Computational study of van der Waals interaction at the sub‐nanometer scale and its influence on the molecular behavior under confinement conditions in graphene‐ 2D h‐BN heterostructure

The atomistic features of the van der Waals interaction between graphene and 2D h‐BN layer are investigated with and without doping using density functional theory. It is computationally shown, how different types of 2D materials can form heterojunctions with each other without the need for close lattice matching if the atomic species are neighbors in the periodic table. H 2 , N 2 , and O 2 are introduced as the dopants separately to investigate the van der Waals interaction at the sub‐nanometer scale and its influence on the molecules and interlayer coupling. The geometrical forms and formation energies of differently bonded molecules and atoms immersed in van der Waals forces in the heterostructure are predicted accurately. The spatial dependence of the van der Waals energy between graphene and h‐BN and its effect on the confined molecule/atoms is well brought out in the present investigation. The weak van der Waals forces between graphene and h‐BN do introduce minor changes at the nanoscale but maintain the original band structure which is dominated by graphene. The present graphene and 2D h‐BN van der Waals heterostructure, with enhanced features, offers a unique opportunity to fabricate new materials with different properties. They will become the building blocks in engineering new functional materials.