Atomic-Scale Mechanisms of MoS₂ Oxidation for Kinetic Control of MoS₂/MoO₃ Interfaces

Oxidation of transition metal dichalcogenides (TMDs) occurs readily under a variety of conditions. Therefore, understanding the oxidation processes is necessary for successful TMD handling and device fabrication. Here, we investigate atomic-scale oxidation mechanisms of the most widely studied TMD, MoS₂. We find that thermal oxidation results in α-phase crystalline MoO₃ with sharp interfaces, voids, and crystallographic alignment with the underlying MoS₂. Experiments with remote substrates prove that thermal oxidation proceeds via vapor-phase mass transport and redeposition, a challenge to forming thin, conformal films. Oxygen plasma accelerates the kinetics of oxidation relative to the kinetics of mass transport, forming smooth and conformal oxides. The resulting amorphous MoO₃ can be grown with subnanometer to several-nanometer thickness, and we calibrate the oxidation rate for different instruments and process parameters. Our results provide quantitative guidance for managing both the atomic scale structure and thin-film morphology of oxides in the design and processing of TMD devices.