Full orientation control of epitaxial MoS2 on hBN assisted by substrate defects

Inversion asymmetry in two-dimensional materials grants them fascinating properties such as spin-coupled valley degrees of freedom and piezoelectricity, but at the cost of inversion domain boundaries, if their epitaxy with a polar substrate cannot adequately distinguish the near-degenerate 0{\deg} and 180{\deg} orientations. Here we report the lifting of this near-degeneracy in the growth of monolayer MoS2 on hexagonal boron nitride, with ~90% consistency in the orientation of as-grown triangular MoS2 flakes. These flakes have the potential to merge into a single-crystal monolayer film free of inversion domain boundaries. The orientational preference and chemical composition of these fully epitaxial MoS2/hBN heterostructures are verified using atomic resolution aberration-corrected scanning/transmission electron microscopy. First-principles calculations suggest that the strong orientational preference originates from the energetic distinction between the eclipsed and staggered configurations for N and S atoms surrounding a local defect that acts as the nucleation site. This defect-enhanced orientational epitaxy could provide a general mechanism to break the near-degeneracy of 0/180{\deg} orientations of polar 2D materials on polar substrates, overcoming this long-standing hurdle towards scalable synthesis of single-crystal 2D semiconductors.