SOLAR ASIA – 2013
2nd INTERNATIONAL CONFRENCE ON
SOLAR ENERGY MATERIALS, SOLAR CELLS AND SOLAR ENERGY
APPLICATIONS
22-24 August 2013
Centre for Ionics University of Malaya (CIUM)
Faculty of Science, University of Malaya, Kuala Lumpur, Malaysia
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TEMPLATE FOR FULL PAPER: SOLAR ASIA 2013
DYE-SENSITIZED SOLAR CELL
M.H. BURAIDAH1, L.P. TEO1, M.A. CAREEM1,2 AND A.K. AROF1*
1Centre
for Ionics University Malaya, Department of Physics, Faculty of Science,
University of Malaya, 50603 Kuala Lumpur, Malaysia.
2Deaprtment of Phyasics, University of Peradeniya, Peradeniya, Sri Lanka
*Corresponding Author: akarof@um.edu.my
ABSTRACT
Anthocyanin dye extracted in ethanol from black rice was employed as sensitizer in dye-sensitized
TiO2 solar cell. The anthocyanin dye was characterized using UV-Visible spectra and absorbance
peak at 541 nm is observed. Upon complexation between anthocyanin and TiO2, the absorbance
peak was shifted to lower energy at 555 nm. Three types of polymer electrolytes i.e. (chitosanPEO)-NH4I, (chitosan-PVA)-NH4I and chitosan-NH4I-IL were prepared by the solution cast
technique. Ionic liquid (IL) 1-butyl-3-methylimidazolium iodide (BMII) is used. Some iodine (I2)
crystals were added into the polymer electrolytes to provide the I-/I3- redox couple. Dye-sensitized
solar cells were fabricated by sandwiching the chitosan-based polymer electrolytes between
TiO2/dye photoelectrode and Pt counter electrode, respectively. The cell sensitized with black rice
exhibits short circuit current density, Jsc of 1.705 mA cm-2, open circuit voltage, Voc of 385 mV, fill
factor of 0.39 and efficiency, η of 0.256 %.
Keywords: anthocyanin, chitosan, ionic liquid
1. INTRODUCTION
Photoelectrochemical application based on dye-sensitized nanostructured TiO2 solar
cell has attracted much attention as a low cost alternative to conventional silicon solar cells
[1]. In 1991, dye-sensitized solar cell (DSSC) based on liquid electrolyte with efficiency about
11 % was first reported by O’ Regan and Gra¨tzel [2]. Guo et al. [3] reported that the dyesensitized solar cell with electrolyte containing 0.1 mol L-1 LiI, 0.35 mol L-1 I2 and 0.5 mol L-1
N-Methylbenzimidazole (NMBI) in pure S-propyltetrahydrothiophenium iodide (T 3I) exhibits
short-circuit photocurrent density (Jsc) of 11.22 mA cm-2 and open circuit voltage (Voc) of 0.61
V. TiO2/CdSe(6)/0.5M Na2S-0.1M S-0.2M KCl/gold solar cell has been reported by Chong et
al. [4]. Short-circuit photocurrent density (Jsc) of 7.43 mA cm-2 and open circuit voltage (Voc)
of 0.37 V was obtained. Due to problems with liquid electrolytes, polymer electrolytes are
actively used in solar cell research [5-7].
Extensive studies on polymer electrolytes have been done by researchers in order to
solve the problems that exist in liquid electrolytes specifically leakage and solvent
evaporation. The use of polymer electrolytes in solar cell applications provide advantages such
as compatibility, easy to prepare in different forms, no leakage, electrochemically stable and
easy to process [8-9]. Chitosan has been the subject of interest due to its specific properties
such as biodegradability, biocompatibility, odorless, homogeneity with high mechanical
strength [10,11]. It is non-toxic and thus environmental friendly [12]. Singh and co-authors
[13] have reported an open-circuit voltage of 0.53 V and short-circuit current density of 2.62
mA cm-2 from dye-sensitized solar cell employing polymer electrolyte based on chitosan with
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sodium iodide (NaI), iodine crystals and ionic liquid. Ionic liquid (IL) are also known as room
temperature molten salts and are non-volatile, non-flammable and high solvating capability
[14].
2. EXPERIMENTAL
2.1 Materials
Highly viscous chitosan was purchased from Fluka and PEO from Aldrich. Both
iodine (I2) and ammonium iodide (NH4I) were procured from Ajax chemicals and glacial
acetic acid from Ajax Finechem. Titanium dioxide (TiO2) paste was purchased from JGC
Catalysts & Chemicals Ltd.
2.1 Electrolyte preparation
Chitosan-NH4I-IL, (Chitosan-PEO)-NH4I and (Chitosan-PVA)-NH4I electrolytes
were prepared by the solution cast technique. The solutions were then cast in different Petri
dishes and allowed to evaporate slowly at ambient temperature to form films. Impedance of
the films was measured by the complex impedance technique using the HIOKI 3531-01 LCR
Hi-Tester in the frequency range from 50 Hz to 1 MHz.
2.2 Device assembly
Ti(IV) bis(ethyl acetoacetato)-diisopropoxide (0.38 M) was coated on indium tinoxide (ITO) glass as a blocking layer and heated at 723 K for 30 minutes. The ITO glass was
previously cleaned with acetone and distilled water. After that, TiO 2 paste was coated on the
blocking layer using doctor-blade method and the thickness of the layer was controlled using
adhesive tape of thickness 100 m. The TiO2 layer was then heated at 773 K for 1 hour. The
resistance of TiO2 was found to increase from 5 Ω cm-2 to 11 Ω cm-2 after heating. After
cooling to 373 K, the TiO2 electrode was soaked into the anthocyanin solution which has been
extracted from black rice for 24 hours. The J-V characteristics of the dye-sensitized solar cells
were obtained under white light illumination (100 mW cm-2) using Keithley 2400
electrometer.
3. RESULTS AND DISCUSSION
Fig. 1 shows the absorption spectra of anthocyanin extracted from black rice in
solution and absorbed onto the TiO2. It can be observed that the spectrum of anthocyanin show
a broad absorption band in the visible region ascribed to charge transfer transitions from
highest occupied molecular orbital (HOMO) to lowest unoccupied molecular orbital (LUMO)
[26,27].The absorption peak of anthocyanin in solution is observed at λmax = 541 nm while
anthocyanin absorbed onto the TiO2 electrode showed maximum absorption at λ max = 555 nm.
The shift to lower energy is due to the reaction between the anthocyanin and TiO2 on the
surface. Chemical adsorption of this anthocyanin is the result of condensation of alcoholicbound protons with the hydroxyl groups in the surface of nanostructured TiO 2. Adsorption of
anthocyanin to the TiO2 surface stabilizes the excited state of the HOMO and LUMO of these
anthocyanin pigments, thus affect the energy gap and shift towards the lower energy of the
absorption spectrum [28,29].
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Absorbance (a.u.)
(b)
(a)
400
500
600
700
800
Wavelength, λ (nm)
Fig. 1. The absorption spectra of anthocyanin from black rice (a) in solution and (b) absorbed onto TiO2 electrode
The visible absorption band is pH and solvent sensitive, showing the dye to appear red
flavylium form in acidic solution and purple quinonoidal form as pH increases [27,28,30].
Dye-sensitized solar cells were fabricated by sandwiching electrolytes with TiO2/dye
photoelectrode and platinum (Pt) counter electrode. For solar cell application, 0.04 g iodine
was added to the electrolytes to produce the redox couple (I -/I3-). Redox couple in the
electrolytes is very important in order to complete the circuit for charge flow in the electrolyte.
The performance of dye-sensitized solar cells was evaluated in term of short circuit current
density Jsc, open circuit voltage Voc, fill factor FF and efficiency  % which are tabulated in
Table 1. The fill factor and efficiency were calculated from the following equations:
FF 
Pmax
Voc  J sc
(6)
Voc  J sc  FF
 100
Pin
(7)
 %
Here, Pmax is maximum power output (Pmax = Vmax x Jmax) and Pin is input power. Most of the
efficiency of the natural dye-sensitized solar cells is less than 1%. In the work of Wongcharee
et al. [32], TiO2 DSSC employing dye extracted from blue pea as sensitizer, liquid electrolyte
and Pt counter electrode exhibits Jsc of 0.37 mA cm-2, Voc of 0.37 V, FF of 0.33 and  of 0.05
%, respectively.
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Table 1: Electrolyte composition and photoelectrochemical parameters of DSSCs
Composition
Conductivity, σ
Jsc
Voc (V)
FF
(S cm-1)
(mA cm-2)
27.5 wt. % chitosan-27.5wt.%
1.77 × 10-6
0.19
0.30
0.43
PVA-45 wt. % NH4I
16.5 wt. % chitosan-38.5wt.%
3.66 × 10-6
0.27
0.34
0.40
PEO-45 wt. % NH4I
27.5 wt. % chitosan-22.5 wt. %
1.76 × 10-4
0.31
0.35
0.47
NH4I-80 wt. % BMII
η%
0.02
0.04
0.05
3. CONCLUSIONS
Chitosan based polymer electrolyte was successfully prepared. Highest ionic
conductivity of 1.76 × 10-4 S cm-1 was obtained with incorporating IL. A natural dye of
anthocyanin solution was used in fabrication dye-sensitized solar cells. The cell using
electrolyte with composition 27.5 wt. % chitosan-22.5 wt. % NH4I-80 wt. % BMII exhibited a
better performance compared to other electrolyte.
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