How Substitutional Point Defects in Two-Dimensional WS₂ Induce Charge Localization, Spin–Orbit Splitting, and Strain

Control of impurity concentrations in semiconducting materials is essential to device technology. Because of their intrinsic confinement, the properties of two-dimensional semiconductors such as transition metal dichalcogenides (TMDs) are more sensitive to defects than traditional bulk materials. The technological adoption of TMDs is dependent on the mitigation of deleterious defects and guided incorporation of functional foreign atoms. The first step toward impurity control is the identification of defects and assessment of their electronic properties. Here, we present a comprehensive study of point defects in monolayer tungsten disulfide (WS₂) grown by chemical vapor deposition using scanning tunneling microscopy/spectroscopy, CO-tip noncontact atomic force microscopy, Kelvin probe force spectroscopy, density functional theory, and tight-binding calculations. We observe four different substitutional defects: chromium (Cr_W) and molybdenum (Mo_W) at a tungsten site, oxygen at sulfur sites in both top and bottom layers (O_S top/bottom), and two negatively charged defects (CD type I and CD type II). Their electronic fingerprints unambiguously corroborate the defect assignment and reveal the presence or absence of in-gap defect states. Cr_W forms three deep unoccupied defect states, two of which arise from spin–orbit splitting. The formation of such localized trap states for Cr_W differs from the Mo_W case and can be explained by their different d shell energetics and local strain, which we directly measured. Utilizing a tight-binding model the electronic spectra of the isolectronic substitutions O_S and Cr_W are mimicked in the limit of a zero hopping term and infinite on-site energy at a S and W site, respectively. The abundant CDs are negatively charged, which leads to a significant band bending around the defect and a local increase of the contact potential difference. In addition, CD-rich domains larger than 100 nm are observed, causing a work function increase of 1.1 V. While most defects are electronically isolated, we also observed hybrid states formed between Cr_W dimers. The important role of charge localization, spin–orbit coupling, and strain for the formation of deep defect states observed at substitutional defects in WS₂ as reported here will guide future efforts of targeted defect engineering and doping of TMDs.