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Solar Energy 81 (2007) 529534 www.elsevier.

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Electrodeposition of TiO2/SiO2 nanocomposite for dye-sensitized solar cell


The-Vinh Nguyen 1, Hyun-Cheol Lee, M. Alam Khan, O-Bong Yang
School of Environmental and Chemical Engineering, Chonbuk National University, Jeon-Ju, South Korea Received 2 March 2006; received in revised form 17 June 2006; accepted 11 July 2006 Available online 14 September 2006 Communicated by: Associate Editor Sam-Shajing Sun

Abstract For the working electrode of dye-sensitized solar cell (DSC), TiO2/SiO2 nanocomposite materials were electrodeposited on transparent uorine doped tin oxide-coated glass by cathodic electrodeposition at room temperature. The electrode and DSC fabricated with TiO2/SiO2 nanocomposite were characterized with photocurrent density, X-ray diraction (XRD), eld emission-scanning electron microscopy (FE-SEM) and a photovoltaic performance test. On the electrodeposition, the addition of an appropriate amount of SiO2 in the bath containing TiO2 slurry was essential to achieve the superior crystallinity, photocurrent density and photovoltaic performance of the resulting TiO2/SiO2 electrode, which was signicantly superior to a bare TiO2 electrode. This enhanced performance of optimized TiO2/SiO2 electrode was ascribed to the role of SiO2 as an energy barrier, increasing the physical separation of injected electrons and oxidized dyes/redox couple, and thereby retarding the recombination reactions in the resulting DSC. 2006 Elsevier Ltd. All rights reserved.
Keywords: Dye-sensitized solar cell; Electrodeposition; TiO2/SiO2 nanocomposite; Energy barrier

1. Introduction Dye-sensitized solar cell (DSC) has been known as a promising photovoltaic device to achieve moderate eciency at ultra-low cost (ORegan and Gra tzel, 1991). The use of large surface area semiconductor materials in DSC is necessary to provide sucient light absorption with only one adsorbed mono-layer of dye. For the working electrode in DSC, nanoporous TiO2 thin lm had been prepared by coating the hydrolyzed titanium alkyloxides under acidic conditions on transparent conducting oxide (TCO) glass and calcining at 450 C for ca. 30 min to remove organic compounds. The latter process decreases the level of the specic surface area of TiO2 substrate at
Corresponding author. Tel.: +82 63 270 2313; fax: +82 63 270 2306. E-mail address: obyang@chonbuk.ac.kr (O.-B. Yang). 1 Present address: Faculty of Environment, Hochiminh City University of Technology, Hochiminh City, Viet Nam. 0038-092X/$ - see front matter 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.solener.2006.07.008
*

the high temperature calcination. In order to avoid high temperature calcination of TiO2 thin lm, Pichot et al. reported on the low temperature calcination of TiO2 colloid lms at around 100 C for DSC (Pichot et al., 2000). And Lindstro m et al. reported a new method of non-sintered nanostructured porous electrode preparation as an eort to prepare TiO2 substrate at room temperature without calcination step (Lindstro m et al., 2002). In the present study, TiO2 and TiO2/SiO2 thin lms are prepared at room temperature by using a cathodic electrodeposition method. This technique has been well known to provide simple and inexpensive alternative routes to synthesize nanoparticulate materials and is also feasible to prepare non-at substrates for exible DSCs (Therese and Kamath, 2000). In this work, the electrodeposition conditions were optimized and the properties of electrodeposited electrodes were elucidated in terms of their photocurrent densities and the photovoltaic performance of resulting DSCs. Optimized TiO2/SiO2 nanocomposite thin lms

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Nomenclature FF I ISC g x, n ll factor current density (mA/cm2) short-circuit current density (mA/cm2) overall conversion eciency mol of SiO2 and TiO2 in the complex [(SiO2)x(TiO2)n](nx)+; n P x M V VOC PZC SiO2/TiO2 molar ratio voltage (V) open-circuit voltage (V) point of zero charge

could be prepared by introducing SiO2 as a wide band-gap material, which resulted in a signicant improvement of the performance of corresponding DSC. In the optimized TiO2/SiO2 electrode, SiO2 seemed to act as an energy barrier to suppress recombination at the TiO2/electrolyte interface. 2. Experimental 2.1. Materials TiO2 powder (P25, Degussa), fumed silica (SiO2, specic surface area: 335 m2/g, Aldrich), Eosin Y (Aldrich) as a dye sensitizer were used as received. The supporting substrates were optically transparent uorine doped tin oxide-coated glass supplied by Libbey-Owens-Ford (TEC-8, FTOcoated glass, 8 X/sq, 80% transmittance in the visible). 2.2. Preparation of TiO2 thin lm Cathodic electrodeposition of TiO2 nanoparticles on the optically transparent uorine doped tin oxide-coated (FTO) glass was carried out in an electrochemical bath (100 ml). Negative potentials (V vs. Ag/AgCl) were applied on FTO glass plate (15 mm 15 mm) by the potentiostat in an aqueous slurry containing 0.8 M TiO2. The electrodeposition bath was purged continuously with ultra-pure nitrogen gas under mild magnetic stirring. The bath pH was controlled by 35% HCl (for acid range) or Na2SO3 (for base range). The scanning time of potentiogalvanostat was xed at 600 s for every experiment. After electrodeposition, the resulting TiO2 electrode lm was gently rinsed with distilled and de-ionized water and then dried in air at 75 C for 30 min. For comparison, dried lms were subject to calcining in air at 150 C, 250 C, 350 C, 450 C and 550 C for 30 min. 2.3. Preparation of TiO2/SiO2 nanocomposite thin lm For the preparation of TiO2/SiO2 nanocomposite electrode thin lms, the same procedures for TiO2 thin lm preparation were repeated except for the addition of fumed silica with the SiO2/TiO2 molar ratios of 0.27, 0.40, 0.53, 0.67 and 0.80. The resulting lm was denoted as TiO2/ SiO2M (where M indicates the SiO2/TiO2 molar ratio in the bath). For comparison, electrode thin lms of TiO2

and TiO2/SiO2 were prepared by doctor-blade method with the SiO2/TiO2 molar ratios of 0.07, 0.13 and 0.20, which were represented as DbTiO2 or DbTiO2/SiO2M (Nguyen et al., 2006). 2.4. Fabrication of DSC The sandwich DSC of two electrodes was fabricated by the typically known method with the dye (Eosin Y) adsorbed working electrode of TiO2 or TiO2/SiO2, a Ptsputtered counter electrode and an organic electrolyte (0.3 M LiI, 15 mM I2, and 0.2 M tert-butyl pyridine in acetonitrile) as described elsewhere (Park et al., 2000). The active area of the resulting cell was approximately 0.25 cm2. 2.5. Characterization of electrode thin lm and DSC Electrode thin lms were characterized with XRD (Rigaku, Cu Ka radiation) and FE-SEM (S-4700, Hitachi) equipped energy-dispersive X-ray (EDX) element analysis system (EMAX, Horiba). The photocurrent densities of TiO2-based lms were measured at pH 9 by using a scanning potentiostat (EG&G 273) with the working electrode of TiO2-based lm, the counter electrode of the Pt wire and the reference electrode of Ag/AgCl/3 M NaCl in an electrochemical cell (100 ml) containing 0.1 M Na2SO3 electrolyte. Photocurrentvoltage (IV) curves of DSCs were measured by using two computerized digital multimeters (Model 2000, Keithley) and a variable load. A 150 W Xe lamp (Hamamatsu) with a visible-band pass lter served as a light source and its intensity was adjusted for AM-1.5 irradiation. 3. Results 3.1. Optimization of electrodeposition parameters Photocurrent density correlates well with the charge transfer property of TiO2 lm in DSC (Nguyen et al., 2006). The higher the photocurrent density of TiO2 lm, the higher the short-circuit current of resulting DSC (Nguyen et al., 2006). Thus, we evaluated and optimized the electronic properties of electrodeposited TiO2/SiO2 lms based on their photocurrent densities. The electrodeposition conditions were optimized by studying the eect of deposition parameters on the photocurrent densities of

T.-V. Nguyen et al. / Solar Energy 81 (2007) 529534


300

531

pH5

-4V -5V

0.53

250 200 150 100


-6V pH4 -2V -3V 0.40 0.27 0.67

pH6

0.80 pH2

50 0

TCO

pH9

(a)

(b)

(c)

Fig. 1. The eect of pH (a), deposition potential (b) and molar ratio of SiO2/TiO2 (c) on the photocurrent density at zero DC bias of resulting TiO2/SiO2 lm. Electrodeposition conditions: (a) deposition potential = 4 V, SiO2/TiO2 = 0.53; (b) pH 5, SiO2/TiO2 = 0.53; (c) pH 5, deposition potential = 4 V.

resulting TiO2/SiO2 lms. The eects of various parameters of the deposition bath on the photocurrent densities are summarized in Fig. 1. While a parameter is varied, the others are xed at their preliminarily optimum values. However, the trends shown in Fig. 1 are consistent whatever the other electrodeposition conditions are chosen. Fig. 1a depicts the eect of bath pH on the photocurrent densities of electrodeposited TiO2/SiO2 lms. The photocurrent densities were peaked at pH 5. At pH values higher than the point of zero charge (PZC) of TiO2 (5.5 (Palomares et al., 2003)), the TiO2 nanoparticles would be negatively charged. The negatively charged TiO2 nanoparticles are repelled electrostatically from the cathode surface owing to the negative potential applied at working electrodes. This repelling force may cause weak deposition of TiO2 nanoparticles on FTO glass and increase the resistance, resulting in the low photocurrent density of derived TiO2/SiO2 lm. At very low pH value, hydrogen gas was evolved signicantly at the working electrode, which gives rise to adverse eect on the electrodeposition. Fig. 1b illustrates that 4 V is the optimal potential to deposit eectively TiO2 nanoparticles on FTO. Fig. 1c shows the eect of SiO2 addition on the photocurrent density of derived TiO2/SiO2 lm. The highest photocurrent density was observed in the electrode prepared by adding silica with a SiO2/TiO2 molar ratio of 0.53, indicating the optimal condition in terms of the SiO2 concentration in the bath. In summary, optimal electrodeposition parameters are 4 V of deposition potential, pH 5 and ca. 0.53 of SiO2/TiO2 molar ratio. All of the thin lms used in the characterization and DSC fabrication were prepared under this optimal condition. 3.2. Characterization of electrodeposited thin lms

SEM (Fig. 2) and EDX analysis. It showed that the cross-sectional thickness was ca. 2.3 lm and SiO2/TiO2 molar ratio was 0.1. The amount of deposited silica was just 10%, even though 50% of silica was contained in the bath originally. It could be explained by the fact that positively charged titania particles might be deposited easily as compared to negatively charged silica particles in the bath pH of 5 (PZCTiO2 > 5 > PZCSiO2 ). The morphology and composition of the TiO2/SiO2 lm were not changed after calcination at 450 C. Fig. 3 shows the XRD patterns of bare TiO2 and TiO2/SiO2-0.53 lms. The intensity of anatase peak (2h = 25.5) of TiO2/SiO2-0.53 lm is much higher than that of bare TiO2 lm, indicating the superior crystallinity of the former compared to the latter. The intensities of the anatase peaks are almost the same before and after calcination at 450 C (not shown). Fig. 4 shows the photocurrent densities (at zero DC bias) of bare TiO2 and TiO2/SiO2-0.53 lms as a function of calcination temperature. The photocurrent densities are signicantly improved upon calcination. In DSC, calcination step of TiO2 lm after coating TiO2 gel or slurry on the TCO glass is well known and commonly employed to produce partial sintering between the nanoparticles and between the nanoparticles and TCO glass for establishing an electrical contact among them (ORegan et al., 1990).

Photocurrent density (A/cm2)

Fig. 2. Cross-section FE-SEM image of TiO2/SiO2-0.53 lm as-prepared.

A R

A : anatase R : rutile TiO2 /SiO2 -0.53

Intensity (a.u.)

bare TiO2

TCO glass

20

30

40

50

60

70

80

The thin lm prepared in the optimal electrodeposition condition, TiO2/SiO2-0.53 lm was characterized by FE-

2-theta (degree)
Fig. 3. XRD patterns of bare TiO2 and TiO2/SiO2-0.53 lms as-prepared.

532
0.9

T.-V. Nguyen et al. / Solar Energy 81 (2007) 529534 Table 1 Photovoltaic performance data of DSCs fabricated with various thin lms and Eosin Y sensitizer Thin lm TiO2 as-deposited TiO2/SiO2-0.53 asdeposited TiO2 calcined at 450 C TiO2/SiO2-0.53 calcined at 450 C VOC (V) 0.43 0.46 0.58 0.60 ISC (mA/ cm2) 0.15 0.17 0.37 0.55 FF (%) 48 46 54 54 g (%) 0.03 0.04 0.12 0.18 Photocurrenta 0.214 0.256 0.708 0.854

20.6%

Photocurrent density (mA/cm2)

0.8
17.3%

3.8%

0.7
d

0.6 0.5 0.4 0.3 19.6%


a
12.5%

14.6%

c b

TiO2 TiO2 /SiO2 -0.53


150 250 350 450 550

Photocurrent densities (mA/cm2) of thin lms at zero DC bias.

0.2 50

Temperature (C)
Fig. 4. Photocurrent densities (at zero DC bias) of bare TiO2 and TiO2/ SiO2-0.53 lms as a function of calcination temperature. Numbers on the vertical lines are the percentage increase of photocurrent density of TiO2/ SiO2 lm compared to that of TiO2 lm. Letters af denote the dierences in photocurrent densities between TiO2 and TiO2/SiO2-0.53 lms: a = 0.04, b = 0.05, c = 0.07, d = 0.10, e = 0.15 and f = 0.03 mA/cm2.

the lms calcined at 450 C are much improved in comparison with those fabricated with the as-prepared lms. 4. Discussion 4.1. Eect of SiO2 addition on electrodeposition Since the PZC of TiO2 is 5.5, it becomes positively charged in the optimal experimental conditions (pH 5). Meanwhile, SiO2 releases proton (H+) under this pH value and becomes negatively charged owing to its low PZC of 2 (Palomares et al., 2003). Consequently, positively charged titania and negatively charged silica attract one another to form a titaniasilica complex, [(SiO2)x(TiO2)n](nx)+ in the bath (where x and n stands for the mole of SiO2 and TiO2 in the complex, respectively; n P x). Some of these titaniasilica complexes in the bath are electrodeposited on the working electrode under applied negative potential. While the others are still in the bath and therefore, increase the viscosity of the suspension at a certain value of SiO2 concentration. The addition of SiO2 in the bath accordingly increases the numbers of protons and the viscosity of the suspension. The increase of the number of protons in the bath is benecial to the formation of positively charged titania and the amount of electrodeposited titania would be enhanced on the working electrode. Meanwhile, the high viscosity of suspension gives rise to the suppression of particles electrodeposition. Consequently, as increasing the concentration of SiO2 in the bath, the amount of electrodeposited titania would be increased due to the positive eect of proton, and then decreased owing to the negative eect of viscosity, resulting in maximum photocurrent density on TiO2/SiO2-0.53 lm. 4.2. The role of SiO2 in TiO2/SiO2 electrode In this work, we tried to introduce SiO2 as a wide bandgap material in the working electrode of DSC by electrodeposition method. There are some reports on the formation of energy barrier on semiconductor electrodes by coating a thin layer of insulating oxide such as Al2O3, MgO, SiO2, TiO2, ZnO, ZrO2, etc. (Palomares et al., 2003; Diamant et al., 2003; Kay and Gra tzel, 2002). Energy barrier at the semiconductor/electrolyte interface was found to

The photocurrent densities of TiO2/SiO2-0.53 lms are higher than those of bare TiO2 lms calcined at various temperatures as indicated in Fig. 4. The absolute dierences in photocurrent densities were also increased as a function of calcination temperature except for the value at 550 C as presented by letters of af in Fig. 4.

3.3. Photovoltaic performances of DSCs Fig. 5 and Table 1 present the photocurrentvoltage (I V) curves and photovoltaic performance data of DSCs fabricated with the electrodeposited lms and Eosin Y as a dye sensitizer. TiO2/SiO2 lm-based DSCs show the superior photovoltaic performance compared to the bare TiO2 lm counterparts. The performances of DSCs fabricated with
3

Photocurrent density (mA/cm2)

(d)
2

(b)
1

(c) (a)

0 -1000

-500

Voltage (mV vs. Ag/AgCl)


Fig. 5. Photocurrent densities of TiO2/SiO2 lms prepared by doctorblade method as a function of SiO2/TiO2 molar ratio: DbTiO2/SiO2-0.20 (a), DbTiO2/SiO2-0.13 (b), DbTiO2/SiO2-0.07 (c) and DbTiO2 (d).

T.-V. Nguyen et al. / Solar Energy 81 (2007) 529534

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decrease the interaction between the photo-excited electrons in the semiconductor electrode and the electrolyte ions (Palomares et al., 2003; Diamant et al., 2003; Kay and Gra tzel, 2002). The suppression of charge recombination has been known due to the tunneling eect (Kay and Gra tzel, 2002; Tennakone et al., 2002) that allows electron injection across the barrier (thin insulating oxide layer) and prevents the electron leakage from the semiconductor to the electrolyte ions. The role of SiO2 as an energy barrier in TiO2/SiO2-0.53 lm could be explained by the results shown in Fig. 4. The photocurrent density dierence between TiO2/SiO2-0.53 and TiO2 lm as-deposited (dried at 75 C without calcination) is 0.04 mA/cm2, which is consistent with the superior crystallinity of the former compared to the latter as presented in Fig. 3. As increasing the calcination temperature, the photocurrent densities of both lms are signicantly improved owing to the enhancement of bonding between TiO2 nanoparticles and between the TiO2 nanoparticles and TCO glass (ORegan et al., 1990). The absolute dierences of photocurrent densities between TiO2/SiO2-0.53 and TiO2 lm become larger as the calcination temperature increases up to 450 C: 0.05 mA/cm2 at 150 C, 0.07 mA/ cm2 at 250 C, 0.10 mA/cm2 at 350 C and 0.15 mA/cm2 at 450 C. On the lm as-deposited (dried at 75 C), the bonding between TiO2 and SiO2 may not be chemically strong enough to generate the function of energy barrier. However, the chemical bonding between TiO2 and SiO2 would be formed tightly at around 450 C, in which the function of SiO2 as the energy barrier might be developed signicantly to suppress the charge recombination at the TiO2/SiO2-0.53 lm/electrolyte interface. By this energy barrier function of SiO2, the superior photovoltaic performance of TiO2/SiO2-0.53 electrode could be explained well. At 550 C, slight decreasing of photocurrent density dierence between TiO2/SiO2-0.53 and TiO2 lm seems to be due to the conductivity decreasing of TCO glass after calcination at high temperature (Meng and Placido, 2003). To further elucidate the role of SiO2 as an energy barrier material in TiO2/SiO2 lm, we compared the electronic properties of electrodeposited lms with those of lms prepared by doctor-blade method. Fig. 5 shows the photocurrent densities of DbTiO2 and DbTiO2/SiO2 lms prepared with the physical mixture of TiO2 and SiO2 by doctor-blade method and calcined at 450 C. In contrast to the electrodeposited TiO2/SiO2 lm, photocurrent density of DbTiO2/SiO2 lm was decreased drastically as compared to the bare DbTiO2 lm. The synergistic eect of silica addition was not observed in the lm prepared by doctor-blade method whatever the molar ratios of SiO2/ TiO2 are, which seems to be due to the insulating nature of SiO2 [band-gap energy of 8.08.9 eV (Zacheis et al., 2001)] dispersed physically in TiO2 network. This random mixed structure is not advantageous to the charge transport in the DbTiO2/SiO2 network and between this network and TCO glass, resulting in the low photocurrent density of DbTiO2/SiO2 lm as compared to DbTiO2

lm. However, in electrodeposition process, the electrostatical attractions between TiO2 and SiO2 nanoparticles formed a titaniasilica complex, [(SiO2)x(TiO2)n](nx)+ which has the intimate contacts between them in comparison with doctor-blade method. Consequently, the presence of SiO2 in TiO2/SiO2 lms prepared by electrodeposition method gives rise to the decrease of charge recombination owing to the ecient role of SiO2 as an energy barrier. The role of SiO2 as an energy barrier in TiO2/SiO2-0.53 lm is well consistent and supported by the photovoltaic performance data of DSCs in Fig. 5 and Table 1. TiO2/ SiO2 lm-based DSCs show the superior photovoltaic performance compared to the bare TiO2 lm counterparts. The superior performance is signicant on the DSC fabricated with TiO2/SiO2-0.53 calcined at 450 C. Consistency between the short-circuit current and the photocurrent density is observed on all of the cells, suggesting that the electronic property of thin lm is correlated well with the photovoltaic performance of resulting DSC. The open-circuit potential (VOC) is theoretically determined by the difference between the potential of redox electrolytes and the quasi-Fermi level of electrons in TiO2 in the light, which strongly depends on the density of photo-excited electrons injected from the adsorbed dye, Eosin Y, into TiO2 network. When the TiO2-based lms are calcined at 450 C, the nanoparticles in TiO2-based network are subjected to partial sintering that renders them chemically bonded. This process not only increases the charge transport rate due to the enhanced number of interconnections between the particles (Frank et al., 2004) but also improves the dispersion of photo-excited electrons in the TiO2 network. The latter could suppress the charge recombination that brings about the increase in the density of photoexcited electrons in the TiO2-based network and therefore negatively shifts its quasi-Fermi level (Frank et al., 2004). Consequently, DSCs fabricated with the calcined

600

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I (A/cm2)

400

(c)

300

200

(b) (a)

100

0.0

0.1

0.2

0.3

0.4

0.5

0.6

V (V)
Fig. 6. Photocurrentvoltage (IV) curves of DSCs fabricated with Eosin Y sensitizer and various thin lms: (a) TiO2 as-prepared, (b) TiO2/SiO20.53 as-prepared, (c) TiO2 calcined at 450 C and (d) TiO2/SiO2-0.53 calcined at 450 C.

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TiO2-based lms exhibit very high VOC in comparison to those fabricated with the as-prepared counterparts (Fig. 6). 5. Conclusions A novel cathodic electrodeposition of TiO2/SiO2 nanocomposite lm was elucidated and optimized for the preparation of electrode materials of DSC. The optimal electrodeposition condition was 4 V of deposition potential and bath pH 5. The addition of SiO2 around the SiO2/ TiO2 molar ratio of 0.53 was essential to obtain the superior TiO2/SiO2 electrode (TiO2/SiO2-0.53). The resulting TiO2/SiO2-0.53 nanocomposite electrode facilitated the increase of ca. 20% of photocurrent density and ca. 30% of photovoltaic eciency in comparison with the bare TiO2 electrode. The insulating tunneling role of SiO2 as an energy barrier was observed in the electrodeposited TiO2/SiO2-0.53 lm, which may suppress the charge recombination at the TiO2/electrolyte interface. This synergistic eect of silica addition was not recognized in the physically mixed TiO2/SiO2 thin lm prepared by doctorblade method. Introduction of SiO2 as an energy barrier by electrodeposition consequently resulted in the improvement of photocurrent density of the derived TiO2/ SiO2-0.53 lm and the photovoltaic performance of corresponding DSC. This electrodeposition method can be applied as an advanced microscopic way to control the electrochemical properties of the electrodes. Acknowledgements We gratefully acknowledge the nancial support from the Korea Industry Technology Foundation (KITF) by the program of Human Resources Development for Regional Innovation and the Center for Ultra Micro Chemical Process Systems (CUPS) sponsored by Korea Science and Engineering Foundation (KOSEF). T.-V. Nguyen and M. Alam Khan thanks for the nancial support from the KOSEF through the foreigner scholarship program.

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