Band Alignments, Electronic Structure, and Core-Level Spectra of Bulk Molybdenum Dichalcogenides (MoS₂, MoSe₂, and MoTe₂)

Abstract

A comprehensive study of bulk molybdenum dichalcogenides is presented with the use of soft and hard X-ray photoelectron (SXPS and HAXPES) spectroscopy combined with hybrid density functional theory (DFT). The main core levels of MoS₂, MoSe₂, and MoTe₂ are explored. Laboratory-based X-ray photoelectron spectroscopy (XPS) is used to determine the ionization potential (IP) values of the MoX₂ series as 5.86, 5.40, and 5.00 eV for MoSe₂, MoSe₂, and MoTe₂, respectively, enabling the band alignment of the series to be established. Finally, the valence band measurements are compared with the calculated density of states which shows the role of p-d hybridization in these materials. Down the group, an increase in the p-d hybridization from the sulfide to the telluride is observed, explained by the configuration energy of the chalcogen p orbitals becoming closer to that of the valence Mo 4d orbitals. This pushes the valence band maximum closer to the vacuum level, explaining the decreasing IP down the series. High-resolution SXPS and HAXPES core-level spectra address the shortcomings of the XPS analysis in the literature. Furthermore, the experimentally determined band alignment can be used to inform future device work.