  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
towards 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 (WS$_2$) grown by chemical vapor
deposition (CVD) 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$_{\text{W}}$) and molybdenum
(Mo$_{\text{W}}$) at a tungsten site, oxygen at sulfur sites in both bottom and
top layers (O$_{\text{S}}$ top/bottom), as well as two negatively charged
defects (CDs). Their electronic fingerprints unambiguously corroborate the
defect assignment and reveal the presence or absence of in-gap defect states.
The important role of charge localization, spin-orbit coupling, and strain for
the formation of deep defect states observed at substitutional defects in
WS$_2$ as reported here will guide future efforts of targeted defect
engineering and doping of TMDs.
