A computational elucidation of the structure-property relationships in graphene-organic 2D crystal heterostructures

Abstract The integration of graphene with porous organic 2D crystals (O2DCs) represents an emerging class of van der Waals heterostructures that can possess controllable superlattice effects without complex moiré engineering. In this work, we investigate the structure-property relationships in graphene-O2DC (G-O2DC) heterostructures and the role of substrate interactions through computational studies. We demonstrate how O2DCs impose well-defined corrugation on graphene. The amplitude and superlattice of the graphene layer are directly governed by O2DC pore dimensions and substrate, with larger pores and substrate interactions significantly enhancing the corrugation effect. Despite significant structural modulation, the Dirac cone and linear band dispersion of graphene stay only slightly perturbed across all investigated configurations, demonstrating a decoupling between structural corrugation and electronic properties. These insights establish G-O2DC heterostructures as a viable platform for superlattice engineering in graphene, providing a robust foundation for their rational design and optimization and paving the way for applications in diverse fields such as electronics, catalysis, and energy storage.