Hydrogen-Assisted Epitaxial Growth of Monolayer Tungsten Disulfide and Seamless Grain Stitching

Recently, research on transition metal dichalcogenides (TMDCs) has been accelerated by the development of large-scale synthesis based on chemical vapor deposition (CVD). However, in most cases, CVD-grown TMDC sheets are composed of randomly oriented grains, and thus contain many distorted grain boundaries (GBs) which deteriorate the physical properties of the TMDC. Here, we demonstrate the epitaxial growth of monolayer tungsten disulfide (WS₂) on sapphire by introducing a high concentration of hydrogen during the CVD process. As opposed to the randomly oriented grains obtained in conventional growth, the presence of H₂ resulted in the formation of triangular WS₂ grains with the well-defined orientation determined by the underlying sapphire substrate. Photoluminescence of the aligned WS₂ grains was significantly suppressed compared to that of the randomly oriented grains, indicating a hydrogen-induced strong coupling between WS₂ and the sapphire surface that has been confirmed by density functional theory calculations. Scanning transmission electron microscope observations revealed that the epitaxially grown WS₂ has less structural defects and impurities. Furthermore, sparsely distributed unique dislocations were observed between merging aligned grains, indicating an effective stitching of the merged grains. This contrasts with the GBs that are observed between randomly oriented grains, which include a series of 8-, 7-, and alternating 7/5-membered rings along the GB. The GB structures were also found to have a strong impact on the chemical stability and carrier transport of merged WS₂ grains. Our work offers a novel method to grow high-quality TMDC sheets with much less structural defects, contributing to the future development of TMDC-based electronic and photonic applications.