Defect-Mediated Alloying of Monolayer Transition-Metal Dichalcogenides

Alloying plays a central role in tailoring the material properties of 2D transition-metal dichalcogenides (TMDs). However, despite widespread reports, the details of the alloying mechanism in 2D TMDs have remained largely unknown and are yet to be further explored. Here, we combine a set of systematic experiments with ab initio density functional theory (DFT) calculations to unravel a defect-mediated mechanism for the alloying of monolayer TMD crystals. In our alloying approach, a monolayer MoSe₂ film serves as a host crystal in which exchanging selenium (Se) atoms with sulfur (S) atoms yields a MoS_2xSe_2(1–x) alloy. Our study reveals that the driving force required for the alloying of CVD-grown films with abundant vacancy-type defects is significantly lower than that required for the alloying of exfoliated films with fewer vacancies. Indeed, we show that pre-existing Se vacancies in the host MoSe₂ lattice mediate the replacement of chalcogen atoms and facilitate the synthesis of MoS_2xSe_2(1–x) alloys. Our DFT calculations suggest that S atoms can bind to Se vacancies and then diffuse throughout the host MoSe₂ lattice via exchanging the position with Se vacancies, further supporting our proposed defect-mediated alloying mechanism. Beside native vacancy defects, we show that the existence of large-scale defects in CVD-grown MoSe₂ films causes the fracture of alloys under the alloying-induced strain, while no such effect is observed in exfoliated MoSe₂ films. Our study provides a deep insight into the details of the alloying mechanism and enables the synthesis of 2D alloys with tunable properties.