We describe the use of highly ordered transparent TiO(2) nanotube arrays in dye-sensitized solar cells (DSCs). Highly ordered nanotube arrays of 46-nm pore diameter, 17-nm wall thickness, and 360-nm length were grown perpendicular to a fluorine-doped tin oxide-coated glass substrate by anodic oxidation of a titanium thin film. After crystallization by an oxygen anneal, the nanotube arrays are treated with TiCl(4) to enhance the photogenerated current and then integrated into the DSC structure using a commercially available ruthenium-based dye. Although the negative electrode is only 360-nm-thick, under AM 1.5 illumination the generated photocurrent is 7.87 mA/cm(2), with a photocurrent efficiency of 2.9%. Voltage-decay measurements indicate that the highly ordered TiO(2) nanotube arrays, in comparison to nanoparticulate systems, have superior electron lifetimes and provide excellent pathways for electron percolation. Our results indicate that remarkable photoconversion efficiencies may be obtained, possibly to the ideal limit of approximately 31% for a single photosystem scheme, with an increase of the nanotube-array length to several micrometers.

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In this study highly ordered titania nanotube arrays of variable wall thickness are used to photocleave water under ultraviolet irradiation. We demonstrate that the wall thickness and length of the nanotubes can be controlled via anodization bath temperature. We find that the nanotube wall thickness is a key parameter influencing the magnitude of the photoanodic response and the overall efficiency of the water-splitting reaction. For 22 nm inner pore diameter nanotube arrays, those fabricated in a 5 degrees C anodization bath, 224 nm length and 34 nm wall thickness produced a photoanodic response that was thrice that of a nanotube array fabricated in a 50 degrees C anodization bath, 120 nm length and 9 nm wall-thickness. At high anodic polarization, above 1 V, the quantum efficiency under 337 nm illumination was greater than 90%. For the 5 degrees C anodization bath samples (22 nm pore-diameter, 34 nm wall thickness), upon 320-400 nm illumination at an intensity of 100 mW/cm(2), hydrogen gas was generated at the power-time normalized rate of 960 micromol/h W (24 mL/h W) at an overall conversion efficiency of 6.8%. To the best of our knowledge, this hydrogen generation rate is the highest reported for a titania-based photoelectrochemical cell.

The fabrication of highly-ordered TiO2 nanotube arrays up to 134 µm in length by anodization of Ti foil has recently been reported (Paulose et al 2006 J. Phys. Chem. B 110 16179). This work reports an extension of the fabrication technique to achieve TiO2 nanotube arrays up to 220 µm in length, with a length-to-outer diameter aspect ratio of ≈1400, as well as their initial application in dye-sensitized solar cells and hydrogen production by water photoelectrolysis. The highly-ordered TiO2 nanotube arrays are fabricated by potentiostatic anodization of Ti foil in fluoride ion containing baths in combination with non-aqueous organic polar electrolytes including N-methylformamide, dimethyl sulfoxide, formamide, or ethylene glycol. Depending upon the anodization voltage, the inner pore diameters of the resulting nanotube arrays range from 20 to 150 nm. As confirmed by glancing angle x-ray diffraction and HRTEM studies, the as-prepared nanotubes are amorphous but crystallize with annealing at elevated temperatures.