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Hole- and electron-injection driven phase transitions in transition metal dichalcogenides and beyond: A unified understanding

The phase transitions among polymorphic two-dimensional (2D) transition metal dichalcogenides (TMDs) have attracted increasing attention for their potential in enabling distinct functionalities in the same material for making integrated devices. Electron-injection to TMDs has been proved to be a feasible way to drive structural phase transition from the semiconducting H-phase to the semimetal dT-phase. In this contribution, based on density-functional theory (DFT) calculations, firstly we demonstrate that hole-injection drives the transition of the H-phase more efficiently to the metallic T-phase than to the semimetallic dT-phase for group VI-B TMDs (MoS2, WS2, and MoSe2, etc.). The origin can be attributed to the smaller work function of the T-phase than that of the dT-phase. Our work function analysis can distinguish the T and dT phases quantitatively while it is challenging for the commonly used crystal field splitting analysis. In addition, our analysis provides a unified understanding for both hole- and electron-injection induced phase transitions for 2D materials beyond TMDs, such as the newly synthesized MoSi2N4 family. Moreover, the hole-driven T-phase transition mechanism can explain the recent experiment of WS2 phase transition by hole-doping with yttrium (Y) atoms. Using 1/3 Y-doped WS2 and MoSe2 as examples, we show that the Mo and W valency increases to 5+. These above findings open up an avenue to obtain the metallic T-phase, which expands the possible stable phases of 2D materials.