In Situ Raman Investigation of TiO₂ Nanotube Array-Based Ultraviolet Photodetectors: Effects of Nanotube Length

TiO₂ nanotube arrays (TNAs) with tube lengths of 4, 6, and 7 μm were prepared via two-step anodization. Thereafter, ultraviolet (UV) photodetectors (PDs) with Au/TiO₂/Au structures were prepared using these TNAs with different tube lengths. The effects of TNA length and device area on the performance of the device were investigated using in situ Raman spectroscopy. The maximum laser/dark current ratio was achieved by using a TNA with a size of 1 × 1 cm² and a length of 7 μm, under a 532 nm laser. In addition, when the device was irradiated with a higher energy laser (325 nm), the UV Raman spectrum was found to be more sensitive than the visible Raman spectrum. At 325 nm, the laser/dark current ratio was nearly 24 times higher than that under a 532 nm laser. Six phonon modes of anatase TNAs were observed, at 144, 199, 395, 514, and 635 cm^-1, which were assigned to the E_g(1), E_g(2), B_1g(1), A_1g/B_1g(2), and E_g(3) modes, respectively. The strong low-frequency band at 144 cm^-1 was caused by the O-Ti-O bending vibration and is a characteristic band of anatase. The results show that the performance of TNA-based PDs is length-dependent. Surface-enhanced Raman scattering signals of 4-mercaptobenzoic acid (4-MBA) molecules were also observed on the TNA surface. This result indicates that the length-dependent performance may be derived from an increase in the specific surface area of the TNA. In addition, the strong absorption of UV light by the TNAs caused a blueshift of the E_g(1) mode.