Improved conversion efficiency of dye sensitized solar cell using Zn doped TiO2-ZrO2

nanocomposite
Laxmi J. Tomar, Piyush J. Bhatt, Rahul K. Desai, B. S. Chakrabarty, and C. J. Panchal

Citation: 1731, 050132 (2016); doi: 10.1063/1.4947786

View online: http://dx.doi.org/10.1063/1.4947786
View Table of Contents: http://aip.scitation.org/toc/apc/1731/1
Published by the American Institute of Physics
 Improved Conversion Efficiency of Dye Sensitized Solar
Cell Using Zn Doped TiO2-ZrO2 Nanocomposite
Laxmi J. Tomar*, Piyush J. Bhatt, Rahul K. Desai, B. S. Chakrabarty, C. J.
Panchal

Department of Applied Physics, Faculty of Technology and Engineering, The M. S. University of Baroda,
Vadodara, India-390003
*
Email: laxmi_tomar86@yahoo.com

Abstract. TiO2-ZrO2 and Zn doped TiO2-ZrO2 nanocomposites were prepared by hydrothermal method for dye
sensitized solar cell (DSSC) application. The structural and optical properties were investigated by X –ray diffraction
(XRD) and UV-Visible spectroscopy respectively. XRD results revealed the formation of material in nano size. The
average crystallite size is 22.32 nm, 17.41 nm and 6.31 nm for TiO 2, TiO2-ZrO2 and Zn doped TiO2-ZrO2
nanocomposites respectively. The optical bandgap varies from 2.04 eV to 3.75 eV. Dye sensitized solar cells were
fabricated using the prepared material. Pomegranate juice was used as a sensitizer and graphite coated conducting glass
plate was used as counter electrode. The I – V characteristics were recorded to measure photo response of DSSC.
Photovoltaic parameter like open circuit voltage, power conversion efficiency, and fill factor were evaluated for
fabricated solar cell. The power conversion efficiency of DSSC fabricated with TiO2, TiO2-ZrO2 and Zn doped TiO2-
ZrO2 nanocomposites were found 0.71%, 1.97% and 4.58% respectively.
Keywords: Hydrothermal method; Nanocomposites; TiO2-ZrO2; Dye Sensitized Solar Cells.
PACS: 81.07.Bc; 78.67.Bf; 78.20.Ci; 88.40.H

INTRODUCTION composites were prepared by hydrothermal method.

Dye sensitized solar cell based on TiO2
nanoparticles have attracted extensive attentions [1, 2].
The highest efficiency of DSSC reported so far is for
photo anode prepared with TiO2. The photo anode is
the key component for enhancing the efficiency.
Several parameters including the particle size of TiO2
play an important role in improving the efficiency. The
particle size of TiO2 and porosity can be varied by
mixing it with another oxide [3]. New crystallographic
phases with quite different properties than the original
oxides can be also produced by mixing of the oxides
[4]. It has been reported that incorporation of ZrO 2
leads to decrease in particle size of TiO2 [5]. In the
present work we have tried to change structural and
optical properties of TiO2 by mixing with ZrO2 and by
doping with Zn+2 ion and tried to improve the
efficiency of DSSC.
EXPERIMENTAL
TiO2 nanoparticles were purchased from Loba
chemicals. TiO2-ZrO2 and Zn doped TiO2-ZrO2
TiO2-ZrO2 composite was prepared in 70-30% molar
ratio. Zn was doped in 2% molar ratio. Titanium
isopropoxide, Zirconium propoxide, Isopropanol, Zinc
nitrate, and Nitric acid were used as starting materials.
All the chemicals were used as procured. A dilute
HNO3 was added drop wise in to mixture of Titanium
isopropoxide and Zirconium propoxide prepared in
Isopropanol and kept under vigorous stirring at room
temperature for 30 minutes. 2 mol% Solution of Zinc
nitrate was added to above solution. After alkoxide
hydrolysis the alcogel was obtained. The solids were
obtained by transferring the alcogel to an autoclave.
The temperature was raised to 240 ºC and the sample
was maintained under autogenic pressure for 24 h. The
sample was oven-dried at 100 ºC (2 h) and finally
calcined at 450 ºC for 4 hours under static air
atmosphere.
For the fabrication of DSSC, the prepared
nanocrystalline powder was grinded in an agate mortar
with dilute acetic acid for 1 hour. The obtained paste
was coated on ITO glass plate by glass rod, using
adhesive tapes (3M) as spacers. The films were dried
in air at room temperature and the coated ITO glass
plate was sintered at 450 °C for 30 min. Then, this

DAE Solid State Physics Symposium 2015

AIP Conf. Proc. 1731, 050132-1–050132-3; doi: 10.1063/1.4947786
Published by AIP Publishing. 978-0-7354-1378-8/$30.00

050132-1
electrode (working electrode) was immersed in
pomegranate juice for 18h for dye adsorption. This
electrode was fabricated into thin-layer, sandwich-type
solar cells. A thin graphite layer was coated on
conducting glass plate by pencil (counter electrode)
and kept in contact with dyed electrode. The redox
electrolyte comprising of iodide/triiodide solution was
introduced into the gap between the counter electrode
and the working electrode by the capillary force.
Results and Discussion
X-ray Diffraction
FIGURE 1. X-ray diffraction pattern of prepared samples.
Figure 1 shows the XRD pattern of prepared
samples. The broad peaks indicate formation of
crystals with smaller size. The JCPDS database
(Anatase TiO2-21-1272, Rutile TiO2-21-1276,
Monoclinic ZrO2-83-0944, and Tetragonal ZrO2-79-
1770) was used for powder crystalline phase
identification. TiO2 exists in two different phases
Anatase and Rutlie whereas ZrO2 is present in two
phases Monoclinic and Tetragonal. XRD pattern does
not show any peaks for impurity ion which indicate the
formation of pure oxides composition. The average
crystallite size was evaluated by Scherrer formula D =
0.9λ/βcosθ, where ‘β’ represents the full width at half
maximum (FWHM) of XRD lines. The average
crystallite size was found to be 22.32 nm, 17.41 nm,
and 6.31 nm for TiO2, TiO2-ZrO2 and Zn doped TiO2-
ZrO2 composites. The decrease in crystallite size may
be attributed to the ionic radius of Zn+2(0.074 nm),
Zr+4(0.072 nm) and Ti+4(0.069 nm). Zn and Zr cannot
replace a regular cation position due to large ionic
radii but it can take interstitial position in channels of
TiO2 and inhibit the crystal growth. The mass fractions
of Anatase to Rutile in all the samples were calculated
by fA = [1 + 1.26(IA/IR)]-1, Where ‘fA’ is the mass
050132-2
fraction of Anatase, ‘IA’ is the intensity of (101)
reflection of Anatase, and ‘IR’ is the intensity of (110)
reflection of Rutile. The Anatase content in TiO2,
TiO2-ZrO2 and Zn doped TiO2-ZrO2 is found to be
79.60%, 48.71% and 88.03%, respectively. As Anatase
phase is preferred phase for DSSC application it is
expected to get higher efficiency for DSSC prepared
using this material.
UV-Visible Spectroscopy
FIGURE 2. UV-Visible absorption spectra of prepared
samples.
Figure 2 shows UV-Visible absorption spectra of
all the samples. The absorption spectra shows red shift
for the samples doped with ZrO2 and Zn. Optical
bandgap was evaluated by establishing relation
between (αhν)2 and hν (Tauc’s relation). The optical
bandgap and calculated refractive index of all the
samples are given in Table 1. The new energy levels
will be introduced below the conduction band of TiO2
by ZrO2 and Zn, when light incident on material, less
energy will be required to move electrons from
valence band to the new energy level and thereby, the
bandgap may be decreased.
TABLE 1. Optical bandgap and refractive index of prepared
samples.
Sample Optical Refractive
Bandgap (eV) Index
TiO2 3.75 2.21
TiO2-ZrO2 2.15 2.63
Zn doped TiO2-ZrO2 2.05 2.67
Photovoltaic Characteristics and Performance
In order to examine the DSSC performance, the
photocurrent ‘I’ – voltage ‘V’ characteristics have
been measured under illumination. The fill factor (FF)
and the overall light to electrical energy conversion
efficiency (η) of DSSC were calculated according to
the following equations.
TABLE 2: Photovoltaic parameters of DSSC prepared from different photo electrode materials.
Sample Area (cm2) Jsc (mA/cm2) Voc (mV) FF η%
TiO2 3.61 0.0087 200 0.061 0.71
TiO2-ZrO2 1.15 0.0031 377 0.256 1.97
Zn doped TiO2-ZrO2 1 0.0059 369 0.312 4.58
Vmax u J max inhibit the recombination of electrons with oxidizing
FF species like triiodide ions in the electrolyte and dye.
Voc u J sc The metal doping has introduced new energy levels
Voc u J sc u FF below conduction band and improved the conductivity
K and response of photocurrent. Due to high refractive
Pin index, incident light can stay longer inside the material
Where, Jsc is the short circuit current density and get trapped and provide more photons to generate
(mAcm-2), Voc is the open circuit voltage (mV), Pin is electron.
the incident light power, where as Jmax (mAcm-2) and The X-ray diffraction and UV-Visible analysis
Vmax (mV) are the current density and voltage at the implies that the Zn doped TiO2-ZrO2 sample exhibit
point of maximum power output on the I – V curves, smallest crystallite size, highest Anatase content
respectively. (88%), smallest bandgap and highest refractive index
compare to other samples. This could be the reason for
highest efficiency of Zn doped TiO2-ZrO2
nanocomposite.

CONCLUSION
TiO2-ZrO2 and Zn doped TiO2-ZrO2
nanocomposites have been prepared successfully. In
corporation of ZrO2 and Zn+2 into TiO2 lowered the
crystallite size and optical bandgap and increased the
refractive index. A basic and inexpensive DSSC
prepared by the material produces a good amount of
photocurrent. The Zn doping has introduced new
energy levels and lowered the recombination. The
highest efficiency of 4.58% has been observed for Zn
doped TiO2-ZrO2 nanocomposite.

ACKNOWLEDGMENTS
The authors would like to acknowledge UGC for
sponsoring RFSMS fellowship.
FIGURE 3: The I – V curves of DSSC prepared from
different photo electrode materials. REFERENCES
Figure 3 shows I-V characteristics of DSSC. The
photovoltaic parameters are summarized in Table 2. 1. B. O’Regan, M. Gratzel, Nature. 335, 737 (1991).
The power conversion efficiency increases with 2. M. Gratzel, Nature. 338, 414 (2001).
addition of ZrO2 and Zn+2. The highest efficiency of 3. A. Kitiyanan, S. Pavasupree, T. Kato, Y. Suzuki, S.
4.58% has been observed for Zn doped TiO2-ZrO2 Yoshikawa, As. J. Energy Env. 6, 165 (2005).
4. N. I. Kuznetsova, L. I. Kuznetsova, L. G. Detusheva, V.
sample. The increment in efficiency might be due to
A. Likholobov, G. P. Pez, H. Cheng, J. Mol. Catal. A
the change in structural and optical properties of 161, 1 (2000).
material. It has been observed from the x-ray 5. X. Fu, L. A. Clark, Q. Yang, M.A. Anderson, Environ.
diffraction analysis that the crystallite size decreases Sci. Technol. 30, 647 (1996).
with doping and this will provide higher surface area
to adsorb more dye molecules on photo electrode
material; this might be the reason for increase in
efficiency of DSSC with doping. Table 1 shows that
the optical bandgap decreases and refractive index
increases with doping. The reduction in bandgap will

050132-3