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Molybdenum disulfide (MoS2) on the c-plane sapphire has been a very popular system to study in the two-dimensional (2D) materials community. Bottom-up synthesis of monolayer (ML) MoS2 with excellent electrical properties has been achieved on sapphire by various methods, making it a very promising candidate to be used in the next generation nano-electronic devices. However, large-area ML MoS2 with comparable quality as the relatively small size exfoliated ML remains quite a challenge. To overcome this bottle neck, a comprehensive understanding of the structure of the as-grown ML material is an essential first step. Here, we report a detailed structural characterization of wafer-scale continuous epitaxial ML MoS2 grown by metalorganic chemical vapor deposition on sapphire using an azimuthal reflection high-energy electron diffraction (ARHEED) technique. With ARHEED we can map not only 2D but also 3D reciprocal space structure of the ML statistically. From the oscillation in the ARHEED intensity profile along the vertical direction of the ML, we derived a real space distance of ~3 Å at the interface of ML and sapphire. Quantitative diffraction spot broadening analyses of the 3D reciprocal space map reveals low density defects and a small angular misalignment of orientation domains in ML MoS2. Based on atomic force microscopy height distribution analysis, cross-section scanning transmission electron microscopy, and density functional theory calculations, we suggest that there exists a passivation layer between MoS2 ML and sapphire substrate. This ARHEED methodology also has been applied to ML WS2 and is expected to be applicable to other ML transition metal dichalcogenides on arbitrary crystalline or non-crystalline substrates.

Defects have a profound impact on the electronic and physical properties of crystals. For two-dimensional (2D) materials, many intrinsic point defects have been reported, but much remains to be understood about their origin. Using scanning transmission electron microscopy imaging, this study discovers various linear arrays of W-vacancy defects that are explained in the context of the crystal growth of coalesced, monolayer WS2. Atomistic-scale simulations show that vacancy arrays can result from steric hindrance of bulky gas-phase precursors at narrowly separated growth edges, and that increasing the edge separation leads to various intact and defective growth modes, which are driven by competition between the catalytic effects of the sapphire substrate and neighboring growth edge. Therefore, we hypothesize that the arrays result from combined growth modes, which directly result from film coalescence. The connections drawn here will guide future synthetic and processing strategies to harness the engineering potential of defects in 2D monolayers.