Investigation of Surface Modification Effects on the Optical and Electrical Hydrogen Sensing Characteristics of WO3 Films

The development of hydrogen energy is advancing rapidly, while the progress of hydrogen sensors has been relatively lagging behind and cannot meet the stringent performance requirements of hydrogen energy applications. WO₃ has attracted significant attention due to its highly complementary optical and electrical responses to hydrogen. In this study, hydrogen-sensitive WO₃ thin films characterized by vertically aligned crystallites were fabricated by modulating the substrate temperature and oxygen pressure during pulsed laser deposition. Building upon this foundation, a comprehensive investigation into surface modification strategies for enhancing sensitivity was undertaken. The surface modifications encompassed eight distinct metals and four different metal oxides. Among the metal-modified samples, palladium (Pd) Pd exhibited a markedly enhanced electrical response, defined as the ratio of the resistance in hydrogen-free air to that in hydrogen, of 1022, corresponding to ~45 times higher than the value of 22.4 achieved for Pt-modified films and 120 times higher than the value of 8.4 for Au-modified films. In addition, Pd/WO₃ films showed a measurable optical transmittance change of 9.7%, while all other metal-modified samples exhibited negligible optical responses (<1%). This enhancement is attributable to the catalytic and electronic sensitisation effects of Pd. Conversely, metals such as platinum (Pt), gold (Au), and silver (Ag) elicited negligible optical responses, suggesting minimal catalytic activity. The electrical response in these cases was primarily governed by electronic sensitization effects related to the work function of the metal, with higher work function values correlating with more pronounced sensitization. Regarding metal oxide modifications, the sensitization effect was more substantial when the disparity in work function between the oxide and WO₃ was greater, and this enhancement was found to be independent of the charge carrier type of the modifying oxide. These results offer significant insights into the design principles underlying high-performance WO₃-based hydrogen sensors and underscore the pivotal influence of surface modification in governing their sensing characteristics.