Growth mechanism and atomic structure of group-IIA compound-promoted CVD-synthesized monolayer transition metal dichalcogenides

Abstract

Developing promoters that can boost the growth quality, efficiency, and robustness of two-dimensional (2D) transition metal dichalcogenides is significant for their industrial applications. Herein a new group (group IIA) of promoters in the periodic table has been disclosed, whose chlorides (especially CaCl₂ and SrCl₂) exhibit a versatile promoting effect on the CVD growth of various TMD monolayers, including hexagonal MoS₂, MoSe₂, Re doped MoS₂, and triclinic ReS₂. The promoting effect of group IIA promoters relies on the appropriate dose and is strongly substrate-dependent. The performances of five typical group IA-IIA metal chlorides are ranked by quantitative investigations, displaying periodic variations closely related to the electronegativities of the metal elements. A brand-new acid–base match model is proposed, attributing the promoting mechanism to an increase of the substrate basicity due to the usage of promoters, thus leading to the sufficient adsorption of the acidic precursor. Aberration-corrected annular dark field scanning transmission electron microscopy (ADF-STEM) was applied, unveiling anomalous grain boundaries (GBs) with a low density of coincident sites in the as-grown ReS₂ and detailed atomic configurations of Re doped MoS₂. This work expands the promoter library and gives an insight into GB engineering for the CVD growth of 2D TMDs.