Natural dye -sensitized mesoporous ZnO solar cell

Qishuang Wu, Yue Shen*, Guizhi Wu, Linyu Li, Meng Cao, Feng Gu
School of Materials Science and Engineering, Shanghai University, Shanghai 200072, China
ABSTRACT
Natural dye-sensitized solar cells (N-DSSCs) were assembled using chlorophyll sensitized mesoporous ZnO (based on
FTO) as the photoanode and platinum plate as the cathode. The natural dyes (chlorophyll) were extracted from spinach
by simple procedure. The absorption spectrum and fluorescence spectrum of chlorophyll were studied. Mesoporous ZnO
(m-ZnO) applied to the N-DSSCs was synthesized through hydrothermal method. The structures and morphologies were
characterized by X-ray Diffraction (XRD) and diffuse reflection. The results indicated that the samples had an average
pore size of 17 nm and the m-ZnO was hexagonal wurtzite structure. The performances of the N-DSSCs were
investigated under AM 1.5G illumination. The Voc of the N-DSSCs was about 480mv, and the Isc was about 470A.
The performance of the N-DSSCs could be further improved by adjusting its structure.
Keywords: Natural dye, Mesoporous ZnO, Dye-sensitized solar cell, Spinach

1. INTRODUCTION
Dye-sensitized solar cell (DSSC) has a bright prospect in the conversion of visible light into electrical energy. Many
people exploit it using various methods from different directions. In recent years, nanocrystalline mesoporous metal
oxide films applied to DSSCs has attracted much attention [1~2]. Nanocrystalline TiO2 was the most widely used
photoanode material in DSSCs from the beginning. While people still continue to develop new materials. By research,
ZnO is a wide gap semiconductor with good electron mobility, which is much higher than in TiO2 and it can be used as
the photoanode due to its stability against photo-corrosion and photochemical properties similar to TiO2 [3~4]. In 1994,
DSSC based on m-ZnO with an energy conversion efficiency of 0.4% had been reported by Redmond and Grtzel et al
[5]. Since then, m-ZnO has received lots of research and a great deal of effort was given to successfully synthesize
m-ZnO powders [6~7]. M-ZnO was expected to replace nanocrystalline TiO2 as photoanode material for DSSCs.
The performance of a DSSC mainly depends on dyes that used as photosensitizer [8]. In the past, people used heavy
metal dyes such as N719, but those dyes were very expensive. While natural dyes, which can be extracted from fruit,
flower and leaves of plants by simple procedure, are cheep, convenient and safe, and now have attracted more and more
attention. In this research, the natural dyes (chlorophyll) extracted from spinach were used as photosensitizer and m-ZnO
was used as photoanode to build N-DSSCs. Because of the simple preparation technique, widely source, and cheap cost,
natural dye as an alternative photosensitizer for dye-sensitized solar cell is promising.

2. EXPERIMENTAL
2.1 Preparation of the mesoporous ZnO layer
M-ZnO powder was successfully synthetized by the hydrothermal method using P123 surfactant as the template agent
and zinc acetate dihydrate as the inorganic precursor via the following procedure: 1.1g Zn(CH3COO)22H2O (>99%
purity), 1.5g CO(NH2)2 (>99% purity) and 0.548g P123 were mixed in 100ml deionized water and churned until the
solution became transparent and uniform. Acetic acid was added to make the PH of the solution to about 4. After stirring
for 2 h, the solution was transferred into an autoclave at 90 for 24 h and then filtrated. The solid product filtered off
was dried in an oven at 90 first. Then the solid was slowly heated to 350 C and aged at this temperature for 4 h.
Finally the resulting m-ZnO powder was manufactured to films based on FTO by screen printing.
2.2 Synthesis of the cell
*

E-mail address:yueshen@staff.shu.edu.cn
Seventh International Conference on Thin Film Physics and Applications,
edited by Junhao Chu, Zhanshan Wang, Proc. of SPIE Vol. 7995, 799532
2011 SPIE CCC code: 0277-786X/11/$18 doi: 10.1117/12.888318
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The natural dyes (chlorophyll) were extracted from spinach by simple procedure and the solvent was ethanol. The
m-ZnO films were immersed into the chlorophyll ethanol solution for 4 h. The N-DSSCs were assembled using natural
dyes sensitized m-ZnO (based on FTO) as the photoanode and platinum plate as the cathode. The electrolyte solution
was introduced between the electrodes by the capillary action.
2.3 Characterization
The m-ZnO films were characterized by XRD (X-ray diffractometer, RigakuD/MAX-2550, Tokyo) with Cu K radiation
(=1.54056), operated at 40kV and 200mA. The fluorescence spectrum of the chlorophyll ethanol solution and the
sensitized m-ZnO photoanode were characterized by 970CRT fluorospectro photometer. A JASCO V570 UV/VIS/NIR
spectrophotometer was used to measure the optical spectra of the films. The photocurrent-voltage (J-V) measurements
were done using an AM1.5 solar simulator (SDSB-09022, Newport Corporation, USA) as the irradiation source. The
incident light intensity was 100mW/cm2 calibrated with a standard Si solar cell. The current-voltage curves were
obtained by the linear sweep voltammetry (LSV) method using an electrochemical workstation (CHI660B, Shanghai
Huachen Co., China).

3. RESULTS AND DISCUSSION

3.1 Structure of mesoporous ZnO

Fig.1 The small angle X-ray diffraction of M-ZnO

Fig.2 The wide angle X-ray diffraction of M-ZnO films and FTO substrates

The SAXRD and WAXRD of m-ZnO are shown in Fig.1 and Fig.2 respectively. The scanning range of the SAXRD is
from 0.5 to 3 with a scanning rate of 0.5/min. There is a characteristic peak at about 1.1, but its not very sharp. The
result shows that m-ZnO structure was successfully built through the hydrothermal method by using p123 as the template
agent and zinc acetate dihydrate as the inorganic precursor, but it is ordered only in short range. When extending to large
range, the ordered arrangement disappears. In Fig.2, the curve (a) is the WAXRD of the m-ZnO based on FTO. In
comparison, the WAXRD of FTO is lay below (curve b). The WAXRD was set from 10 to 90 and there exist eight
obvious diffraction peaks at 2 of ca 31.92 , 34.54, 36.24, 47.67, 56.70, 63.04, 67.96 and 69.39, which match
with the standard data according to JCPDS card (No. 36-1451). These peaks can be indexed to (100)(002)(101)
( 102)(110)(103)(200) and (201), respectively. It indicates that the sample has a hexagonal wurtzite structure and is
well crystallized after calcinations at 350 C. According to Scherrer equation: D=0.89/cos (D is the crystallite size,
is the X-ray wavelength with a value of 1.54056 , is full width at half maximum (FWHM) of the diffraction peak),
the average crystallite size is 17 nm when the (101) diffraction peak is used for the evaluation.
3.2 Properties of chlorophyll
The absorption spectrum and fluorescence spectrum of chlorophyll were studied and shown in Fig.3 and Fig.4,
respectively. From Fig.3, it can be seen that the curve has two absorption peaks at about 430nm and 670nm. According
to the sorts of chlorophyll, this absorption spectrum explains that the chlorophyll extracted by the method above is
chlorophyll a [9]. The absorption spectrum of the chlorophyll is from ultraviolet to near infrared, which helps to improve
the properties of the N-DSSCs. Fig.4 was the fluorescence spectrum of the chlorophyll. There was an obvious peak at the
wavelength of 680nm (the excited wavelength was 429nm).

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Fig.3 The light absorption spectrum of the chlorophyll

Fig.4 The fluorescence spectrum of the chlorophyll

3.3 Photoelectric properties of the N-DSSCs

Fig.5 shows the diffuse reflection curves of pure m-ZnO and sensitized m-ZnO. From the oblique line, the energy gap
( Eg ) of m-ZnO can be calculated by the equation: hv=hc/=1243.125/. Eg of m-ZnO is 3.34eV, which is much close
to the data of bulk material (3.37eV). Curve (b) has two more reflection peaks at 416nm and 653nm. Compared with the
light absorption spectrum of Fig.3the two peaks of the diffuse reflection curve b of sensitized m-ZnO come from the
absorption of chlorophyll, and the absorption peaks of sensitized m-ZnO show blue shift: one peak shifts from 430nm to
416nm, another peak shifts from 670nm to 653nm.

Fig.5 The diffuse reflection and the energy gap ( Eg ) of M-ZnO

before sensitized(a) and after sensitized(b)

Fig.6 Current-voltage characteristics of DSSCs based on

mesoporous ZnO photoanodes sensitized by natural dyes
(chlorophyll) extracted from spinach

The current-voltage characteristics under AM1.5 irradiation of DSSCs based on m-ZnO photoanodes sensitized by
natural dyes (chlorophyll) was shown in Fig.6. It can be seen that the open circuit (Voc) was 0.478 V and the short circuit
current density (Jsc) was 0.472mA/cm2. The fill factor (FF) was 59.4% calculated by multiplying Voc and Isc. The
photoelectric conversion efficiency was calculated about 0.133 % from the relationship = ImVm /FF 100%. Compared
to other solar cells, this Jsc is too low. According to reference [10], it may be mainly caused by the leakage current. The
leakage current in our cells can be classified to many circumstances, such as cracks and holes, nonlinear edge shunts and
scratches [10]. Cracks and holes in readily processed solar cells lead to a weak nonlinear edge recombination current,
similar to nonlinear edge shunts. A scratch at the surface of a solar cell across the m-ZnO layer brings a high density of
recombination centers. However, the leakage current of the N-DSSCs can be further improved by adjusting its structure.

4. CONCLUSION
In conclusion, mesoporous ZnO can be successfully synthesized through the hydrothermal method and all the
information demonstrate that the mesoporous ZnO can be used as efficient photoanode material in DSSCs. The natural
dye-sensitized solar cell (N-DSSC) had an open circuit (Voc) of 0.478 V, a short circuit current density (Jsc) of 0.472
mA/cm2 and a photoelectric conversion efficiency of 0.133%. The low photoelectric conversion efficiency may mainly

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due to the big leakage current and the properties of the natural dyes (chlorophyll). The performance of N-DSSCs could
be further improved by reducing the leakage current.

ACKNOWLEDGEMENTS
The work was supported by National Basic Research Program of China (2010CB933700), Shanghai City Committee of
Science and Technology (AM 08520741600), Innovation Program of Shanghai University (SHUCX102240), Innovation
Program of Shanghai City (CXSJ09-052) and Shanghai Leading Academic Disciplines (S30107). We thank Dr. Bo Lu
for his assistance in the measurement at Shanghai University.

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