Edge Reconstruction-Dependent Growth Kinetics of MoS₂

Understanding the growth mechanisms of multielement two-dimensional (2D) crystals is challenging because of the unbalanced stoichiometry and possible reconstruction of their edges. Here, we present a systematic theoretical study on the chemical vapor deposition (CVD) growth mechanism of MoS₂. We found that the growth kinetics of MoS₂ highly depends on its edge reconstruction determined by concentrations of Mo and S in the growth environment. Based on the calculated energies of nucleation and propagation of various MoS₂ edges, we predicted the transition of a MoS₂ island growth from a regime of a triangle enclosed by Mo-terminated zigzag edges that are passivated by 50% S (Mo-II edges), to a regime of continuous evolution within a triangle, hexagon, and inverted triangle with 75%-S-terminated edges (S-III edges) and Mo-II edges, and finally to a regime of triangles with Mo-terminated zigzag edges that are passivated by 100% S (Mo-III edges) by tuning the growth condition from Mo-rich to S-rich, which provides a reasonable explanation to many experimental observations. This study provides a general guideline on theoretical studies of 2D crystals' growth mechanisms, deepens our understanding on the growth mechanism of multielement 2D crystals, and is beneficial for the controllable synthesis of various 2D crystals.