Defect evolution behaviors from single sulfur point vacancies to line vacancies in monolayer molybdenum disulfide

Two-dimensional monolayer transition metal dichalcogenides (TMDs) are promising candidates for many novel nanoelectronic and optoelectronic applications due to their exceptional electronic, optical, chemical and mechanical properties. Experimentally, single chalcogen point vacancies caused by electron beam irradiation are found to agglomerate into line vacancy defects in monolayer TMDs. Herein, the corresponding defect evolution behaviors from single sulfur point vacancies to line vacancies in the monolayer molybdenum disulfide (MoS₂) have been systematically studied using molecular dynamics and first principles calculations. The experimental observations of the defect evolution from single sulfur point vacancies to line vacancies are reproduced at the atomic level. The results indicate that the di-vacancy line defect and a point vacancy separated by a sulfur atom in a line evolve into tri-vacancy line defects, and the di-vacancy line defects can rotate 60° clockwise or counterclockwise. Moreover, two adjacent di-vacancy line defects with an angle of 120° can evolve into tri-vacancy line defects. High temperature and large vacancy concentrations promote the defect evolution from point vacancies to line vacancies. Intriguingly, compared with the randomly distributed point vacancy defects, the line vacancy defects formed after the defect evolution significantly decrease the mechanical properties, such as the ultimate strength, ultimate strain and Young's modulus of monolayer MoS₂. In addition, the mechanical properties decrease with increasing vacancy concentration and temperature for the final configurations after defect evolution in monolayer MoS₂ with different vacancy concentrations at different temperatures. The band gaps of monolayer MoS₂ with line vacancy defects are smaller than those with randomly distributed point vacancy defects. Therefore, our study clarifies the defect evolution behaviors from single sulfur point vacancies to line vacancies in monolayer MoS₂ and opens an opportunity for the novel nanoelectronic and optoelectronic applications of monolayer TMDs.