Oxidation Notably Accelerates Nonradiative Electron-Hole Recombination in MoS2 by Different Mechanisms: Time-Domain Ab Initio Analysis

Two-dimensional transition metal dichalcogenides (TMDs) experience degradation in optoelectronic properties under ambient conditions. By performing nonadiabatic (NA) molecular dynamics simulations, we demonstrate that the MoS2 monolayer containing substitutional oxygen and oxygen adatom accelerates nonradiative electron-hole recombination by a factor of about 1.5 compared to perfect film but operates by different mechanisms. The substitutional oxygen creates no midgap states while enhancing NA coupling by increasing the overlap between electron and hole wave functions, accelerating electron-hole recombination. In contrast, electrons significantly populate the deep trap state created by the oxygen adatom because the trap is modestly delocalized and coupled strongly to free charges. The trap mediated instead of the direct pathway dominates the electron-hole recombination. The generated insights uncover the mechanisms for different types of defects on influencing charge dynamics in TMDs and suggest that the oxygen defects should be avoided for the design of high-performance optoelectronic devices.