Influence of tungsten doping on nonradiative electron–hole recombination in monolayer MoSe₂ with Se vacancies

Two-dimensional transition metal dichalcogenides (TMDs) are receiving significant attention due to their excellent electronic and optoelectronic properties. The material quality is greatly affected by defects that are inevitably generated during material synthesis. Focusing on chalcogenide vacancies, which constitute the most common defect, we use the state-of-the-art simulation methodology developed in our group to demonstrate that W doping of MoSe₂ with Se vacancies reduces charge carrier losses by two mechanisms. First, W doping makes the formation of double Se vacancies unfavorable, while it is favorable in undoped MoSe₂. Second, if a Se vacancy is present, the charge carrier lifetimes are extended in the W-doped MoSe₂. Combining ab initio real-time time-dependent density functional theory with nonadiabatic molecular dynamics, the simulations show that the nonradiative carrier losses in the presence of Se vacancies proceed by sub-10 ps electron trapping and relaxation down the manifold of trap states, followed by a 100 ps recombination of trapped electrons with free holes. The electron–vibrational energy exchange is driven by both in-plane and out-of-plane vibrational motions of the MoSe₂ layer. The atomistic studies advance our understanding of the influence of defects on charge carrier properties in TMDs and guide improvements of material quality and development of TMD applications.