Hydrogen‐induced Sulfur Vacancies on the MoS2 Basal Plane Studied by Ambient Pressure XPS and DFT Calculations

Sulfur vacancy on an MoS2 basal plane plays a crucial role in device performance and catalytic activity; thus, an understanding of the electronic states of sulfur vacancies is still an important issue. We investigate the electronic states on an MoS2 basal plane by ambient‐pressure X‐ray photoelectron spectroscopy (AP‐XPS) and density functional theory calculations while heating the system in hydrogen. The AP‐XPS results show a decrease in the intensity ratio of S 2p to Mo 3d, indicating that sulfur vacancies are formed. Furthermore, low‐energy components are observed in Mo 3d and S 2p spectra. To understand the changes in the electronic states induced by sulfur vacancy formation at the atomic scale, we calculate the core‐level binding energies for the model vacancy surfaces. The calculated shifts for Mo 3d and S 2p with the formation of sulfur vacancy are consistent with the experimentally observed binding energy shifts. Mulliken charge analysis indicates that this is caused by an increase in the electronic density associated with the Mo and S atoms around the sulfur vacancy as compared to the pristine surface. The present investigation provides a guideline for sulfur vacancy engineering. Electronic states on the MoS2 basal plane due to the formation of sulfur vacancies while annealing in hydrogen are revealed using ambient pressure XPS and DFT calculations. The XPS spectra shows the development of new components in Mo 3d due to the formation of sulfur vacancies with increasing temperature. The DFT calculations with appropriate vacancy models reproduce the core‐level shifts.