Defect dependent electronic properties of two-dimensional transition metal dichalcogenides (2H, 1T, and 1T' phases)

Transition metal dichalcogenides (TMDs) exhibit a wide range of electronic properties due to their structural diversity. Understanding their defect-dependent properties might enable the design of efficient, bright, and long-lifetime quantum emitters. Here, we use density functional theory (DFT) calculations to investigate the 2H, 1T, and 1T' phases of MoS₂, WS₂, MoSe₂, WSe₂ and the effect of defect densities on the electronic band structures, focusing on the influence of chalcogen vacancies. The 2H phase, which is thermodynamically stable, is a direct band gap semiconductor, while the 1T phase, despite its higher formation energy, exhibits metallic behavior. 1T phases with spin-orbit coupling show significant band inversions of 0.61, 0.77, 0.24 and 0.78 eV for MoS₂, MoSe₂, WS₂ and WSe₂, respectively. We discovered that for all four MX₂ systems, the energy difference between 2H, 1T and 1T phases decreases with increasing concentration of vacancies (from 3.13% to 21.88%). Our findings show that the 2H phase also has minimum energy values depending on vacancies. TMDs containing W were found to have a wider bandgap compared to those containing Mo. The band gap of 2H WS₂ decreased from 1.81 eV (1.54 eV with SOC included) under GGA calculations to a range of 1.37 eV to 0.79 eV, while the band gap of 2H MoSe₂ reduced from 1.43 eV (1.31 eV with SOC) under GGA to a range of 0.98 eV to 0.06 eV, depending on the concentration. Our findings provide guidelines for experimental screening of 2D TMD defects, paving the way for the development of next-generation spintronic, electronic, and optoelectronic devices.