Photoelectrochemical Properties of TiO₂ Nanowire Arrays: A Study of the Dependence on Length and Atomic Layer Deposition Coating

We report that the length and surface properties of TiO(2) nanowires can have a dramatic effect on their photoelectrochemical properties. To study the length dependence, rutile TiO(2) nanowires (0.28-1.8 μm) were grown on FTO substrates with different reaction times (50-180 min) using a hydrothermal method. Nanowires show an increase in photocurrent with length, and a maximum photocurrent of 0.73 mA/cm(2) was measured (1.5 V vs RHE) for 1.8 μm long nanowires under AM 1.5G simulated sunlight illumination. While the incident photon to current conversion efficiency (IPCE) increases linearly with photon absorptance (1-10(-α×length)) with near band gap illumination (λ = 410 nm), it decreases severely at shorter wavelengths of light for longer nanowires due to poor electron mobility. Atomic layer deposition (ALD) was used to deposit an epitaxial rutile TiO(2) shell on nanowire electrodes which enhanced the photocatalytic activity by 1.5 times (1.5 V vs RHE) with 1.8 μm long nanowires, reaching a current density of 1.1 mA/cm(2) (61% of the maximum photocurrent for rutile TiO(2)). Additionally, by fixing the epitaxial rutile shell thickness and studying photoelectrochemical (PEC) properties of different nanowire lengths (0.28-1.8 μm), we found that the enhancement of current increases with length. These results demonstrate that ALD coating improves the charge collection efficiency from TiO(2) nanowires due to the passivation of surface states and an increase in surface area. Therefore, we propose that epitaxial coating on materials is a viable approach to improving their energy conversion efficiency.