Tuning Optical and Photoelectrochemical Properties of TiO₂/WO_x Heterostructures by Reactive Sputtering: Thickness-Dependent Insights

Metal-oxide heterostructures represent an effective strategy to overcome the limitations of pristine TiO₂, including its ultraviolet-only light absorption and rapid electron–hole recombination, which hinder its performance in solar-driven applications. Among various configurations, coupling TiO₂ with tungsten oxide (WO_x) forms a favorable type-II band alignment that enhances charge separation. However, a comprehensive understanding of how WO_x overlayer thickness affects the optical and photoelectrochemical (PEC) behavior of device-grade thin films remains limited. In this study, bilayer TiO₂/WO_x heterostructures were fabricated via reactive DC magnetron sputtering, with controlled variation in WO_x thickness to systematically investigate its influence on the structural, optical, and PEC properties. Adjusting the WO_x deposition time enabled precise tuning of light absorption, interfacial charge transfer, and donor density, resulting in markedly distinct PEC responses. The heterostructure obtained with 30 min of WO_x deposition demonstrated a significant enhancement in photocurrent density under AM 1.5G illumination, along with reduced charge-transfer resistance and improved capacitive behavior, indicating efficient charge separation and enhanced charge storage at the electrode–electrolyte interface. These findings underscore the potential of sputtered TiO₂/WO_x bilayers as advanced photoanodes for solar-driven hydrogen generation and light-assisted energy storage applications.