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 TiO2 nanowires can have a dramatic effect on their photoelectrochemical properties. To study the length dependence, rutile TiO2 nanowires (0.28-1.8 mu m) 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 mu m long nanowires under AM 1.56 simulated sunlight illumination. While the incident photon to current conversion efficiency (IPCE) increases linearly with photon absorptance (1-10(-alpha xlength)) with near band gap illumination (lambda = 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 TiO2 shell on nanowire electrodes which enhanced the photocatalytic activity by 1.5 times (1.5 V vs RHE) with 1.8 mu m long nanowires, reaching a current density of 1.1 mA/cm(2) (61% of the maximum photocurrent for rutile TiO2). Additionally, by fixing the epitaxial rutile shell thickness and studying photoelectrochemical (PEC) properties of different nanowire lengths (0.28-1.8 mu m), we found that the enhancement of current increases with length. These results demonstrate that ALD coating improves the charge collection efficiency from TiO2 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.