Energy gap modulation of graphene nanoribbons by F termination

Under the generalized gradient approximation (GGA), the electronic properties are studied for the F-terminated graphene nanoribbons (GNRs) with either zigzag edge (ZGNRs) or armchair edge (AGNRs) by using the first-principles projector augmented wave potential within the density function theory (DFT) framework. The results show that an edge state appears at the Fermi level EF in the broader F-terminated ZGNRs, but does not appear in all the F-terminated AGNRs due to their dimerized C–C bonds at edge. The density of states (DOS) and projected DOS (PDOS) analyses show that the F-terminated ZGNRs are metallic and have a sharp peak at the Fermi level when the width is large enough. In contrast, the AGNRs are always semiconductors independent of their width. The charge density contours analyses shows that the C–F bond is an ionic bond due to a much stronger electronegativity of the F atom than that of the C atom. However, all kinds of the C–C bonds display a typical nonpolar covalent bonding feature.