Selective Engineering of Chalcogen Defects in MoS₂ by Low-Energy Helium Plasma

Structural defects in two-dimensional transition-metal dichalcogenides can significantly modify the material properties. Previous studies have shown that chalcogen defects can be created by physical sputtering, but the energetic ions can potentially displace transition-metal atoms at the same time, leading to ambiguous results and in some cases, degradation of material quality. In this work, selective sputtering of S atoms in monolayer MoS₂ without damaging the Mo sublattice is demonstrated with low-energy helium plasma treatment. Based on X-ray photoelectron spectroscopy analysis, wide-range tuning of S defect concentration is achieved by controlling the ion energy and sputtering time. Furthermore, characterization with scanning transmission electron microscopy confirms that by keeping the ion energy low, the Mo sublattice remains intact. The properties of MoS₂ at different defect concentrations are also characterized. In situ device measurement shows that the flake can be tuned from a semiconducting to metallic-like behavior by introducing S defects due to the creation of mid-gap states. When the defective MoS₂ is exposed to air, the S defects are soon passivated, with oxygen atoms filling the defect sites.