Adsorption Behavior of the Hydroxyl Radical and Its Effects on Monolayer MoS2.

Abstract

Based on first-principles density functional theory calculations, we investigated a modified routine using hydroxyl adsorption that recently demonstrated the controlled growth of MoS2 monolayers. The new growth approach impedes the deposition of a second MoS2 layer; however, the hydroxyl adsorption and its effects have been mostly unexplored. Through this study, we first explored the adsorption behaviors of the hydroxyl radical (OH) on monolayer MoS2 and briefly discussed its effects on the stability and electronic structure. Monolayer MoS2 repels charged OH–, whereas the adsorption of the neutral OH radical is energetically favorable; the corresponding adsorption energies are 0.09 eV and −1.35 eV, respectively. The diffusion barrier of the OH radical on MoS2 is 0.52 eV, indicating that the molecule can quickly diffuse. Next, the study demonstrated that for multiple OH adsorptions, a concerted reaction including OH dissociation and H2O formation is more energetically favorable than the adsorption of two OH molecules by 2.50 eV, which in turn results in a mixed adsorption configuration of O and OH. In addition, we revealed that the OH adsorption creates a mid-gap state and facilitates the reconstruction of the MoS2 edge.