Stability of charged sulfur vacancies in 2D and bulk MoS$_2$ from plane-wave density functional theory with electrostatic corrections

Abstract: Two-dimensional (2D) semiconducting transition metal dichalcogenides such as MoS$_2$ have attracted extensive research interests for potential applications in optoelectronics, spintronics, photovoltaics, and catalysis. To harness the potential of these materials for electronic devices requires a better understanding of how defects control the carrier concentration, character, and mobility. Utilizing a correction scheme developed by Freysoldt and Neugebauer to ensure the appropriate electrostatic boundary conditions for charged defects in 2D materials, we perform density functional theory calculations to compute formation energies and charge transition levels associated with sulfur vacancies in monolayer and layered bulk MoS$_2$. We investigate the convergence of these defect properties with respect to vacuum spacing, in-plane supercell dimensions, and different levels of theory. We also analyze the electronic structures of the defects in different charge states to gain insights into the effect of defects on bonding and magnetism. We predict that both vacancy structures undergo a Jahn-Teller distortion, which helps stabilize the sulfur vacancy in the $-1$ charged state.