Nano-TiO₂/TiN Systems for Electrocatalysis: Mapping the Changes in Energy Band Diagram across the Semiconductor|Current Collector Interface and the Study of Effects of TiO₂ Electrochemical Reduction Using UV Photoelectron Spectroscopy

TiO 2 is the most widely used material in photoelectrocatalytic systems. A key parameter to understand its efficacy in such systems is the band bending in the semiconductor layer. In this regard, knowledge on the band energetics at the semiconductor/current collector interface, especially for a nanosemiconductor electrode, is extremely vital as it will directly impact any charge transfer processes at its interface with the electrolyte. Since direct investigation of interfacial electronic features without compromising its structure is difficult, only seldom are attempts made to study the semiconductor/current collector interface specifically. This work utilizes ultraviolet photoelectron spectroscopy (UPS) to determine the valence band maximum ( E VBM ) and Fermi level ( E F ) at different depths in a nano-TiO 2 /TiN thin-film system reached using an Ar gas-clustered ion beam (GCIB). By combining UPS with GCIB depth profiling, we report an innovative approach for truly mapping the energy band structure across a nanosemiconductor/current collector interface. By coupling it with X-ray photoelectron spectroscopy (XPS), correlations among chemistry, chemical bonding, and electronic properties for the nano-TiO 2 /TiN interface could also be studied. The effects of TiO 2 in situ electrochemical reduction in aqueous electrolytes are also investigated where UPS confirmed a decrease in the semiconductor work function (WF) and an associated increase in n-type Ti 3+ centers of nano-TiO 2 electrodes post use in a 0.2 M potassium chloride solution. We report the use of UPS to precisely determine the energy band diagrams for a nano-TiO 2 /TiN thin-film interface and confirm the increase in TiO 2 n-type dopant concentrations during electrocatalysis, promoting a much more comprehensive and intuitive understanding of the TiO 2 activation mechanism by proton intercalation and therefore further optimizing the design process of efficient photocatalytic materials for solar conversion.