Dual Catalytic and Self‐Assembled Growth of Two‐Dimensional Transition Metal Dichalcogenides Through Simultaneous Predeposition Process

Abstract The recent introduction of alkali metal halide catalysts for chemical vapor deposition (CVD) of transition metal dichalcogenides (TMDs) has enabled remarkable two‐dimensional (2D) growth. However, the process development and growth mechanism require further exploration to enhance the effects of salts and understand the principles. Herein, simultaneous predeposition of a metal source (MoO₃) and salt (NaCl) by thermal evaporation is adopted. As a result, remarkable growth behaviors such as promoted 2D growth, easy patterning, and potential diversity of target materials can be achieved. Step‐by‐step spectroscopy combined with morphological analyses reveals a reaction path for MoS₂ growth in which NaCl reacts separately with S and MoO₃ to form Na₂SO₄ and Na₂Mo₂O₇ intermediates, respectively. These intermediates provide a favorable environment for 2D growth, including an enhanced source supply and liquid medium. Consequently, large grains of monolayer MoS₂ are formed by self‐assembly, indicating the merging of small equilateral triangular grains on the liquid intermediates. This study is expected to serve as an ideal reference for understanding the principles of salt catalysis and evolution of CVD in the preparation of 2D TMDs.