A scalable process for fabricating graphene/hexagonal boron nitride (h-BN) heterostructures is disclosed herein. The process includes (BN)XHy-radical interfacing with active sites on silicon nitride coated silicon (Si3N4/Si) surfaces for nucleation and growth of large-area, uniform and ultrathin h-BN directly on Si3N4/Si substrates (B/N atomic ratio=1:1.11±0.09). Further, monolayer graphene van der Waals bonded with the produced h-BN surface benefits from h-BN's reduced roughness (3.4 times) in comparison to Si3N4/Si. Because the reduced surface roughness leads to reduction in surface roughness scattering and charge impurity scattering, therefore an enhanced intrinsic charge carrier mobility (3 folds) for graphene on h-BN/Si3N4/Si is found.