Most photoanodes commonly applied in solar fuel research (e.g., of Fe2O3, BiVO4, TiO2, or WO3) are only active and stable in alkaline electrolytes. Silicon (Si)-based photocathodes on the other hand are mainly studied under acidic conditions due to their instability in alkaline electrolytes. Here, we show that the in-diffusion of nickel into a 3D Si structure, upon thermal annealing, yields a thin (sub-100 nm), defect-free nickel silicide (NiSi) layer. This has allowed us to design and fabricate a Si microwire photocathode with a NiSi interlayer between the catalyst and the Si microwires. Upon electrodeposition of the catalyst (here, nickel molybdenum) on top of the NiSi layer, an efficient, Si-based photocathode was obtained that is stable in strongly alkaline solutions (1 M KOH). The best-performing, all-earth-abundant microwire array devices exhibited, under AM 1.5G simulated solar illumination, an ideal regenerative cell efficiency of 10.1%.
Vijselaar, W., Tiggelaar, R. M., Gardeniers, H., & Huskens, J. (2018). Efficient and Stable Silicon Microwire Photocathodes with a Nickel Silicide Interlayer for Operation in Strongly Alkaline Solutions. ACS Energy Letters, 3(5), 1086-1092. https://doi.org/10.1021/acsenergylett.8b00267