Band Edge Tailoring in Few-Layer Two-Dimensional Molybdenum Sulfide/Selenide Alloys

Chemical alloying is a powerful approach to tune the electronic structure of semiconductors and has led to the synthesis of ternary and quaternary two-dimensional (2D) dichalcogenide semiconductor alloys (e.g., MoSSe₂, WSSe₂, etc.). To date, most of the studies have been focused on determining the chemical composition by evaluating the optical properties, primarily via photoluminescence and reflection spectroscopy of these materials in the 2D monolayer limit. However, a comprehensive study of alloying in multilayer films with direct measurement of electronic structure, combined with first-principles theory, is required for a complete understanding of this promising class of semiconductors. We have combined first-principles density functional theory calculations with experimental characterization of MoS_(2(1-x))Se_(2x) (where x ranges from 0 to 1) alloys using X-ray photoelectron spectroscopy to evaluate the valence and conduction band edge positions in each alloy. Moreover, our observations reveal that the valence band edge energies for molybdenum sulfide/selenide alloys increase as a function of increasing selenium concentration. These experimental results agree well with the results of density functional theory calculations showing a similar trend in calculated valence band edges. Our studies suggest that alloying is an effective technique for tuning the band edges of transition-metal dichalcogenides, with implications for applications such as solar cells and photoelectrochemical devices.