Direct In Situ Growth of Centimeter-Scale Multi-Heterojunction MoS₂/WS₂/WSe₂ Thin-Film Catalyst for Photo-Electrochemical Hydrogen Evolution

To date, the in situ fabrication of the large-scale van der Waals multi-heterojunction transition metal dichalcogenides (multi-TMDs) is significantly challenging using conventional deposition methods. In this study, vertically stacked centimeter-scale multi-TMD (MoS₂/WS₂/WSe₂ and MoS₂/WSe₂) thin films are successfully fabricated via sequential pulsed laser deposition (PLD), which is an in situ growth process. The fabricated MoS₂/WS₂/WSe₂ thin film on p-type silicon (p-Si) substrate is designed to form multistaggered gaps (type-II band structure) with p-Si, and this film exhibits excellent spatial and thickness uniformity, which is verified by Raman spectroscopy. Among various application fields, MoS₂/WS₂/WSe₂ is applied to the thin-film catalyst of a p-Si photocathode, to effectively transfer the photogenerated electrons from p-Si to the electrolyte in the photo-electrochemical (PEC) hydrogen evolution. From a comparison between the PEC performances of the homostructure TMDs (homo-TMDs)/p-Si and multi-TMDs/p-Si, it is demonstrated that the multistaggered gap of multi-TMDs/p-Si improves the PEC performance significantly more than the homo-TMDs/p-Si and bare p-Si by effective charge transfer. The new in situ growth process for the fabrication of multi-TMD thin films offers a novel and innovative method for the application of multi-TMD thin films to various fields.