Solid–Vapor Reaction Growth of Transition‐Metal Dichalcogenide Monolayers

Abstract Two‐dimensional (2D) layered semiconducting transition‐metal dichalcogenides (TMDCs) are promising candidates for next‐generation ultrathin, flexible, and transparent electronics. Chemical vapor deposition (CVD) is a promising method for their controllable, scalable synthesis but the growth mechanism is poorly understood. Herein, we present systematic studies to understand the CVD growth mechanism of monolayer MoSe2, showing reaction pathways for growth from solid and vapor precursors. Examination of metastable nanoparticles deposited on the substrate during growth shows intermediate growth stages and conversion of non‐stoichiometric nanoparticles into stoichiometric 2D MoSe2 monolayers. The growth steps involve the evaporation and reduction of MoO3 solid precursors to sub‐oxides and stepwise reactions with Se vapor to finally form MoSe2. The experimental results and proposed model were corroborated by ab initio Car–Parrinello molecular dynamics studies.