In situ strain-induced phase transition and defect engineering in CVD-synthesized atomically thin MoS₂

Abstract Alkali metal halides have recently received great attention as additives in the chemical vapor deposition (CVD) process to promote the growth of transition metal dichalcogenides (TMDs). However, the multi-faceted role of these halide salts in modulating the properties and quality of TMD monolayers remains mechanistically unclear. In this study, by introducing excessive gaseous sodium chloride (NaCl) into the CVD system, we demonstrate that preferential NaCl deposition along the monolayer edges causes large in situ strain that can invoke localized domains of high defect density and 2H to 1T phase transition. High-resolution scanning transmission electron microscopy, Raman mapping and molecular dynamics simulations revealed that higher NaCl concentrations can promote the coalescence of independent local strain domains, further increasing the 1T/2H phase ratio and defect density. Furthermore, excessive NaCl was also proven by density functional theory calculations to convert thermodynamic growth to kinetic growth, accounting for the unique cloud-shaped MoS₂ crystals acquired. Compared with post-growth strain processing methods, this one-step approach for phase and defect engineering not only represents a deeper understanding of the role that NaCl plays in the CVD process, but also provides a convenient means to controllably synthesize conductive/defect-rich materials for further electrocatalysis and optoelectronic applications.