Functional hybrid multilayered van der Waals heterostructures from graphene and self-assembled supramolecular 2D crystals

Abstract We demonstrate the soft realization of a new generation of functional hybrid van der Waals (vdW) heterostructures alternating two-dimensional (2D) materials and surface-confined supramolecular self-assemblies of porous crystals into three-dimensional (3D) stacks. We show that graphene can be transferred on top of a graphite-confined self-assembled 2D porous network, the cavities of which might be filled with functional guests. Subsequent growth of a new 2D host-guest self-assembled monolayer on top of this intermediate vdW heterostructure further extends it into the third dimension. Thus, this versatile approach, potentially not limited in the number of layers, allows creating on demand sequences by the careful choice of the 2D materials and of the presence or not and choice of guest molecules and permits to envisage innovative structures such as record-density bulk heterojunctions.