Abstract
Two-dimensional (2D) materials exhibit unique electronic, optical, magnetic, mechanical, and thermal properties due to their special crystal structure and thus have promising potential in many fields, such as in electronics and optoelectronics. To realize their real applications, especially in integrated devices, the growth of large-size single crystal is a prerequisite. Up to now, the most feasible way to achieve 2D single crystal growth is the epitaxy: growth of 2D materials of one or more specific orientations with single-crystal substrate. Only when the 2D domains have the same orientation, they can stitch together seamlessly and single-crystal 2D films can be obtained. In this view, four different epitaxy modes of 2D materials on various substrates are presented, including van der Waals epitaxy, edge epitaxy, step-guided epitaxy, and in-plane epitaxy focusing on the growth of graphene, hexagonal boron nitride (h-BN), and transition metal dichalcogenide (TMDC). The lattice symmetry relation and the interaction between 2D materials and the substrate are the key factors determining the epitaxy behaviors and thus are systematically discussed. Finally, the opportunities and challenges about the epitaxy of 2D single crystals in the future are summarized.