Direct In Situ Growth of Centimeter‐Scale Multi‐Heterojunction MoS(2)/WS(2)/WSe(2) 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 (MoS(2)/WS(2)/WSe(2) and MoS(2)/WSe(2)) thin films are successfully fabricated via sequential pulsed laser deposition (PLD), which is an in situ growth process. The fabricated MoS(2)/WS(2)/WSe(2) 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, MoS(2)/WS(2)/WSe(2) 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.