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International Journal of Nanotechnology
and Application (IJNA)
ISSN(P): 2277-4777; ISSN(E): 2278-9391
Vol. 4, Issue 3, Jun 2014, 21-28
TJPRC Pvt. Ltd.


STUDY OF NONLINEAR OPTICAL PROPERTIES OF SODIUM DOPED V
2
O
5
NANOPARTICLES
PRABIN PRADHAN, MURALIKRISHNA MOLLI, LAKSHMAN KUMAR V, LACHIT SAIKIA,
V. SAI MUTHUKUMAR, S. SIVA SANKARA SAI & K. VENKATARAMANIAH
Department of Physics, Sri Sathya Sai Institute of Higher Learning, Prasanthinilayam, Anantapur, Andhra Pradesh, India

ABSTRACT
We report here the nonlinear optical (NLO) properties of vanadium pentoxide (V
2
O
5
) nanoparticles and
improvement in the optical limiting performance due to sodium doping in V
2
O
5
. In this study, V
2
O
5
and Na-doped V
2
O
5
nanoparticles were synthesized by solution combustion method. The as-synthesized samples were further characterized
using XRD, FESEM, EDAX, TEM, and UV-Visible spectroscopy. The electrical conductivity measured using Van der
Pauw method showed that the electrical conductivity increased with increase in doping concentration. Open-aperture
z-scan technique was employed to study the NLO absorption behavior of the synthesized samples using a second harmonic
(532 nm) of Nd: YAG laser with 15 ns pulse width. We observed that 5 mol % Na-doped V
2
O
5
exhibited enhanced
nonlinear absorption compared to undoped V
2
O
5
and 3 mol % Na- doped V
2
O
5
which we attribute to the enhanced free
carrier concentration due to Na doping. The mechanism of nonlinear absorption (NLA) was found to be a three photon
absorption process.
KEYWORDS: Optical Limiting, Z-Scan, V
2
O
5,
Na-Doped V
2
O
5
, Nonlinear Absorption, Nonlinear Scattering
INTRODUCTION
Transition metal oxides with different morphological structure find their way in various potential applications.
There are series of oxides that form from vanadium which are commonly available as VO, V
2
O
3
, VO
2
, and V
2
O
5
. The most
important of these oxides is V
2
O
5
, and is the most stable member of the series [1].Vanadium pentoxide (V
2
O
5
) has been in
the forefront of applied research in view of its multifunctional properties, which include optical, electronic and
electrochromic properties [2]. Nanostructures of V
2
O
5
are currently used in lithium-ion battery, super capacitors, field
emission, chemical and biosensors and for fabricating various nanodevices. Also, vanadium oxides have been employed in
photonic applications like surface-enhanced Raman spectroscopy and nonlinear optical studies [3].Nonlinear optical
studies were reported on some nanostructures of vanadium oxides in the form of nanotubes [4], nanoflowers [3] and thin
films [5]. In this study, we report the nonlinear optical absorption properties of V
2
O
5
nanoparticles and Na-doped
V
2
O
5
nanoparticles. We found that Na doping has enhanced the nonlinear absorption of V
2
O
5
nanoparticles.
EXPERIMENTAL
Synthesis
V
2
O
5
and Na-doped V
2
O
5
nanoparticles were synthesized through solution combustion method. To synthesize
vanadium pentoxide, 2 g of ammonium metavanadate, 1.28 g glycine and 8 g ammonium nitrate were dissolved in 15 ml of
distilled water. The mixture was taken in a 300 cm
3
pyrex dish and introduced into a muffle furnace (38179 cm
3
)
22


Impact Factor (JCC): 1.8003 Index Copernicus
maintained at 500
0
C.The mixture boils, ignites
immense evolution of gaseous products in the process.
the entire volume of the container. The entire combustion process
yellowish orange colored vandia.
Figure 1: a) PureV
2
O
5
b)
Na was added into the matrix
study was sodium nitrate. Appropriate amount of the sodium nitrate was added to the stoichiometric mixture of ammonium
metavanadate, glycine and ammonium nitrate to synthesize 3 mol% and 5 mol% Na
combustion was vigorous. The Na-doped sample
to dark brown (shown in figure 1).
RESULTS AND DISCUSSIONS
X-Ray Diffraction Studies
The powder XRD patterns for V
using PAN alytical X'pert Pro MPD diffracto
The XRD patterns shown in figure 2 show that a
indexed with orthorhombic V
2
O
5
(JCPDS No: 01
= = = 90
0
. The powder XRD pattern of the samples which are doped with Na can be indexed with
and monoclinic NaV
6
O
15
. Peaks labelled with
undoped V
2
O
5
. The crystallite size of all the samples
table 1. Silicon was used as the standard to subtract the instrument
size values show that the samples are nanocrystalline.
Prabin Pradhan, Muralikrishna Molli, Lakshman Kumar V, Lachit Saikia
V. Sai Muthukumar, S. Siva Sankara Sai & K. Venkataramaniah
Factor (JCC): 1.8003 Index Copernicus
C.The mixture boils, ignites, and burns with an incandescent flame of yellow
immense evolution of gaseous products in the process. The product of combustion is orthorhombic V
the entire volume of the container. The entire combustion process was completed in about 3 min producing about 1.55 g of
b) Na-Doped V
2
O
5
Obtained from Solution Combustion Synthesis
of vanadium pentoxide using their corresponding metal
study was sodium nitrate. Appropriate amount of the sodium nitrate was added to the stoichiometric mixture of ammonium
metavanadate, glycine and ammonium nitrate to synthesize 3 mol% and 5 mol% Na-doped
doped sample showed a significant color change. There wa

for V
2
O
5
, 3 mol% Na-doped V
2
O
5
and 5 mol% Na- doped
alytical X'pert Pro MPD diffracto meter with the following settings: voltage 45 kV and current 30 mA
show that all the samples are crystalline. The powder XRD pattern of V
(JCPDS No: 01-072-0433) with unit cell parametersa = 11.51, b = 4.36 , c = 3.56 ,
The powder XRD pattern of the samples which are doped with Na can be indexed with
. Peaks labelled with * and # in the XRD patterns distinguish the Na
The crystallite size of all the samples were calculated using Debye Scherrer
Silicon was used as the standard to subtract the instruments contribution to the peak broadening. The crystallite
nanocrystalline.
Prabin Pradhan, Muralikrishna Molli, Lakshman Kumar V, Lachit Saikia,
, S. Siva Sankara Sai & K. Venkataramaniah
Factor (JCC): 1.8003 Index Copernicus Value (ICV): 3.0
, and burns with an incandescent flame of yellow-green color with an
The product of combustion is orthorhombic V
2
O
5
, which occupies
completed in about 3 min producing about 1.55 g of

Solution Combustion Synthesis
metal salts. The salt used for this
study was sodium nitrate. Appropriate amount of the sodium nitrate was added to the stoichiometric mixture of ammonium
doped V
2
O
5
. The nature of the
was a color change from orange
doped V
2
O
5
samples were recorded
with the following settings: voltage 45 kV and current 30 mA.
The powder XRD pattern of V
2
O
5
can be
0433) with unit cell parametersa = 11.51, b = 4.36 , c = 3.56 ,
The powder XRD pattern of the samples which are doped with Na can be indexed with orthorhombic V
2
O
5

in the XRD patterns distinguish the Na- doped samples from
calculated using Debye Scherrer formula and tabulated in
contribution to the peak broadening. The crystallite
Study of Nonlinear Optical Properties of Sodium Doped V

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Figure 2: XRD Patterns for Pure
Table 1: Crystallite Size of V

Electron Microscopy
The electron micrograph of the sample was
image of V
2
O
5
is shown in figure 3. The size of the particles is around 200 nm.
Figure
Elemental analysis was performed using EDAX. The atomic percentage of V and O was found to be 28.57% and
71.43% respectively. No other element was found showing that the sample
identified using EDAX as the doping p
well as electrical conductivity measurements where we found that Na doping has actually increased the electrical
conductivity which is reported in the electrical conductivity data.
The TEM micrograph and electron diffraction pattern
Eindhoven, Netherlands and 200 kV). The TEM micrograph and electron diffraction pattern are shown in the fig
Study of Nonlinear Optical Properties of Sodium Doped V2O5 Nanoparticles


Pure V
2
O
5
, 3mol% Na-Doped V
2
O
5
and 5mol% Na-Doped
: Crystallite Size of V
2
O
5
, 3 mol% Na-Doped V
2
O
5
and 5 mol% Na
Sample Crystallite Size (nm)
V
2
O
5
163
3 mol % Na- V
2
O
5
82
5 mol % Na- V
2
O
5
163
The electron micrograph of the sample was collected using FESEM (Zeiss Model Gemini Ultra 55).
The size of the particles is around 200 nm.

ure 3: FESEM Micrograph of V
2
O
5
Nanoparticles
Elemental analysis was performed using EDAX. The atomic percentage of V and O was found to be 28.57% and
71.43% respectively. No other element was found showing that the sample was not contaminated.
identified using EDAX as the doping percentage was very small. The presence of Na was
well as electrical conductivity measurements where we found that Na doping has actually increased the electrical
conductivity which is reported in the electrical conductivity data.
and electron diffraction pattern of V
2
O
5
were recorded using HRTEM (Tecnai F30, FEI,
Eindhoven, Netherlands and 200 kV). The TEM micrograph and electron diffraction pattern are shown in the fig
23
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Doped V
2
O
5
Nanoparticles
and 5 mol% Na-Dopedv
2
o
5

collected using FESEM (Zeiss Model Gemini Ultra 55). The FESEM
Elemental analysis was performed using EDAX. The atomic percentage of V and O was found to be 28.57% and
not contaminated. Sodium could not be
confirmed from XRD data as
well as electrical conductivity measurements where we found that Na doping has actually increased the electrical
were recorded using HRTEM (Tecnai F30, FEI,
Eindhoven, Netherlands and 200 kV). The TEM micrograph and electron diffraction pattern are shown in the figure 4.
24


Impact Factor (JCC): 1.8003 Index Copernicus
Figure 4: (a) Electron Diffraction
UV-Visible Absorption Spectroscopy
The absorption spectra of the samples were recorded using UV
Samples were dispersed in HPLC water and the spectra were recorded between 200 and 800 nm. The UV
absorption spectra for V
2
O
5
, 3 mol% and 5 mol% Na
Figure 5: UV-Vis Spectra
Electrical Conductivity Measurements
The electrical conductivity of pure V
method. The plot of conductivity vs. temperature is shown in fig
Prabin Pradhan, Muralikrishna Molli, Lakshman Kumar V, Lachit Saikia
V. Sai Muthukumar, S. Siva Sankara Sai & K. Venkataramaniah
Factor (JCC): 1.8003 Index Copernicus
Diffraction Pattern and (b) TEM Micrograph of V
2
O

of the samples were recorded using UV-Visible Spectrophotometer (Shimadzu UV
Samples were dispersed in HPLC water and the spectra were recorded between 200 and 800 nm. The UV
, 3 mol% and 5 mol% Na-doped V
2
O
5
samples are shown in the figure

Spectra for Pure V
2
O
5
, 3 mol% and 5 mol% Na-Doped
Conductivity Measurements
of pure V
2
O
5,
3 mol% and 5 mol% Na-doped V
2
O
5
was measured using Van der Pauw
The plot of conductivity vs. temperature is shown in figure 6.
Prabin Pradhan, Muralikrishna Molli, Lakshman Kumar V, Lachit Saikia,
, S. Siva Sankara Sai & K. Venkataramaniah
Factor (JCC): 1.8003 Index Copernicus Value (ICV): 3.0

O
5
Nanoparticles
Visible Spectrophotometer (Shimadzu UV-2450).
Samples were dispersed in HPLC water and the spectra were recorded between 200 and 800 nm. The UV-Visible
les are shown in the figure 5.

Doped V
2
O
5

measured using Van der Pauw
Study of Nonlinear Optical Properties of Sodium Doped V2O5 Nanoparticles 25

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Figure 6: Electrical Conductivity Measurements of V
2
O
5
, 3 mol% and 5 mol% Na- Doped V
2
O
5

The plot shows increase in conductivity of Na-doped V
2
O
5
samples which can be attributed to increase in free
carrier concentration. With increase in doping concentration of Na the electrical conductivity is increased.
Nonlinear Optical Studies
We employed popular open aperture z-scan technique [6] to study the NLO properties of these samples.
In particular, we adopted open aperture z-scan configuration to measure nonlinear optical absorption and scattering losses.
In a conventional open aperture z-scan setup, the sample of interest is translated across the focal plane of a converging lens
which focuses the incident laser beam. The transmittance of the sample is recorded as a function of sample position by a
calibrated photodetector. The temporal fluctuations of the incident laser pulses are monitored through another reference
photodetector. We have used a high power Nd: YAG laser with 532 nm excitation line and 15 ns pulse width.
The repetition of laser pulses was restricted to 1 Hz and the whole experiment was automated using Lab VIEW interfacing
that enabled easier sample translation and data collection. In order to infer and quantify the presence of nonlinear scattering
in these samples, we fixed a third photodetector at about 45
0
on the same translation stage in very close proximity to the
sample holder. 1.8 mg of each sample was dispersed in 5 ml HPLC water in three different 5 ml sample bottles.
Each sample was taken in a 1mm thick fused silica cuvette and the linear transmittance of the samples was adjusted to be
around 70% at 532nm.
The samples were found to exhibit large optical nonlinearity, leading to optical limiting (OL) behavior. Optical
limiting can be due to a variety of nonlinear optical processes such as reverse saturable absorption (RSA), multiphoton
absorption, and thermal scattering. Optical limiters based on nonlinear absorption mechanisms are known to be very
efficient[3].We find that the data fits best to a three-photon type absorption process, given by the expression [7]
I =
(1-R)
2
cxp(-
O
L)
nP
O
] lnj1 +P
0
2
exp(2t
2
) + P
0
exp(t
2
)[ Jt

-
(1)
Here, z is the sample position with respect to the focal point,
0
is the linear absorption coefficient, R is the
Fresnel reflection at the interface of the sample material with air, L (= l ) is the sample length, and
( 1) 0
0 0
0
1 exp( )
(1 )
n n n n
n l
p n R I
n

+

=


, I
0
being the intensity at the focal point
0 0
n
p q = for a two photon absorption process with
26


Impact Factor (JCC): 1.8003 Index Copernicus
n=1. The values of the three-photon absorption coefficient
0.7 x 10
-23
m
3
w
2
/ ,2.1 x 10
-23
m
3
w
2
/ ,
respectively. The fitted transmittance
figure 8a for input laser energy of 200 J
As shown in figure 8b, the V
Na-doped V
2
O
5
, the transmittance decreases sharply indicating strong OL effect at lower thresholds
applications. The limiting threshold for the
decreased to limiting threshold level of
saturable absorption (SA) at low intensities and strong nonlinear attenuation of laser pulses at higher intensities due to the
simultaneous contributions from NLA &
of near resonant absorption arising from
exhibited optical limiting performance due to signif
samples plausibly arises from the formation of m
samples [8].
Figure 8: a) Overlay of Experimental Data
c) Nonlinear Scattering Data
Considering the fact that the sample is semitransparent at the excitation wavelength, the observed nonlinearity
will have contributions from excited-state absorption involving real excited states.
absorption coefficient of V
2
O
5
with increasing doping of concentration Na can also be attributed to the enhanced free
carrier concentration. Hence, it is appropriate to consider the observed nonlinearity as an effective three
where both genuine 3PA and sequential three
CONCLUSIONS
In this study, we report the NLO
V
2
O
5
nanoparticles. Open-aperture z-
synthesized samples using a second harmonic (532 nm) of Nd: YAG laser with 15 ns pulse width. The z
fitted using the Matlab code to decipher the mechanism of optical nonlinearity in V
We found three-photon absorption to be the best fit for our data. The nanoparticles exhibited combined SA and RSA
behavior at different input laser energies. From the study, we found that 5 mol % Na
Prabin Pradhan, Muralikrishna Molli, Lakshman Kumar V, Lachit Saikia
V. Sai Muthukumar, S. Siva Sankara Sai & K. Venkataramaniah
Factor (JCC): 1.8003 Index Copernicus
photon absorption coefficient obtained from the theoretical fit of the z
, 3.6 x 10
-23
m
3
w
2
/ , for V
2
O
5
,3 mol% Na-doped V
2
curve for pure V
2
O
5
and 3mol% and 5mol% Na-doped V
for input laser energy of 200 J
V
2
O
5
nanoparticles do not show significant OL threshold whereas in the case of
, the transmittance decreases sharply indicating strong OL effect at lower thresholds
applications. The limiting threshold for the 3 mol% Na-doped V
2
O
5
was found to be 24.4 Jcm
of 1.18 Jcm
-2
in case of 5 mol% Na-doped V
2
O
5
.V
2
O
5
at low intensities and strong nonlinear attenuation of laser pulses at higher intensities due to the
simultaneous contributions from NLA &nonlinear scattering (NLS). The presence of SA may be attributed to the presence
from linear absorption of V
2
O
5
nanoparticles near 532 nm excitation
performance due to significant NLS at higher intensities as shown in figure 8c
samples plausibly arises from the formation of microplasma and microbubble scattering centers in nanostructured
Experimental Data and Theoretical Fitting of Z-Scan Data
Scattering Data of V
2
O
5
, 3 Mol % Na-Doped V
2
O
5
, 5 mol % Na
Considering the fact that the sample is semitransparent at the excitation wavelength, the observed nonlinearity
state absorption involving real excited states. The enhancement in the nonlinear
with increasing doping of concentration Na can also be attributed to the enhanced free
Hence, it is appropriate to consider the observed nonlinearity as an effective three
sequential three-photon absorption contribute to the phenomenon
NLO absorption properties of vanadium pentoxide (V
2
O
-scan technique was employed to study the NLO
synthesized samples using a second harmonic (532 nm) of Nd: YAG laser with 15 ns pulse width. The z
er the mechanism of optical nonlinearity in V
2
O
5
and Na
photon absorption to be the best fit for our data. The nanoparticles exhibited combined SA and RSA
behavior at different input laser energies. From the study, we found that 5 mol % Na-doped V
Prabin Pradhan, Muralikrishna Molli, Lakshman Kumar V, Lachit Saikia,
, S. Siva Sankara Sai & K. Venkataramaniah
Factor (JCC): 1.8003 Index Copernicus Value (ICV): 3.0
rom the theoretical fit of the z-scan data are
O
5
, 5 mol% Na- doped V
2
O
5

doped V
2
O
5
are shown in the
do not show significant OL threshold whereas in the case of
, the transmittance decreases sharply indicating strong OL effect at lower thresholds-ideal for practical
was found to be 24.4 Jcm
-2
which prolifically
5
nanoparticles exhibited weak
at low intensities and strong nonlinear attenuation of laser pulses at higher intensities due to the
. The presence of SA may be attributed to the presence
near 532 nm excitation. All our samples
as shown in figure 8c. The NLS in our
icroplasma and microbubble scattering centers in nanostructured

Scan Data, b) OL Response,
, 5 mol % Na-Doped V
2
O
5

Considering the fact that the sample is semitransparent at the excitation wavelength, the observed nonlinearity
The enhancement in the nonlinear
with increasing doping of concentration Na can also be attributed to the enhanced free
Hence, it is appropriate to consider the observed nonlinearity as an effective three-photon process,
photon absorption contribute to the phenomenon [3].
O
5
) nanoparticles and Na-doped
NLO absorption behavior of the
synthesized samples using a second harmonic (532 nm) of Nd: YAG laser with 15 ns pulse width. The z-scan data was
and Na-doped V
2
O
5
nanoparticles.
photon absorption to be the best fit for our data. The nanoparticles exhibited combined SA and RSA
doped V
2
O
5
exhibited enhanced NLA
Study of Nonlinear Optical Properties of Sodium Doped V2O5 Nanoparticles 27

www.tjprc.org editor@tjprc.org
compared to undoped V
2
O
5
which we attribute to the enhanced free carrier concentration due to Na doping. The OL
threshold of 5 mol% Na-doped V
2
O
5
was found to be 1.18Jcm
-2
with input laser energy of 200 J.
ACKNOWLEDGEMENTS
Authors express their gratitude to Bhagawan Sri Sathya Sai Baba, the founder chancellor of SSSIHL, for his
constant support and lab facilities. Authors also thank UGC and DST for the financial support.
REFERENCES
1. B. Yan, L. Liao, Y. You, X. Xu, Z. Zheng, Z. Shen, J. Ma, L. Tong, T. Yu, 2009,Singlecrystalline V
2

O
5
ultralongnanoribbon waveguides, Adv. Mater. 21, pp. 24362440.
2. Wang, Y.; Cao, G., 2006, Synthesis and Enhanced Intercalation Properties of Nanostructured Vanadium
Oxides, Chem Mater 18, pp. 2787-2804.
3. Manas R. Parida, C. Vijayan, C. S. Rout, C. S. Suchand Sandeep, Reji Philip, P. C. Deshmukh, 2011, Room
Temperature Ferromagnetism and Optical Limiting in V
2
O
5
Nanoflowers Synthesized by a Novel Method,
J. Phys. Chem. C115, pp. 112117.
4. J. F. Xu et. al., 2002, Nonlinear optical transmission in VOx nanotubes and VOx nanotube composites,
Appl. Phys. Letters 81, pp. 1711-1713.
5. W. Wang, et. al., 2006, Dynamic optical limiting experiments on vanadium dioxide and vanadium pentoxide thin
films irradiated by a laser beam, Appl. Opt. 45, pp. 3378-3381.
6. M. Sheik Bahae et al., 1990, Sensitive Measurement of Optical Nonlinearities Using a Single Beam, IEEE J.
Quantum Electron. QE-26, pp. 760.
7. Sutherland RL. Handbook of Nonlinear optics, New York: Marcel Dekker Inc.; 1996. pp. 509-11.
8. V. Joudrier, P. Bourdon, F. Hache, C. Flytzanis, 1998, Nonlinear light scattering in a two-component medium:
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