A detailed understanding of charged defects in two-dimensional semiconductors is needed for the development of ultrathin electronic devices. Here, we study negatively charged acceptor impurities in monolayer ${\mathrm{WS}}_2$ using a combination of scanning tunneling spectroscopy and large-scale atomistic electronic structure calculations. We observe several localized defect states of hydrogenic wave function character in the vicinity of the valence band edge. Some of these defect states are bound, while others are resonant. The resonant states result from the multivalley valence band structure of ${\mathrm{WS}}_2$, whereby localized states originating from the secondary valence band maximum at $\mathrm{\Gamma }$ hybridize with continuum states from the primary valence band maximum at $K/K^{\prime }$. Resonant states have important consequences for electron transport as they can trap mobile carriers for several tens of picoseconds.

• Received 15 August 2019
• Revised 8 December 2019
• Accepted 6 February 2020

DOI:https://doi.org/10.1103/PhysRevB.101.081201