The Role of Oxygen Atoms on Excitons at the Edges of Monolayer WS₂

We clarify that the chemisorption of oxygen atoms at the edges is a key contributor to the frequently observed edge enhancement and spatial non-uniformities of photoluminescence (PL) in WS₂ monolayers. Here we have investigated with momentum- and real-space nanoimaging of the chemical and electronic density inhomogeneity of WS₂ flakes. Our finding from a large panoply of techniques together with density functional theory calculation confirms that the oxygen chemisorption leads to the electron accumulation at the edges. This facilitates the trion dominance of PL at the edges of WS₂ flakes. Our results highlight and unravel the significance of chemisorbed oxygen at the edges in the PL emission and electronic structure of WS₂, providing a viable path to enhance the performance of transition-metal-dichalcogenide-based devices.