Improved Stability of Atomic Layer Deposited Amorphous TiO2 Photoelectrode Coatings by Thermally Induced Oxygen Defects

Amorphous titanium dioxide (a-TiO2) combined with an electrocatalyst has shown to be a promising coating for stabilizing traditional semiconductor materials used in artificial photosynthesis for efficient photoelectrochemical solar-to-fuel energy conversion. In this study we report a detailed analysis of two methods of modifying an undoped thin film of atomic layer deposited (ALD) a-TiO2 without an electrocatalyst to affect its performance in water splitting reaction as a protective photo electrode coating. The methods are high-temperature annealing in ultrahigh vacuum and atomic hydrogen exposure. A key feature in both methods is that they preserve the amorphous structure of the film. Special attention is paid to the changes in the molecular and electronic structure of a-TiO2 induced by these treatments. On the basis of the photoelectrochemical results, the a-TiO2 is susceptible to photocorrosion but significant improvement in stability is achieved after heat treatment in vacuum at temperatures above 500 degrees C. On the other hand, the hydrogen treatment does not increase the stability despite the ostensibly similar reduction of a-TiO2. The surface analysis allows us to interpret the improved stability to the thermally induced formation of O- species within a-TiO2 that are essentially electronic defects in the anionic framework.