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Solar Energy Materials & Solar Cells 79 (2003) 495505

Improved performance of a dye-sensitized solar cell using a TiO2/ZnO/Eosin Y electrode

Seok-Soon Kim, Jun-Ho Yum, Yung-Eun Sung*
Department of Materials Science and Engineering, Kwangju Institute of Science and Technology(K-JIST), Kwangju 500-712, South Korea Received 8 September 2002; received in revised form 16 January 2003

Abstract TiO2/ZnO/Eosin Y structure lms were prepared by a one-step cathodic electrodeposition method and used as a photoanode in a dye-sensitized solar cell (DSSC). Using this TiO2/ZnO/ Eosin Y electrode in DSSC, the degradation of the cell with time was reduced and ISC, VOC and ll factor values were increased. The use of a thin ZnO layer, permitted the formation of an energy barrier at the electrode/electrolyte interface, thus reducing recombination rate and improving cell performance. In addition, the adsorbed dye molecules prepared by onestep cathodic electrodeposition with ZnO were very stable compared with that prepared by conventional immersing method, as evidenced by UV/vis absorption spectroscopy measurements. r 2003 Elsevier Science B.V. All rights reserved.
Keywords: Dye-sensitized solar cell; One-step cathodic electrodeposition; ZnO layer; Recombination rate; Energy barrier

1. Introduction Dye-sensitized solar cells (DSSC) are a new type technology for converting light energy into electrical energy. It is composed of a dye-modied wide band semiconductor electrode such as TiO2, ZnO, Nb2O5 and a counter electrode and redox electrolyte. When a DSSC is illuminated by sunlight, the dyes absorb the light and become excited. The absorption of light by the dyes is followed by the injection of an electron from the excited state of the dye to the conduction band of the
*Corresponding author. Tel.: +82-62-970-2370; fax :+82-62-970-2304. E-mail address: ysung@kjist.ac.kr (Y.-E. Sung). 0927-0248/03/$ - see front matter r 2003 Elsevier Science B.V. All rights reserved. doi:10.1016/S0927-0248(03)00065-5

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semiconductor. Simultaneously the oxidized dye is reduced by the electron donor in the electrolyte and returns the ground state. The electrons in the conduction band of the semiconductor are collected at the back contact electrode and ow through the external circuit. These electrons arrive at the counter electrode and have an effect on the reverse reaction of the redox couple. Through these processes, radiant energy is converted into electricity [13]. Because of its low fabrication cost, its robust nature, environmental compatibility, and the simplicity of the process, interest in DSSC has grown considerably [4,5]. Although the cost of DSSC fabrication is 20% compared with a silicon solar cell, for practical application an improved efciency and longterm stability is needed. One of the most important problems is the recombination of the photoinjected electrons in the conduction band of the semiconductor with the oxidized dyes and the triiodide in the electrolyte. In DSSC, the individual particle size is so small that the formation of a space charge region is impossible [69]. This indicates that the recombination rate of the photoinjected electrons is very high due to the absence of an energy barrier at the electrode/electrolyte interface [7]. So many studies to reduce the recombination at the interface were tried such as fabrication of bilayer electrode, preparation of composite semiconductor electrode, and passivation of semiconductor electrode using electropolymerization method and so on [1013]. Tennakone et al. and Tai prepared semiconductor composite by chemical method to reduce the recombination rate at the electrode/electrolyte interface [10,11]. Then the electrode was immersed the dye solution as conventional method. In addition, Kamat et al. also prepared coupled semiconductor systems using several material such as ZnO/CdS, TiO2/CdSe, SnO2/TiO2 and so on. Especially, they prepared the CdSe lm on SnO2 by electrochemical deposition method and obtained highly efcient DSSC [13]. In an attempt to reduce the recombination rate, we report here on the preparation of a bilayer semiconductor electrode to provide an inherent energy barrier. The promising materials used in this study was ZnO, the conduction band edge of which was more negative than that of the TiO2, about 100 mV, and thus, the formation of an energy barrier at the electrode/electrolyte interface would be expected [14]. In this study, a dye-modied TiO2/ZnO electrode was prepared by the one-step cathodic electrodeposition of dye and ZnO on a TiO2-coated ITO glass substrate and used in a DSSC. The structure of the electrode was examined by X-ray diffraction (XRD) and transmission electron microscope images and cell performance was tested by IV curve measurement, chronoamperommetry, AC impedance spectroscopy, and UV/vis absorption spectroscopy. The cell fabricated using the new TiO2/ZnO/dye electrode was compared with that of a conventional TiO2/dye electrode.

2. Experimental details To form the TiO2/ZnO/Eosin Y photoanode structure, a TiO2 coating was rst applied using a conventional method [15,16]. A viscous slurry of TiO2 (Degussa P 25

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powder) was prepared by mixing it with surfactants such as Triton X-100, acetylaceton, polyethylene oxide, and polyethylene glycol and this slurry was deposited on the ITO-coated glass with a glass rod, followed by sintering at 425 C for 1 h under air. The TiO2/ZnO/Eosin Y electrode was prepared by the one-step cathodic electrodeposition in an aqueous solution containg 0.1 M Zn(NO3)2 6H2O and 3 104 M Eosin Y. In this process, TiO2-coated ITO glass was used as the working electrode and Pt wire and a Ag/AgCl electrode were used as the counter and reference electrodes, respectively. The potential applied to the cell during the deposition time was determined by cyclic voltammetry. Thus, the TiO2/ZnO/Eosin Y photoanode structure which had the area of 2 cm2 was prepared by chronoamperometric deposition at the determined potential. To conrm the existence of ZnO, wide angle XRD patterns were obtained using a Rigaku X-ray diffractometer and EDX was also applied. Counter electrodes were prepared by the sputtering of Pt on the ITO-coated glass and electrolyte was composed of 0.5 M LiI, 0.05 M I2, and 0.05 M hydroquinone in acetonitrile. Hydroquinone is a redox agent used in photoelectrochemical experiments [17]. If it is added to the electrolyte the regeneration of oxidized dye can be enhanced and, consequently, the improvement of cell performance is expected. Using these components, a sandwich type conguration could be fabricated and this was employed to measure the performance of the cell. Cell performance was measured using a xenon light source and AM 1.5 lter. The area of electrode was 2 cm2 and the power of incident white light from a Xe lamp was 4.5 mW/cm2. The photocurrentvoltage (IV) measurement and the stability measurement via chronoamperommetry were performed using an Autolab PGSTAT30 Potentiostat/Galvanostat. AC impedance spectra were obtained using an Autolab FRA2 over a frequency range from 0.01 to 10 kHz with an AC amplitude of 5 mV. Finally, the stability of the adsorbed dye molecules was determined by UV/vis absorption spectra measurement at room temperature with a Perkin-Elmer Lambda 12 UV/vis spectrophotometer.

3. Results and discussion Fig. 1(a) shows the schematic diagrams of the energy band of the TiO2/dye and TiO2/ZnO/dye electrodes. When a ZnO layer is present between the electrode and electrolyte, the decreased recombination of photoinjected electrons would be expected. In this gure, a dashed arrow represents two possible recombination mechanisms: (i) recombination between the injected electron and the oxidized dye molecule, (ii) recombination between the injected electron and triiodide in the electrolyte. Due to the fast neutralization of oxidized dye by the redox couple, the recombination of electrons by oxidized dye can be ignored [18]. To ensure the possibility of the formation of an energy barrier by ZnO, voltammograms of TiO2, ZnO and ZnO/TiO2 were measured. In this work, 0.1 M KCl was used as the supporting electrolyte and TiO2 or ZnO or ZnO/TiO2-coated ITO glass was used as the working electrode. A Pt wire and Ag/AgCl electrode was used as a counter electrode and reference electrode, respectively. Fig. 1(b) shows the results. The

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S/S + S/S+

CB
A/A S/S+ TiO2 Dye

CB A/A VB
+

VB

S/S

TiO2 ZnO

Dye

(a)

0.0

Current density (mA/cm )

-0.3

-0.6

-0.9

ZnO ZnO/TiO 2 TiO2

-1.2

-1.5 -1.0 -0.5 0.0

(b)

Voltage (V vs. Ag/AgCl)

Fig. 1. (a) Schematic diagrams of (left) the electrode structure of a conventional DSSC and (right) DSSC modied with ZnO. (b) Voltammograms of TiO2, ZnO, and TiO2/ZnO electrodes in 0.1 M KCl aqueous solution.

solution had a pH of ca. 6.6 and was degassed by the pure nitrogen gas before cycling. For more accurate work, the lm thickness and electrode area were controlled uniformly about 3 mm and 2 cm2, respectively. The steady-state cathodic current was increased with applying cathodic potential and the onset potential indicates the conduction band edge of the semiconductor. In Fig. 1(b), the onset potential of ZnO is more negative than that of TiO2, thus ensuring the formation of an energy barrier by the ZnO layer and which tendency was same as the results of other groups [14]. Moreover, the negative shift of TiO2 conduction band edge as the result of adding ZnO to the TiO2 would be expected to lead to an increase of VOC : VOC is the difference between the conduction band edge and the redox potential of redox couple and this value is the maximum obtainable voltage from the cell. Fig. 2 shows the cyclic voltammogram of 3 104 M Eosin Y in an aqueous solution and that of aqueous solution of 0.1 M Zn(NO3)2 6H2O and 3 104 M Eosin Y. In this process, the TiO2-coated ITO glass was used as the working electrode. The potential cycling was performed at the rate of 50 mV/s and cycling was succeeded three times. The study of electrodeposition of ZnO was well studied by Yoshida et al. [19,20]. When ZnO electrodeposition was conducted without dye molecules, ne particles composed of at disk-stacks that were oriented

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499

Current density (mA/cm )

0.2 0.0 -0.2 -0.4 -0.6 -0.8 -1.0 -1.2 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2

-1.17

(a)

Voltage (V vs. Ag/AgCl)

0.0

Current density (mA/cm )

-0.2

-0.4

-0.6

-0.96 V

-0.8

-1.0 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2

(b)

Voltage (V vs. Ag/AgCl)

Fig. 2. Cyclic voltammograms of TiO2-coated ITO in (a) a solution containing 3 104 M Eosin Y and (b) a solution containing 0.1 M Zn(NO3)2 6H2O and 3 104 M Eosin Y.

perpendicular to the substrate according to the following reactions: ZnNO3 2 6H2 O H2 O-Zn2 2NO3 7H2 O; Zn2 NO 2e -ZnO NO ; 3 2 When Eosin Y existed, the growth of ZnO was signicantly changed. During the process, Eosin Y molecules were adsorbed to ZnO planes by forming complex with Zn2+ and simultaneously blocked the growth of ZnO. Consequently, nanosized Eosin Y modied ZnO lm on TiO2 was obtained. These phenomena could be conrmed by the cyclic voltammograms. Fig. 2(a) shows that the cyclic voltammogram of Eosin Y has a reversible shape and the cathodic peak corresponding to the reduction of Eosin Y is ca. 1.17 V and the anodic peak presents at ca. 0.67 V. Fig. 2(b) is the cyclic voltammogram of the solution containing both 0.1 M Zn(NO3)2 6H2O and 3 104 M Eosin Y. In this Figure, the cathodic peak for Eosin Y is ca. 0.96 V and the anodic peak has disappeared. This indicates that when Zn(NO3)2 6H2O and Eosin Y are both present in the solution, the Eosin Y is irreversibly reduced. It means that Eosin Y is reduced and makes a stable complex

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with Zn2+ and does not oxidized again. Based upon this result, the chronoamperometric deposition was performed at 1.10 V for 1 h at room temperature. Thus, the TiO2/ZnO/Eosin Y photoanode structure could be prepared and this phenomenon was veried from the change in lm color after exposure to air due to the reoxidation of Eosin Y by oxygen [19]. The more accurate mechanism of the co-reduction of ZnO/Eosin Y requires further study and those are currently underway. Fig. 3(a) shows the IV curves of a DSSC fabricated by a conventional TiO2/Eosin Y electrode and a new TiO2/ZnO/Eosin Y electrode. By providing an inherent energy barrier that led to a decrease in recombination rate, the value of ISC ; VOC ; the ll factor, and efciency increased from 0.87 to 0.96 mA, from 0.57 to 0.64 V, from 46.2% to 63.8%, and from 2.6% to 4.4%, respectively. The VOC and ISC represent the maximum photovoltage and photocurrent obtainable from the cell, respectively, and ll factor was calculated from these values and can be expressed by the following equation: FF Im V m : ISC VOC

In this equation, Im Vm is the maximum power and can be obtained from the cell. When the ll factor value was close to 1, it can be considered as an efcient cell. So a number of trials aimed at improving this value were conducted. To reduce the recombination rate, we provided an inherent energy barrier and, consequently, the ll factor value dramatically increased. In addition, the amount of adsorbed dye on both electrodes was compared by the UV/vis absorption spectra measurement. Since the amount was similar, the surface area assumed to be similar and the effect of amount of adsorbed dye on cell performance could be ignored. An increase in the ISC in the case of the TiO2/ZnO/Eosin Y structure was observed by AC impedance spectra as well. Fig. 3(b) shows the resulting Nyquist plots of the cell in the short-circuit condition at illuminated state. The circle of DSSC using a TiO2/ZnO/Eosin Y electrode was smaller than that of DSSC using a TiO2/Eosin Y electrode. In an inset of Fig. 3(b), at high frequency, a small semicircle corresponding to the charge transfer resistance from TiO2 to ITO was observed and the charge transfer resistance from excited dye was appeared at low frequency. To interpret the resulting curves, dye-coated TiO2 electrode was modeled by an equivalent circuit proposed by Hauch et al. [21]. In this process, it was assumed that the dye-coated TiO2 electrode was composed of a multiplayer structure and four resistances can be assumed in the circuit. The resistance of electrolyte solutions, the charge transfer resistances at the electrolyte/TiO2 interface and the TiO2/ITO interface, and nally the resistance of the electrons in the TiO2 lm can be considered. This indicates that the charge transfer resistance was decreased when the TiO2/ZnO/Eosin Y electrode was used and this provides evidence that the photocurrent is increased. The charge transfer resistance at the electrolyte/TiO2 means the charge transfer resistance from excited dye to the TiO2 and this could be regarded as a relative measure of barrier height of the electron injection from excited dye molecules to the conduction band of the TiO2 [9]. In other words, the lower the charge transfer resistance, the larger the electron injection driving force and, consequently, a larger ISC can be obtained. By

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0.6

501

Current density (mA/cm2)

0.5

0.4

0.3

0.2

0.1

TiO2 /ZnO/Eosin Y TiO2 /Eosin Y

-0.1 -0.2 -0.3 -0.4 -0.5 -0.6 -0.7 -0.8

0.0 0.0

(a)
12000 10000 8000

Voltage (V)
TiO2 /ZnO/Eosin Y TiO2 /Eosin Y

-Z" ( )

6000 4000 2000 0 -2000 0 2000 4000 6000 8000

-Z" ( )

Z ' ( )

10000

12000

14000

(b)
0. 8

Z' ( )

0. 6

JSC (mA/cm2)

0. 4

0. 2

T iO2 /ZnO /Eosin Y T iO2 /Eosin Y

0. 0 0 500 1000 1500 2000 2500 3000 3500 4000

(c)

Time (s)

Fig. 3. (a) IV curves of a DSSC fabricated by a conventional TiO2/Eosin Y electrode and a TiO2/ZnO/ Eosin Y electrode. (b) Nyquist plots of the cells in short-circuit condition. (c) Change in ISC with increasing time.

using the TiO2/ZnO/Eosin Y electrode the simulated and tted charge resistance was decreased from 13.42 to 0.83 kO, which explains the increase in ISC : The charge transfer resistance from TiO2 to electrolyte is important but in this study we focused on the charge transfer resistance from excited dye to semiconductor electrode. When

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the ZnO/Eosin Y was prepared on the TiO2 surface, electron injection from the Eosin Y into the semiconductor electrode was easier due to the help of the ZnO. Because of the existence of thin ZnO, electron can be moved step-by-step to TiO2 more rapidly. Of course, if the ZnO was thick, the charge transfer from the ZnO to the electrolyte would be higher due to low electron effective mass of ZnO [22]. In this case, the recombination will increase and cell performance will be worse than the conventional electrode system. But as we mentioned, when ZnO is electrodeposited with the Eosin Y, the growth of ZnO was hindered and limited by the Eosin Y. Fig. 3(c) shows the change in ISC with increasing time. In the case of the TiO2/Eosin Y cell, the ISC was decreased with increasing time and the degradation was reduced using the TiO2/ZnO/Eosin Y electrode. This phenomenon can be attributed to two causes: (i) a decrease in recombination rate, (2) an improved stability of the adsorbed dye molecules during illumination time. Eosin Y is an efcient dye but has poor stability. Therefore, when Eosin Y is adsorbed using a conventional immersing method, desorption of the dye is a serious issue. However, when the Eosin Y was prepared by one-step cathodic electrodeposition with ZnO, the stability of dye was improved considerably. These facts were veried by the UV/ vis absorption spectra measurement of the desorbed dye solutions. To compare the degree of the desorption of adsorbed Eosin Y, we prepared the solution of desorbed dye. That is, the dye-modied electrodes were immersed in the solvent that used to dye adsorption process. TiO2/ZnO/Eosin Y electrode was fabricated from the aqueous solution of Zn (NO3)2 and Eosin Y and, so, it was immersed in water for 5 h. TiO2/Eosin Y electrode was immersed in the ethanol during same time due to the use of ethanol in the dye adsorption process. The lled triangles in Fig. 4 represent the absorption spectroscopy of the desorbed dye from the TiO2/ZnO/Eosin Y electrode and open triangles show that of the desorbed dye from the TiO2/Eosin Y

Absorbance (a.u)
400

450

500

550

600

650

700

750

Wavelength (nm)
Fig. 4. UV/vis absorption spectra of desorbed dye solutions, (m) from TiO2/ZnO/Eosin Y prepared by a one-step cathodic electrodeposition and (n) from TiO2/Eosin Y prepared by an immersing method.

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electrode, respectively. The maximum absorption peak of the two solutions appeared at about 532 nm, consistent with the lmax of Eosin Y. The position of the peak was same, while the difference in absorption intensity was large. In the case of open triangles, the absorption intensity was about nine times more intense than for the lled triangles. In addition, to remove the effect of solvent, dye adsorption in TiO2/ Eosin Y electrode was conducted in the water and the result was same as Fig. 4. This indicates that the desorption of Eosin Y from the TiO2/Eosin Y electrode is more extensive than that of Eosin Y from the TiO2/ZnO/Eosin Y electrode. In other words, the stability of the dye prepared by the immersing method was much worse than that co-deposited with ZnO. By fabrication of TiO2/ZnO/Eosin Y electrode, we were able to improve both cell performance and stability. To conrm the role of ZnO and eliminate the effect of the different dye adsorption method, we prepared the TiO2/ZnO electrodes by cathodic electrodeposition from an aqueous solution containing only Zn(NO3)2 6H2O under different conditions. These TiO2/ZnO electrodes were then immersed in the dye solution with the reference TiO2 electrode and then applied to the DSSC. Six TiO2/ZnO electrodes were prepared by electrodeposition at the same voltage of 1.0 V for periods of 10, 20, 30, 40, 50, and 60 min, respectively. The formation ZnO on TiO2 was veried by XRD, EDX, and TEM images. Fig. 5(a) shows the XRD patterns for the electrodes. In Fig. 5(a), the crystalline peaks of 25.3 , 27.6 , and 30.1 , 35.0 correspond to TiO2 and ITO. The ZnO has crystalline peaks at 31.8 , 34.4 , 36.2 (see dotted lines). The intensity of the ZnO peak increased with increasing deposition time and when the electrodeposition was conducted for 10, or 20 min, the ZnO pattern was not observed but the existence of ZnO could be veried by EDX. This indicates that the amount of ZnO present increased with increasing deposition time. Figs. 5(b) and (c) show TEM images of the TiO2 electrode and TiO2/ZnO one using a 10 min deposition time for the ZnO. The images were obtained by scratching the deposited lms. Fig. 5(c) shows that thin layer of ZnO nanoparticles were formed on the TiO2. To compare the cell performance, DSSCs were fabricated using Ru 535 (Solaronix Co., Ltd.) and liquid electrolyte as a sensitizer and electrolyte, respectively. When the amount of ZnO was small, cell performance and stability were improved, but when the electrode position process was conducted over a 40 min period, the ISC was largely decreased (not shown here). This is probably due to the extent of reduction of adsorbed dye. In DSSC, one of the most important parameters affecting the photocurrent is the amount of adsorbed dye. When ZnO was deposited over a long period of time, the porosity of the electrode was reduced, to the extent that dyes cannot propagate to the inner space. This was conrmed by SEM images of the electrode surface and cross-section (not shown). In addition, with an increasing amount of ZnO the negative effect of ZnO could affect cell performance. ZnO has a low value of electron effective mass of about 0.2me [22]. This indicates that the ZnO could readily leak the electron injected from the dye. Using these processes, the optimum conditions for electrodeposition could be determined. When the ZnO was deposited during 1020 min the DSSC performance was optimum.

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(1 01) (0 02) (1 00)

ZnO

60 min. 50 min.

Intensity
10

40 min. 30 min. 20 min. 10 min.

20

30

40

50

60

70

(a)
(b)

2 (degree)

(c)

120 nm

120 nm

Fig. 5. (a) XRD patterns of TiO2/ZnO electrodes for different deposition times of ZnO. TEM images of (b) a TiO2 electrode and (c) a TiO2/ZnO electrode, prepared using a 10 min deposition time for ZnO.

4. Conclusions In DSSC, the particle size is too small to support the space charge region. Thus, the recombination rate of photoinjected electrons with triiodide is very high due to the absence of an energy barrier at the electrode/electrolyte interface. In this study, to reduce the recombination rate, a new TiO2/ZnO/dye structure electrode was formed by one-step cathodic electrodeposition using an aqueous solution of Zn(NO3)2 6H2O and Eosin Y. The TiO2/ZnO/Eosin Y lms were then applied in a DSSC and the solar performance was measured by means of IV curves and chronoamperometry. In the case of conventional DSSC, the short-circuit current was decreased with increasing time. In contrast to conventional DSSC, when a new electrode was applied in the DSSC, degradation of the cell was reduced and ISC ; VOC ; and ll factor were increased. This was interpreted as being due to a decreased

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recombination rate and an increased stability of the adsorbed dye molecules. Further studies using other dyes are currently underway.

Acknowledgements This work was supported by the Ministry of Commerce, Industry and Energy and the Brain Korea 21 Project from the Ministry of Education in Korea.

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