particle was optical constants was refractive index. Here we
estimated to be around 11-12nm using XRD. As estimated the refractive index of the nanoparticles
the particle size move towards the nano scale, the through the moss relation [16].The moss equation
agglomeration gets increased. represents the relation between refractive index
and band gap of the material. V.Kumar has
UV-visible Analysis:
reported the modified moss relation for estimating
the index of the materials [17]. The extracted
values based on the above method were closely
matched with the ellipsometery analysis. In this
work the calculated index values 2.01 for pure
SnO2 and 2.06 for Sb, Zn doped SnO2
nanoparticles. The observed index values are
closely agreed to the reported refractive index of
ITO films [18].
Photoluminescence analysis:
The room temperature recorded
photoluminescence spectra for pure, Sb and Zn
doped SnO2 nanoparticles were shown in the fig 5.

Fig 4: UV-vis absorption spectra of pure and

doped SnO2 nanoparticles.
UV-visible absorption spectra of the
samples were shown in fig4. The absorption band
at 370nm which originates from the band gap
transitions and directs the existence of highly
crystalline SnO2. The band gap of the material
was evaluated by Tauc’s relation [14].

( h ) = A (h -Eg)1/2………(1)
Here is the absorption coefficient, A is a
constant and Eg is the band gap. Optical band gap Fig 5: shows the photoluminescence spectra
of the respective materials was estimated by of pure, Sb and Zn doped SnO2 nanoparticles
graph plot between ( h )2vs h (inset figure 4

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 Journal of NanoScience and NanoTechnology | Vol 2 | Issue 6 | Spring Edition | ISSN 2279 – 0381

under the excitation of 325 nm at room

temperature.
Excitation wavelength 325 nm was used References
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Acknowledgement:
The authors are thankful to the DST-
SERB/F/1829/2012-2013 for the partial support.
One of the authors MM, thank the Department of
laser studies, school of physics, Madurai Kamaraj
University for optical measurements. The author
also thank to Ms. C. Abinaya for proof reading.

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