Two-Dimensional Band Structure in Honeycomb Metal–Organic Frameworks

Two-dimensional (2D) metal-organic frameworks (MOFs) have been recently proposed as a flexible material platform for realizing exotic quantum phases including topological and anomalous quantum Hall insulators. Experimentally, direct synthesis of 2D MOFs has been essentially confined to metal substrates, where the strong interaction with the substrate masks the intrinsic electronic properties of the MOF. In addition to electronic decoupling from the underlying metal support, synthesis on weakly interacting substrates (e.g., graphene) would enable direct realization of heterostructures of 2D MOFs with inorganic 2D materials. Here, we demonstrate synthesis of 2D honeycomb MOFs on epitaxial graphene substrate. Using low-temperature scanning tunneling microscopy (STM) and atomic force microscopy (AFM) complemented by density-functional theory (DFT) calculations, we show the formation of a 2D band structure in the MOF decoupled from the substrate. These results open the experimental path toward MOF-based designer electronic materials with complex, engineered electronic structures.