Tunable doping and band gap of graphene on functionalized hexagonal boron nitride with hydrogen and fluorine

Abstract

First-principles calculations have been used to investigate the structural and electronic properties of graphene supported on functionalized hexagonal boron nitride (h-BN) with hydrogen and fluorine atoms. Our results show that the hydrogenation and fluorination of the h-BN substrate modify the electronic properties of graphene. Interactions of graphene with fully hydrogenated or fully fluorinated h-BN and half-hydrogenated and half-fluorinated h-BN with H at N sites and F at the B sites can lead to n- or p-type doping of graphene. The different doping effect may be attributed to the significant charge transfer from graphene to the substrate. Interestingly, when graphene is supported on the functionalized h-BN with H at B sites and F at N sites (G/HBNF), a finite band gap of 79 meV in graphene is opened due to the equivalence breaking of two sublattices of graphene, and can be effectively modulated by changing the interlayer spacing, increasing the number of functionalized BN layers, and applying an external electric field. More importantly, the modification of the band gap in G/HBNF with a functionalized BN bilayer by the electric field is more pronounced than that of the single-layer h-BN, which is increased to 408 meV with 0.8 V Å⁻¹. Thus, graphene on chemically modified h-BN with a tunable and sizeable band gap may provide a novel way for fabricating high-performance graphene-based nanodevices.