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Solar Energy 84 (2010) 1833–1837

www.elsevier.com/locate/solener

Pomegranate leaves and mulberry fruit as natural sensitizers

for dye-sensitized solar cells
Ho Chang *, Yu-Jen Lo
Department of Mechanical Engineering, National Taipei University of Technology, Taiwan

Received 26 February 2010; received in revised form 23 June 2010; accepted 12 July 2010
Available online 1 August 2010

Communicated by: Associate Editor Sam-Shajin Sun

Abstract

This study employs chlorophyll extract from pomegranate leaf and anthocyanin extract from mulberry fruit as the natural dyes for a
dye-sensitized solar cell (DSSC). A self-developed nanofluid synthesis system is employed to prepare TiO2 nanofluid with an average
particle size of 25 nm. Electrophoresis deposition was performed to deposit TiO2 nanoparticles on the indium tin oxide (ITO) conductive
glass, forming a TiO2 thin film with the thickness of 11 lm. Furthermore, this TiO2 thin film was sintered at 450 °C to enhance the thin
film compactness. Sputtering was used to prepare counter electrode by depositing Pt thin film on FTO glass at a thickness of 20 nm. The
electrodes, electrolyte (I 3 ), and dyes were assembled into a cell module and illuminated by a light source simulating AM 1.5 with a light
strength of 100 mW/cm2 to measure the photoelectric conversion efficiency of the prepared DSSCs. According to experimental results,
the conversion efficiency of the DSSCs prepared by chlorophyll dyes from pomegranate leaf extract is 0.597%, with open-circuit voltage
(VOC) of 0.56 V, short-circuit current density (JSC) of 2.05 mA/cm2, and fill factor (FF) of 0.52. The conversion efficiency of the DSSCs
prepared by anthocyanin dyes from mulberry extract is 0.548%, with VOC of 0.555 V and JSC of 1.89 mA/cm2 and FF of 0.53. The con-
version efficiency is 0.722% for chlorophyll and anthocyanin as the dye mixture, with VOC of 0.53 V, JSC of 2.8 mA/cm2, and FF of 0.49.
Ó 2010 Elsevier Ltd. All rights reserved.

Keywords: Dye-sensitized solar cells; Anthocyanin; Chlorophyll; Dye cocktails; Natural dyes

1. Introduction of solar cells (Fang et al., 1997). In 1976, Tsubomura used

porous ZnO as the working electrode of a dye-sensitized
Though dye-sensitization has been studied since 1910s, solar cell and obtained photoelectric conversion efficiencies
these earlier studies mostly focused on searching for possi- of 2.5%. Subsequently, dye-sensitized solar cell has become
ble photosensitization-reduction reactions (Sancun et al., an important topic in solar cell research (Ruikui et al., 2007;
2006). Since the 1950s, studies have paid more attentions Nazeeruddin et al., 2003). In 1991, the successful demon-
to the oxidation reaction of dye-sensitized aggregates stration of dye-sensitized solar cells (DSSCs) introduced a
(Amao and Komori, 2004; Guo et al., 2005). From 1960s novel approach to traditional inorganic silicon solar cells
to 1970s, several scholars did researches on applying dye- (O’Regan and Grätzel, 1991), and due to their lower manu-
sensitizing to improve photoelectric conversion efficiency facturing cost, DSSCs are of great interest. In a typical dye-
sensitized solar cell (DSSC), ruthenium-based complexes
(e.g. N719) have been the preferred materials for the dye
*
Corresponding author. Address: Department of Mechanical Engineering, because of their high electrochemical activity (Grätzel,
National Taipei University of Technology, No. 1, Sec. 3, Chung Hsiao E. 2005; Wang et al., 2006). Recently, solar-to-electrical energy
Rd., Taipei 10608, Taiwan. Tel.: +886 2 27712171x2063; fax: +886 2 conversion efficiencies and open-circuit voltage as high as
27317191.
E-mail address: f10381@ntut.edu.tw (H. Chang).
11% and 0.74 V, respectively, by using ruthenium-based

0038-092X/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.solener.2010.07.009
1834 H. Chang, Y.-J. Lo / Solar Energy 84 (2010) 1833–1837

complexes (e.g. N719 or N3) as sensitizer have been alcohol, each. By indirect hydronic heating in boiling
reported (Chiba et al., 2006; Nazeeruddin et al., 2005; water, they were heated for 20 min to extract anthocyanin
Gao et al., 2008; Park and Kim, 2008). However, the costs and chlorophyll. Solid dregs in the solution were filtered by
of the ruthenium-based complexes restrict their large-scale filter paper to acquire a pure and natural dye solution.
applications in solar cells, stimulating the search for alter- Then, anthocyanin and chlorophyll were blended at the
natives (Zhu et al., 2008). In order to replace the expensive ratio of 1:1 to serve as a natural dye mixture from mulberry
ruthenium compounds, many kinds of organic synthetic fruits and pomegranate leaves.
dyes have been actively studied and tested as low-cost mate- The electrophoresis deposition method was used to
rials (Choi et al., 2007; Tai and Inoue, 2003; Chen et al., deposit the prepared TiO2 nanoparticles on indium tin
2007). oxide (ITO) conductive glass under normal temperature,
In nature, some fruits, flowers, leaves and so on show thus forming a TiO2 thin film. The active area of the DSSC
various colors and contain several pigments that can be eas- is 0.25 cm2 (0.5 cm  0.5 cm). Since there were some elec-
ily extracted and then employed in DSSCs (Calogero and trolytes left on the surface of the thin film, fissures were
Marco, 2008). The leaves of most green plants are rich in produced on its surface. To improve this situation and
chlorophyll (Gratzel, 2003; Tennakone et al., 1996; Zhang increase compactness of the thin film, the TiO2 thin film
et al., 2008), and the application of this kind of natural was sintered at 450 °C for 2 h. Moreover, the TiO2 film
dye has been frequently investigated in many related stud- was consolidated through heat treatment, increasing the
ies. Anthocyanins are natural compounds that give color internal voids of film organization and thus enhancing its
to fruits and plants and are also largely responsible for absorption performance. Then the sintered TiO2 thin film
the purple–red color of autumn leaves and for the red color was immersed in one of natural dyes for 24 h, allowing
of flower buds (Rossetto et al., 2002). Zhu adopted the the natural dye molecules to be adsorbed on the surface
extract of frozen blackberries to serve as photosensitizer of TiO2 nanoparticles. Anhydrous alcohol was used to
and the open-circuit voltage (VOC) of fabricated DSSCs is remove any natural dye that had not been adsorbed on
0.33 V (Zhu et al., 2008). Polo extracted the blue violet the surface of TiO2 nanoparticles. Finally, after cleaning,
anthocyanin of Jaboticaba and Calafate respectively to the DSSCs photoelectrode was complete and ready for
serve as photosensitizer and the VOC of prepared DSSCs testing.
is 0.59 V and 0.4 V respectively (Polo et al., 2006). Patroci- Encapsulation was carried out according to the general
nio used the extract of blueberries and Jaboticaba’s skin to assembly procedures (Fig. 1) of DSSCs. A DSSC is com-
act as photosensitizer and the VOC of prepared DSSCs is prised mainly of ITO conductive glass, TiO2 nanoparticles,
0.59 V and 0.45 V respectively (Patrocinio et al., 2009). In natural dye, electrolyte, counter electrode and spacers. The
this paper, extracts of pomegranate leaf and mulberry fruits counter electrode is fabricated by sputtering a 20 nm thick
were the natural dyes used as dye-sensitizers for the prepa- Pt film on FTO glass. The electrolyte is prepared by 0.05 M
ration of DSSCs. This paper considers the effective extrac- of I2, 0.5 M of LiI and 0.5 M of 4-tert-butylpyridine (4-
tion of dyes from these two plants and the preparation TBP) mixed with dry acetonitrile. One of the most com-
process of the dyes to enhance the overall photoelectric con- monly used additives is 4-TBP, as it has been shown to
version efficiency of DSSCs. increase the open-circuit voltage of the cell. It does this
by suppressing the dark current arising from the recombi-
2. Experimental procedures nation of electrons in the conduction band with the oxi-
dized form of the mediator (I 3 ) (Farahnaz et al., 2007).
This study used the self-developed arc spray nanofluid For assembly, glass insulation spacers in long strips were
synthesis system (ASNSS) with complex ultrasonic orthog- first stuck on the four edges on the base plate of conductive
onal vibration and vortex stirring to fabricate a TiO2 nano- glass at the bottom, forming a space between photoelec-
fluid in which TiO2 nanoparticles could be stably dispersed trode and counter electrode after assembly, and enabling
in the dielectric fluid (Chang et al., 2009a). The main exper- the injection of electrolyte. Then AB glue was used to
imental devices included an electrical utility power, a servo- adhere to the base plate of lower conductive glass carrying
positioning system, a vacuum chamber, a vacuum pump, a the counter electrode with the base plate of upper conduc-
heating source, a cooling system, an ultrasonic vibrator, a tive glass carrying the photoelectrode. The iodide electro-
vortex stirring device and a pressure control unit (Chang lyte solution was injected from the edge of base plates.
et al., 2009b). The main process parameters were vacuum The electrolyte was absorbed by capillary action between
pressure, 30 torr; peak current, 3 A; pulse-on and pulse- the photoelectrode and space until the whole space was
off time, 3 ls; ultrasonic frequency, 23 kHz; and break- filled. The TiO2 photoelectrode and counter electrode were
down voltage, 220 V. In addition, the weight fraction of tightly bonded and fixed by a binder clip to prevent the
the prepared TiO2 nanofluid was 0.01%. The TiO2 nano- production of air bubbles, and a sandwich DSSC was thus
particles thus produced had a mean particle size of around formed. In the performance test of the prepared DSSC,
25 nm. xenon (Xe) light of 150 W was selected to simulate sunlight
First, 10 g of fresh mulberry fruit and 0.4 g of fresh (AM 1.5), and an I–V curve analyzer (Keithley 2400) was
pomegranate leaves were separately put into 200 ml of employed to measure the photoelectric conversion effi-
 H. Chang, Y.-J. Lo / Solar Energy 84 (2010) 1833–1837 1835

Anode Cathode
Copper

TiO2 Pt

Gap Combination
TiO2 Dye Electrolyte
Anode

Pt

Cathode

Electrolyte
Fig. 1. Schematic diagram of the DSSC assembly.

ciency of the prepared DSSC. The measured results was (a)

plotted in an I–V curve, from which the data of open-cir-
cuit voltage VOC (V), short-circuit current density JSC
(mA/cm2), fill factor (FF) and conversion efficiency g%
could be further acquired.

3. Results and discussion

Fig. 2a shows the FE-SEM image of TiO2 nanoparticles

fabricated using the proposed self-developed nanofluid
synthesis system. The TiO2 nanoparticles thus produced
have a mean particle size of around 25 nm. In addition,
Fig. 2b shows the cross-section image of TiO2 thin film pre-
pared by electrophoresis deposition after sintering at
450 °C for 2 h. Because gas still existed in the mesopores (b)
of the TiO2 thin film prepared by EPD, the internal gas
and voids of film layer were eliminated by heat treatment
at 450 °C. This process increases the quantity of TiO2
nanoparticles in a unit area of film, thus enhancing the
adsorptive capability of natural dye molecules.
Fig. 3 shows absorption spectrum of N719 dye and chlo-
rophyll dye extracted from pomegranate leaf. The main
absorption range of N719 is in 400–600 nm; the absorption
range of chlorophyll dye is in 400–500 nm and in 600–
750 nm. Hence, chlorophyll dye’s absorbability is better
in the range of 400–450 nm. But in the range of 500–
600 nm, N719’s absorbability is better than that of chloro-
phyll dye.
Fig. 4 shows the absorption spectrum of N719 dye and
anthocyanin dye extracted from mulberry. It can be seen
that the absorption ranges of the two dyes are very close Fig. 2. FE-SEM image of (a) the fabricated TiO2 nanoparticles and (b)
the cross-section image of TiO2 thin film prepared by electrophoresis
to each other. The absorption peaks of N719 dye and
deposition after heat treatment at 450 °C.
anthocyanin dye are located at 518 and 543 nm, respec-
tively. The absorption wavelengths of the two dyes are
located between 400 and 600 nm. N719 except in the range of 470–550 nm. Different dyes
Fig. 5 shows the absorption spectrum of the dye mixed show different absorption wavelengths due to differences
from chlorophyll dye and anthocyanin dye. It is found that in composition (Polo and Iha, 2006; Hara et al., 2000;
the combination dye’s absorbability is better than that of Bisquert et al., 2004). By observing the absorption range
1836 H. Chang, Y.-J. Lo / Solar Energy 84 (2010) 1833–1837

3.0
Chlorophyll
Chlorophyll Anthocyanin
N719 2.5

Current denisty (mA/cm2)

Dye cocktails
Absorbance (a.u.)

412 2.0

1.5

665 1.0

0.5

400 500 600 700 800 0.0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Wavelength (nm)
Voltage (V)
Fig. 3. Absorption spectrum of N719 dye and chlorophyll dye.
Fig. 6. J–V characteristics of DSSCs with chlorophyll, anthocyanin and
combination extracts dye.

Anthocyanin Table 1
N719 Characteristics of dye-sensitized solar cell.
Dye VOC (V) JSC (mA/cm2) FF g (%)
Absorbance (a.u.)

Chlorophyll 0.560 2.05 0.52 0.597

Anthocyanin 0.555 1.89 0.49 0.548
Dye cocktails 0.53 2.8 0.49 0.722

Table 1 that the conversion efficiency of the DSSCs pre-

pared by chlorophyll dyes from pomegranate leaf extract
is 0.597%, with open-circuit voltage (VOC) of 0.56 V and
400 500 600 700 800 short-circuit current density (JSC) of 2.05 mA/cm2, and fill
Wavelength (nm) factor (FF) of 0.52. The conversion efficiency of the DSSCs
Fig. 4. Absorption spectrum of N719 dye and anthocyanin dye. prepared by anthocyanin dyes from mulberry extract is
0.548%, with VOC of 0.555 V and JSC of 1.89 mA/cm2,
and FF of 0.53. Furthermore, there is conversion efficiency
of 0.722% for chlorophyll and anthocyanin as the dye
Dye cocktails cocktails with VOC of 0.53 V and JSC of 2.8 mA/cm2, and
N719 FF of 0.49. It can be seen from Table 1 that combination
518
dye can improve the photoelectric conversion efficiency of
Absorbance (a.u.)

DSSCs. The VOC of natural dye is lower than that of

540 N719 dye because of molecular structure of natural dye
which mostly has OH ligands and O ligands and lacks
ACOOH ligands that N719 dye has. The ACOOH ligands
665 will combine with hydroxyl of the TiO2 particles to pro-
duce ester and boost coupling effect of electrons on TiO2
conduction band to acquire a rapid electron-transport rate.
400 500 600 700 800 Fig. 7 shows the incident photon-to-electron conversion
Wavelength (nm) efficiency (IPCE) for a DSSC sensitized with chlorophyll,
anthocyanin and dye cocktails. As can be seen from
Fig. 5. Absorption spectrum of N719 dye and cocktail dye.
Fig. 6, when the wavelength of incident light is in the
ranges of 400–460 nm and 460–670 nm, the mixed dye
of a combination dye, it is found that when two natural has higher photon-to-electron conversion efficiency from
dyes are mixed, the absorption range is enhanced, promot- the energy of incident light. In addition, when located at
ing the photoelectric conversion efficiency of a dye-sensi- wavelength of 400 nm, IPCEmax of chlorophyll dye-sensi-
tized solar cell. tized solar cell is 13%, the anthocyanase dye-sensitized
Fig. 6 shows the J–V characteristics of the prepared solar cell is 9% and the combination dye-sensitized solar
DSSC that takes pomegranate leaf extract, mulberry fruits cell is 12%. Therefore, the combination dye has higher con-
extract and cocktail as the natural dye. Table 1 shows the version efficiency for the energy of incident light, and the
data acquired from measuring the photoelectric conversion short-circuit current density (JSC) excited by the mixed
efficiency of DSSCs. As can be seen from Fig. 6 and dye is higher than chlorophyll and anthocyanin extracts.
 H. Chang, Y.-J. Lo / Solar Energy 84 (2010) 1833–1837 1837

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