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Journal of the Korean Physical Society, Vol. 54, No. 3, March 2009, pp.

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E ect of Electrolyte Conductivity on the Formation of a Nanotubular TiO2 Photoanode for a Dye-Sensitized Solar Cell
Kiyoung

Lee, Jiyoung Kim, Hyeyoung Kim, Yujin Lee and Yongsug Tak
Doohun

Department of Chemical Engineering, Inha University, Incheon 402-020

Kim

and Patrik

Schmuki

Department of Material Science, University of Erlangen-Nuremberg, Erlangen, Germany

(Received 16 June 2008) Ordered TiO2 nanotube arrays can be prepared by anodizing of Ti metal. However, the nanotubular TiO2 structure shows a lack of reproducibility when the Ti metal is repetitively anodized in a prepared solution. The TiO2 tube length increases as the number of anodizations increases. In this work, the e ects of the solution conductivity and temperature on the formation of the nanotubular TiO2 structure were analyzed using the measured current transients and tube morphology. Nanotubular TiO2 was tested as an anode for a dye-sensitized solar cell and its performance was interpreted using electrochemical impedance spectroscopy in relation to a morphological study of the TiO2 structure.

PACS numbers: 82.45.+z, 61.43.Gt, 84.60.Jt, 81.65.Mg Keywords: Anodizing, Ti surface treatment, DSSC, Electrochemical analysis, TiO2 nanotube
I. INTRODUCTION

Photovoltaic systems are promising alternative energy sources because they produce electricity directly from light. In order for materials to be used as a photoanode, they should have a high surface area to absorb maximum light and to e ectively utilize the absorbed energy to produce maximum electron-hole pairs [1{3]. TiO2 is an attractive material as a photocatalyst [4], biosensors [5], electrochromics [6] and especially dye-sensitized solar cells (DSSC) [7,8]. Since the band gap energy of TiO2 is $3.2 eV, TiO2 forms electron-hole pairs below 400 nm in wavelength. Ru-based dye-chemisorbed TiO2 is known to be sensitized under visible light. TiO2 can be easily prepared in a nanotubular shape, which has a high aspect ratio and a large surface area [9], by using electrochemical anodization of Ti metal. It can be prepared with di erent methods, such as sol-gel [10], deposition [11] and hydrothermal synthesis [12] methods. However, the anodization method has several advantages over other methods: the formation of highly ordered nanotube array [13,14], a low temperature and a simple experimental apparatus. Since the surface area is an important factor in DSSC, the eciency of DSSC can be increased with a longer

tube that can adsorb more dye, which is an electron source for DSSC [15]. If highly-ordered long nanotubes are to be fabricated, an organic electrolyte containing HF can be used [16]. The suggested mechanism of nanotubular TiO2 formation is [14] Ti + 2H2 O 3 TiO2 + 4H+ + 4e ; TiO2 + 6HF 3 [TiF6 ]2 + 2H2 O + 2H+ (1) (2)

TiO2 tubes can grow up to 500 nm in a HF-based aqueous electrolyte because the chemical dissolution of TiO2 takes place very rapidly [9]. An organic electrolyte, which lacks oxygen, is unfavorable to form TiO2 because chemical dissolution of the oxide is retarded by the hydro uoric acid. This results in longer TiO2 nanotubes in an organic electrolyte than in an aqueous electrolyte [15]. The tube length is also a ected by other factors, such as the pH and the concentration pro le inside the tubes [14,17], the applied potential, the anodizing time and the uoride concentration [18]. In this work, we investigated the e ect of the anodizing solution's conductivity and temperature on the formation of nanotubular TiO2 structures in a HF-based ethylene-glycol solution to apply them as a photoanode for a dye-sensitized solar cell. The e ect of a nanotubular TiO2 structure on the performance of DSSC was analyzed using electrochemical impedance spectroscopy.

E-mail: ystak@inha.ac.kr; Fax: +82-32-866-0587

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Journal of the Korean Physical Society, Vol. 54, No. 3, March 2009

Fig. 1. Variation of the tube length and the solution conductivity with the iterative number of anodizations [anodization temperature: 20  C].
II. EXPERIMENTS AND DISCUSSION

Fig. 2. Current transients measured during anodization at di erent temperatures [conductivity of basic anodization solution: 80 S/cm].

Ti foils (0.127 mm, 99.7 % purity, Aldrich) were cleaned by sonicating in a mixed solution of isopropanol, methanol and acetone. The anodizing solution was prepared with a 0.2-M HF ethylene-glycol solution. The conductivity of the anodization solution was measured with a conductivity meter (Kyoto electronic CO., LTD, CM-115). An anodizing potential of 120 V was applied for 2 h (Agilent, 6035A) and the accompanying current transient was monitored with a digital multimeter (Keithley, model 2000). The TiO2 nanotubular structure is inconsistent with increasing number of successive iterations of anodization in the same solution. The variation in the solution conductivity was thought to in uence the structure of the nanotube. In order to investigate the e ect of the solution's conductivity on the TiO2 morphology, we successively iterated anodization in the same solution at 20  C and we measured the solution's conductivity. Two di erent solutions, 40 S/cm and 80 S/cm at 20  C, were selected as anodizing solutions. The effect of anodizing temperature (0  C, 10  C, 20  C and 30  C) on the tube morphology was investigated in the two solutions. The temperature was controlled by using a thermostat (Lab. Companion, RW1040G). Anodized Ti foils were annealed at 450  C for 2 h in air. The morphology of the TiO2 nanotubes was analyzed with a eld-emission scanning electron microscope (Hitachi, FE-SEM S-4300). The annealed TiO2 nanotubes were soaked in 300-M cis-bis (isothiocyanato)bis (2, 2'-bipyridyl-4, 4'-dicarboxylato)ruthenium(II) bis-tetrabutylammonium (N719) dye (Solaronix) in ethanol for a day. The photoelectrochemical behavior of the specimen was measured in a methoxyacetonitrile solution containing 0.6-M 1-hexyl-2, 3-dimethylimidazolium iodide, 0.05-M I2 , 0.1-M LiI and 0.5-M 4-

tert-butylpyridine. The electrode area was 1 cm 1 cm and Pt sputtered onto ITO glass was used as a counter electrode. The photocurrent (J)-photovoltaic (V) performance of a TiO2 nanotube as an anode for DSSC was measured with a solar simulator that consisted of a light source (SAN-EL electronics Co., XES 301S) and a source meter (Keithly, model 2400). The light was illuminated from the backside. The electrochemical behaviors of the DSSC were analyzed with electrochemical impedance spectroscopy (Zahaner, IM-6). Figure 1 shows that the conductivity of the electrolyte increases almost linearly with increasing number of anodizations. It also indicates that a higher conductivity results in an increased TiO2 nanotube length under the same anodizing conditions. An electrolyte with a higher conductivity reduces the solution Ohmic drop, iRcell , during anodization and induces a higher overpotential,  , for the TiO2 formation at potentiostatic anodization because  = 120V Eeq jiRcell j when the applied potential is 120 V in an electrolytes cell. Figure 2 shows the variation in the measured current transients with temperature during potentiostatic anodization at 120 V. The solution's conductivity was 80 S/cm at 20  C. As the temperature was increased, the peak current density increased, but the time to reach a steady-state current value decreased. The initial current rise is mainly due to the anodic TiO2 lm formation, which retards the subsequent lm growth by its high electrical-resistance, so a decrease in the current ensues. Simultaneously, TiO2 starts to dissolve by the reaction in Eq. (2). When the current reaches a steady-state value, nanotubular TiO2 is formed and starts to grow. At a 30  C anodization, fast growth and dissolution of TiO2 lm induces a high peak current density, the shortest transition time and the highest steady-state current density. Figure 3 shows the e ect of the solution's conductivity on the current transient during anodization. The solu-

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Fig. 3. E ect of the solution conductivity on the incipient current transients during anodization [anodization temperature: 20  C].

Fig. 5. E ect of the anodization temperature on the tube length at di erent solution conductivities.

Fig. 4. Cross-sectional images of anodized TiO2 nanotubes prepared at di erent solution conductivities: (a) 40 S/cm and (b) 80 S/cm.

Fig. 6. Top surface images of anodized TiO2 nanotubes at di erent solution conductivities : (a) 40 S/cm and (b) 80 S/cm.

tion was prepared at 20  C. Lower conductivity increases the Ohmic drop in the reaction in Eq. (2) and causes a decrease in the overpotential for TiO2 formation, which results in a slow growth of TiO2 nanotube. It also decreases the dissolution of the anodized lm, so the transition time to reach a steady-state current increases. Figure 4 shows cross-sectional images of the anodized lm and indicates average lm grow rates of 0.127 m/min at 40 S/cm and 0.229 m min at 80 S/cm. The e ect of the solution's conductivity on the tube growth becomes

more evident at a higher anodization temperature, as shown in Figure 5. Figure 6 shows a top view of a TiO2 nanotubular lm. A ber-like structure was found locally at a low solution conductivity, but a tubular TiO2 structure is observed at a high solution conductivity. As the anodization temperature was increased, the tube's diameter increased, but the tube's wall thickness decreased, as indicated in Table 1. The TiO2 nanotubular structure was partially cleaved into nanowires by a thinning of the wall at an

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Journal of the Korean Physical Society, Vol. 54, No. 3, March 2009

Table 1. TiO2 nanotube diameter and wall thickness at di erent anodizing temperatures (Electrolyte conductivity = 80 S/cm at 20  C). Anodizing temperature 0 C 71.4 36.2 10  C 20  C 30  C 140.4 195.3 265.9 32.9 19.8 16.0

Tube diameter (nm) Tube wall thickness (nm)

Fig. 9. Impedance spectroscopy of DSSC using anodized TiO2 nanotubes prepared at di erent anodizing solution conductivities. The TiO2 tubes were prepared at 10  C and the frequency was varied from 50 mHz to 100 kHz at open circuit voltage.

Fig. 7. J-V curve for a TiO2 photoanode in DSSC [anodization temperature = 10  C; conductivity = 80 S/cm].

with a ll factor of 0.5; the highest cell eciency was 2.64 %. Figure 8 indicates that TiO2 prepared at a high solution conductivity has a higher cell eciency. Since the cell eciency depends on the chemisorbed area between the dye and the TiO2 anode and on the recombination of injected electrons, a longer tube and a well-established nanotubular TiO2 structure may have a higher eciency. Both ber-like structures formed at low solution conductivity and nanowire structures formed at higher anodizing temperature may favor the recombination of injected electrons and drop the cell's eciency. Figure 9 shows the electrochemical impedance spectroscopy (EIS) data obtained at the open circuit voltage. EIS shows three semicircles and a semicircle at low frequency (Z2 ) is attributed to the charge transfer resistance at the anode, the TiO2 /dye/electrolyte interface [19]. This indicates that a TiO2 photoanode prepared in a solution of 80 s/cm has a smaller charge-transfer resistance. Since the longer TiO2 tube has a higher area of contact with the dye solution, it reduces the chargetransfer resistance and, consequently, increases the cell's eciency.

III. CONCLUSIONS

Fig. 8. E ect of the anodization temperature on the eciency of DSSC with a TiO2 photoanode.

anodization temperature of 30  C. An electrochemically-prepared TiO2 nanotubular lm was used as a photoanode for a dye-sensitized solar cell. Figure 7 shows the photocurrent versus cell potential, which exhibits a Jsc of 7.89 mA/cm2 and a Voc of 0.67 V

The e ects of the solution's conductivity and anodizing temperature on the formation of TiO2 nanotube arrays by potentiostatic anodization were investigated. As the number of anodizations was increased, the solution's conductivity increased linearly, as did the tube's length. The surface morphology indicated that the tubular structure was well fabricated at a high solution conductivity, 80 S/cm, but that a ber-like structure was observed at

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a low solution conductivity, 40 S/cm. As the anodization temperature was increased, fast growth and dissolution of the TiO2 lm took place, which drew a higher peak current density, the shortest transition time and the highest steady-state current density and which results in an increase in the nanotube's length. A nanotubular TiO2 photoanode prepared at a high solution conductivity had a higher eciency for a dye-sensitized solar cell because a longer tube increases the chemisorbed area between the dye and the TiO2 anode and because a wellde ned discrete tubular structure reduces the chargetransfer resistance.

ACKNOWLEDGMENTS

This work was supported by Inha University Research Grant.

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