Electronic Structure and Stacking Arrangement of Tungsten Disulfide at the Gold Contact

There is an intensive effort to control the nature of attractive interactions between ultrathin semiconductors and metals and to understand its impact on the electronic properties at the junction. Here, we present a photoelectron spectroscopy study on the interface between WS₂ films and gold, with a focus on the occupied electronic states near the Brillouin zone center (i.e., the Γ point). To delineate the spectra of WS₂ supported on crystalline Au from the suspended WS₂, we employ a microscopy approach and a tailored sample structure, in which the WS₂/Au junction forms a semi-epitaxial relationship and is adjacent to suspended WS₂ regions. The photoelectron spectra, as a function of WS₂ thickness, display the expected splitting of the highest occupied states at the Γ point. In multilayer WS₂, we discovered variations in the electronic states that spatially align with the crystalline grains of underlying Au. Corroborated by density functional theory calculations, we attribute the electronic structure variations to stacking variations within the WS₂ films. We propose that strong interactions exerted by Au grains cause slippage of the interfacing WS₂ layer with respect to the rest of the WS₂ film. Our findings illustrate that the electronic properties of transition metal dichalcogenides, and more generally 2D layered materials, are physically altered by the interactions with the interfacing materials, in addition to the electron screening and defects that have been widely considered.