Space-confined growth of monolayer ReSe₂ under a graphene layer on Au foils

Vertical heterostructures based on two-dimensional (2D) materials have attracted widespread interest for their numerous applications in electronic and optoelectronic devices. Herein, we report the direct construction of an abnormal graphene/ReSe₂ stack on Au foils by a two-step chemical vapor deposition (CVD) strategy. During the second growth stage, monolayer ReSe₂ is found to preferentially evolve at the interface between the first-grown graphene layer and the Au substrate. The unusual stacking behavior is unraveled by in-situ pcutting openq the upper graphene from the defects to expose the lower ReSe₂ using scanning tunneling microscopy (STM). From combination of these results with density functional theory calculations, the domain boundaries and edge sites of graphene are proposed to be adsorption sites for Re and Se precursors, further facilitating the growth of ReSe₂ at the van der Waals gap of graphene/Au. This work hereby offers an intriguing strategy for obtaining vertical 2D heterostructures featured with an ultra-clean interface and a designed stacking geometry.