Hydrogen Sensing Mechanism of WS₂ Gas Sensors Analyzed with DFT and NAP-XPS

Nanostructured tungsten disulfide (WS₂) is one of the most promising candidates for being used as active nanomaterial in chemiresistive gas sensors, as it responds to hydrogen gas at room temperature. This study analyzes the hydrogen sensing mechanism of a nanostructured WS₂ layer using near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) and density functional theory (DFT). The W 4f and S 2p NAP-XPS spectra suggest that hydrogen makes physisorption on the WS₂ active surface at room temperature and chemisorption on tungsten atoms at temperatures above 150 °C. DFT calculations show that a hydrogen molecule physically adsorbs on the defect-free WS₂ monolayer, while it splits and makes chemical bonds with the nearest tungsten atoms on the sulfur point defect. The hydrogen adsorption on the sulfur defect causes a large charge transfer from the WS₂ monolayer to the adsorbed hydrogen. In addition, it decreases the intensity of the in-gap state, which is generated by the sulfur point defect. Furthermore, the calculations explain the increase in the resistance of the gas sensor when hydrogen interacts with the WS₂ active layer.