Solar Energy 76 (2004) 745750 www.elsevier.

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The inuence of acid treatment of TiO2 porous lm electrode on photoelectric performance of dye-sensitized solar cell
Sancun Hao, Jihuai Wu *, Leqing Fan, Yunfang Huang, Jianming Lin, Yelin Wei
Institute of Materials Physical Chemistry, Material Science and Engineering College, Huaqiao University, Quanzhou 362011, China Received 9 July 2003; received in revised form 26 December 2003; accepted 31 December 2003 Communicated by: Associate Editor T.M. Razykov

Abstract A dye-sensitized solar cell (DYSC) was assembled by adsorbing cis-dithiocyanato-bis (2,20 -bipyridyl-4,40 -dicarboxylate) ruthenium (II) onto TiO2 porous lm. The inuence of acid treatment of TiO2 electrode with dierent kinds and concentrations on the photoelectric performance of DYSC was investigated. It was found that DYSC had better photoelectric performance when the TiO2 electrode was treated by hydrochloric acid than that by sulfuric acid, nitric acid and phosphoric acid. When the concentration of hydrochloric acid to treat TiO2 electrode increases from 0 to 0.10 M, the ll factor of DYSC increases, the short-circuit current decreases, the open-circuit photovoltage increases and the absorption amount for TiO2 porous lm to dye molecules decreases. The acid treatment of TiO2 electrode provides useful information on the mechanism of energy conversion of DYSC. 2004 Elsevier Ltd. All rights reserved.
Keywords: Dye-sensitized solar cell; TiO2 porous lm; Fill factor; Acid treatment

1. Introduction Dye-sensitized nanocrystalline TiO2 solar cell (DYSC) has become an alternative photovoltaic device, which provides a more technical and economical lightto-electric converting mode than that based on pn junction. Now a days, this kind of solar cell reaches a photoelectric conversion eciency exceeding 10% under sunlight irradiation (Anuradha et al., 2002), which shows a good prospect for application in solar conversion. The DYSC consists of sensitizing dye, TiO2 porous lm (anode electrode), electrolyte and opposite electrode (cathode electrode). When DYSC is irradiated by sunlight, the electrons of dye are excited from ground state to excited state by adsorbing photons. The excited
Corresponding author. Tel.: +86-595-269-3899; fax: +86595-269-3999. E-mail address: jhwu@hqu.edu.cn (J. Wu).
*

electrons are injected to the conductive band of TiO2 porous lm, and then transfer to the conducting glass through the porous TiO2 lm. Since TiO2 porous lm plays a key role in the enhancement of photoelectric conversion eciency of DYSC, many scientists focus their researches on it. Especially, chemical and physical treatment methods are used to improve the surface state of TiO2 porous lm (Duy et al., 2000; Shingo et al., 2000; Villegas and Pascual, 1999). In this article, a dye-sensitized solar cell is assembled by adsorbing cis-dithiocyanato-bis (2,20 -bipyridyl-4,40 dicarboxylate) ruthenium (II) onto TiO2 porous lm. The inuence of the acid treatment of TiO2 electrode with dierent kinds and concentrations on the photoelectric performance of DYSC is investigated by IV character curve and UVVIS spectra. It is found that acid treatment with a suitable acidity to TiO2 electrode results in the increase of VOC and , and the decreases of ISC for DYSC.

0038-092X/$ - see front matter 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.solener.2003.12.010

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Nomenclature I ISC ll factor current (A) short-circuit current (A) M V Voc mol concentration (mol/l) voltage (V) open-circuit voltage (V)

2. Experimental 2.1. Materials Conducting glass plates (ITO glass, uorine-doped SnO2 over-layer, sheet resistance 8X/cm2 , made by Beijing Building Material Factory, China) were used as a substrate for precipitating TiO2 porous lm on and were cut into 2 1.5 cm2 sheets. Sensitizing dye cis[(dcbH2 )2 Ru(SCN)2 ] was purchased from SOLARONIX SA, and TiO2 powder (P-25) was purchased from Degussa AG. All other reagents (from Xilong Chemicals) were used without further purication. 2.2. Preparation of nanocrystalline TiO2 electrode TiO2 porous lm electrode was manufactured by using a technique published in Ref. (Kei et al., 1995, 1997, 1998). A TiO2 paste was prepared by blending 3 g TiO2 powder in 5 ml of acid solution and 0.1 ml of acetylacetone solution in an agate mortar, and then the mixture was ground for 30 min. Finally, 1 ml of alcohol containing 0.1 ml of emulsication agent (octylphenylaether polyethylene) was slowly added with grinding continuously for the other 30 min. A conducting glass sheet was immersed in an isopropanol solution for 48 h to remove any impurities. A plastic adhesive tape was xed on the four sides of conducting glass sheet to restrict the thickness and area of TiO2 porous lm. About 1 1 0.01 cm3 of TiO2 paste was spread onto the conducting glass by using a doctor scraping technique. Finally, the TiO2 porous lm was solidied and sintered by ring the conducting glass sheet at 450 C in air for 30 min. After cooled to 353363 K, the glass sheet was immersed in a 2.5 104 M ethanol solution of cis[(dcbH2 )2 Ru(SCN)2 ] for 24 h to absorb the dye adequately, the other impurities were washed up with anhydrous ethanol and dried in moisture-free air. After that, a TiO2 porous lm electrode absorbed dye was prepared. 2.3. Assembling of the DYSC A DYSC was assembled by lling an electrolyte solution (0.5 M KI + 0.05 M I2 dissolving in the solution of ethylene glycol + acetonitrile with a volume ratio of

1:4) between a TiO2 porous lm electrode (anode electrode) and a Pt plated conducting glass sheets (cathode electrode, prepared by electrodepositing). The two electrodes were clipped together and a cyanoacrylate adhesive was used as sealant to prevent the electrolyte solution from leaking. 2.4. Characterization of nanocrystalline TiO2 electrode The photovoltaic test of DYSC was carried out by measuring the IV character curves under irradiation of white light from a 100 W xenon arc lamp (XQ-500W, Shanghai Photoelectricity Device Company, China) in ambient atmosphere. The (ll factor) of DYSC was obtained according to ff I V max =ISC VOC by I V curves. The absorption spectra and reectance spectra of the samples were measured by using a UV-3100 UV VIS spectrophotometer (Shimadzu Corporation, Japan). The TGA curve of TiO2 lm was measured by a SDT 2960 simultaneous DSC-TGA device (USA TA Instrument).

3. Results and discussion 3.1. Inuence of type of acid on TiO2 electrode The photoelectric performance of the dye-sensitized solar cell relates to the acid treatment of TiO2 electrode. Fig. 1 shows IV character curves of DYSC whose TiO2 electrode treated by dierent acid at pH 1. When hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid was used, the of DYSC was 65.50%, 50.24%, 31.07% and 23.62%, respectively. In the same conditions, the TiO2 electrode treated by hydrochloric acid shows best photoelectric performances in four kinds of acid. The better photoelectric performances for TiO2 electrode treated by hydrochloric acid than by other acids may be is due to that hydrochloric acid is a strong and nonoxidatic acid, when it is used, a suitable active point can be formed on TiO2 particles, the surface structure of TiO2 lm is not destroyed and no new impurities are imported into TiO2 particles. When TiO2 lm treated by hydrochloric acid is sintered in 723 K, water, organic compound and hydrochloric acid remainders all can be removed completely; impurities

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pH=1 HCl treat, ff=65.5% pH=1 HNO3 treat, ff=50.24% pH=1 H2SO4 treat, ff=31.07% pH=1 H3PO4 treat, ff=23.62% 3 Current (mA/cm2)

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3.2. Inuence of acid concentration on the short-circuit current and open-circuit photovoltage The concentration of hydrochloric acid will aect the property of TiO2 electrode and ISC of DYSC. From Fig. 3, when the concentration of hydrochloric acid increases from 0.01 to 3 M, the ISC gradually decreases from 3.89 to 0.8 mA. Acid treatment changes the surface state of TiO2 porous lm, creates defects centers on the surface of TiO2 particle, these defect can capture the electrons on the excited state of sensitized-dye molecules and prevent the electrons from transferring in nanocrystalline TiO2 grid, which makes lower electrons transportation eciency. On the other hands, the size of the TiO2 particles become larger and the surface areas become smaller with the enhancement of the concentration of hydrochloric acid treated to TiO2 lm, which makes the smaller contact area between the particles, more dicult ow for electrons and smaller ISC . In addition, H may absorb to surface of TiO2 particles and form bond with O on surface of the TiO2 particles. Some researches (Duy et al., 2000; Huber et al., 2002; Vargas and Niklasson, 2001; Yasuhiro et al., 2002) believe that O on surface of TiO2 particles may relate to combination between dye molecules and TiO2 lm, as well as the process of electrons injecting from excited energy level of dye molecules to TiO2 conduction band, these processes are tied up to ISC closely, with the add of H , the concentration of O in surface of TiO2 particle will be reduced, which lead to the decrease of ISC in some extent. Opposite to the trend of ISC , VOC has a lightly enhancement with the increase of the concentration of hydrochloric acid treating to TiO2 electrode. From Fig. 4, when the concentration of hydrochloric acid increases from 0 to 0.1 M, the VOC gradually increase from 530 to 598 mV. According the fundamental principle of DYSC (Jrg et al., 1998), VOC is the potential dierence between o the reversible redox couple I =I3 in electrolyte and the Fermi level of TiO2 . Since the electrolyte is the same in
4

0 0.0 0.2 0.4 Voltage(V) 0.6

Fig. 1. The IV character curves of DYSC, whose TiO2 electrode was treated by HCl, HNO3 , H2 SO4 and H3 PO4 at pH 1, respectively.

100

weight (%)

95

90

85 100 200 300 temperature (C) 400 500

Fig. 2. The TGA curve of TiO2 lm treated by 0.1 M hydrochloric acid.

cannot be imported into TiO2 lm by hydrochloric acid treatment, which can be concluded from the TGA curve in Fig. 2. However, nitric acid is a strong oxidatic acid, it can demolish the surface structure of TiO2 porous lm, the bond between NO and the surface of TiO2 particles 3 is weak, so the inuence of treatment with nitric acid on the adsorption of TiO2 lm to dye molecules is small. Although sulfuric acid or phosphoric acid is nonoxidatic acid at pH 1, SO2 or PO3 can absorb on to the 4 4 surface of TiO2 particles and bond with O of the surface of the TiO2 porous lm, especially for PO3 . 4 The bond between SO2 or PO3 and O will block the 4 4 adsorption for TiO2 lm to dye molecules, since the bond between SO2 or PO3 and O are stronger more 4 4 than the bond between COOH and O (Nazeeruddin et al., 2000). Based on the above, hydrochloric acid was chosen as treatment agent to TiO2 electrode.

3 ISC ( mA/cm2 )

1 0.0 0.5 1.0 1.5 2.0 2.5 HCl concentration ( mol/l ) 3.0

Fig. 3. Infulence of HCl concentration on ISC .

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0.7

0.6 VOC ( V )

0.5

ITO lm increased quickly from 116.5 to 1227.6 X cm1 , so the conductivity of ITO may be aected by additional acid treatment through the porous TiO2 layer, which inevitably results in the increase of internal resistance of DYSC. Higher internal resistance may mean lower ISC and eciency, which is consistent with the result of ISC in our experiment. 3.4. Inuence of acid concentration on adsorption capacity of TiO2 lm to dye
0 1 2 HCl concentration ( mol/l ) 3

0.4

0.3

Fig. 4. Inuence of HCl concentration on VOC .

the experiments, we can conclude that Fermi level of TiO2 may be shifted to more plus when the concentration of hydrochloric acid treating to TiO2 electrode increased from 0 to 0.10 M, which is consistent with the fact that TiO2 particles develop a pH-dependent double layer to produce a at-band potential shift (59 mV/pH), but the increase of VOC in the experiment is lower than the shift of TiO2 at-band potential, it may be due to the lower actual acidity for TiO2 electrodes comparing to the acidity of acid solution. When beyond the 0.10 M of the concentration of hydrochloric acid, the VOC decrease. When the concentration of hydrochloric acid is 3 M, the VOC is only 450 mV. High acid concentration, such as 3 M, will strongly destroy the surface of TiO2 electrode, which results in the mismatch of the TiO2 potential and energy level of dye, and the diculty (see 3.4) of dye molecular bonding with TiO2 lm and thus the decrease of VOC . 3.3. Inuence of acid treat on resistance of ITO and contact with TiO2 lm From Fig. 5, the conductivity of ITO lm is aected strongly by the acid. When hydrochloric acid concentration increases from 0 to 3 M, the surface resistance of

Fig. 6 shows the absorption spectra of cis[(dcbH2 )2 Ru(SCN)2 ]. There are two absorption peaks lying in the wavelength about 397 and 534 nm, respectively, which result from metal-to-ligand charge transfer (MLCT) in dye molecular (Grtzel, 1999). Fig. 7 shows a the UVVIS reection spectrum of dye-sensitized TiO2 porous lm treated by dierent concentrations hydrochloric acid.

ABS

0 400 600 wavelength (nm) 800

Fig. 6. cis-[(dcbH2 )2 Ru(SCN)2 ] absorption spectrum in ethanol solution.

60 3.0M HCl treat 1.5M HCl treat 0.7M HCl treat 0.1M HCl treat 0.01M HCl treat

3mol/l HCl concentration

R%

40

1.5mol/l 0.7mol/l 0.1mol/l 0.01mol/l 0 0 400 800 Resistance (/cm) 1200

20

0 200

400 600 wavelength (nm)

800

Fig. 5. Surface resistance of ITO with HCl concentration.

Fig. 7. Reection spectrum of dye-sensitized TiO2 lm treated by HCl with dierent concentrations.

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Comparing to Figs. 6 and 7, it can be seen that (1) the 534 nm absorption peak of dye molecules still exists in the dye-sensitized TiO2 porous lm, but the 397 nm absorption peak disappears, which attributes to the reaction between dye molecules, TiO2 lm and ITO glass. (2) With the increase of the concentration of hydrochloric acid treated to TiO2 lm, the reectivity of the sample increases, which indicates the decrease of adsorption amount of TiO2 porous lm to dye molecules. The reason may be that with the increase of the concentration of hydrochloric acid treating to TiO2 porous lm, TiO2 particles aggregate more easily and the size of TiO2 particles becomes larger and the surface area of TiO2 lms becomes smaller, which results in the decline of adsorption amount to dye molecules. In despite of reducing adsorption amount when the concentration of hydrochloric acid increased from 0 to 0.10 M, the adsorption is eectual and mono-molecule layer, which is advantageous for enhancing the and VOC of DYSC. This explanation is consistent with the increase of VOC with the increase of acid concentration in some extent. 3.5. The inuence of hydrochloric acid concentration on the ll factor The of DYSC changes greatly with the increase of the concentration of hydrochloric acid treated to TiO2 electrode. From Fig. 8, when TiO2 electrode is treated by hydrochloric acid with the concentration of 3, 1.5, 0.7, 0.1 and 0.01 M, the of DYSC is 23.2%, 39.5%, 43.8%, 65.5% and 61.8%, respectively. Comparing to 57.5% for no treatment by acid, there is a little increase for 0.10
no HCl treat, ff=57.5% 0.01M HCl treat, ff=61.8% 0.1M HCl treat, ff=65.5% 0.7M HCl treat, ff=43.8% 1.5M HCl treat, ff=39.5% 3.0M HCl treat, ff=23.2%

and 0.01 M of hydrochloric acid treated. When hydrochloric acid concentration is beyond 0.10 M, will decline largely. The reveals energy losses coming from the inherent resistance of the photovoltaic device, higher means less internal energy lose and better photoelectric performance for DYSC. Acid treatment, on the one hand, will produce active point on the surface of TiO2 lm, which is advantageous for the adsorption to molecules and enhancement of the photoelectric performance of TiO2 electrode. On the other hand, higher acid concentration will result in the appearance of the defect, the growth of TiO2 nanocrystal and decline of the surface area of TiO2 , which is disadvantageous to the enhancement of the of DYSC. So there is an optimum concentration for hydrochloric acid treated to TiO2 electrode, in our experiment, when the concentration of hydrochloric acid is about 0.10 M, the of DYSC is better (65.5%).

4. Conclusion From the results of the tests described, the following conclusions may be drawn. (1) A dye-sensitized solar cell was assembled by adsorbing cis-dithiocyanato-bis (2,20 bipyridyl-4, 40 -dicarboxylate) ruthenium (II) onto TiO2 porous lm. (2) DYSC has better photoelectric performance when the TiO2 electrode was treated by hydrochloric acid than those by sulfuric acid, nitric acid and phosphoric acid, which reveals that the surface acidity of TiO2 relates to ISC , VOC and eciency of DYSC closely. (3) When the concentration of hydrochloric acid treated to TiO2 electrode increased from 0 to 0.10 M, the ll factor of DYSC increased, the short-circuit current decreased, the open-circuit photovoltage increased and the absorption amount for TiO2 porous lm to dye molecules decreased. (4) Additional acid treatment aects the resistance of ITO lm through the TiO2 porous layer, which may result in the increase of internal resistance of DYSC.

4 Current ( mA/cm2 )

Acknowledgements The authors thank for jointly supporting by the National Natural Science Foundation of China (nos. 50082003, 50372022), the Provincial Natural Science Foundation of Fujian, China (nos. 2001I006, E0210023, E0110026).

0 0.0

0.2

0.4

0.6

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Fig. 8. IV curves of DYSC, whose TiO2 electrode treated by HCl.

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