Big Bandgap in Highly Reduced Graphene Oxides

It is generally believed that the bandgap of the graphene oxide is proportional to the concentration of the oxygen atoms and a highly reduced graphene oxide (rGO) without vacancy defects should be gapless. We show here from first principles calculations that the bandgap can be effectively opened even in low oxidation level with the absorption of oxygen atoms either symmetrically or asymmetrically. The properly arranged absorption can induce a bandgap up to 1.19 eV for a C/O ratio of 16/1 in a symmetric system and a bandgap up to 1.58 eV for a C/O ratio of 32/3 in an asymmetric system, at generalized gradient approximation (GGA) level. The hybridization between the in-plane p_<i>xy</i> orbitals of oxygen atoms and the out-of-plane p_<i>z</i> frontier orbital of graphene is responsible for the opening of the bandgap. This finding sheds new light on the bandgap engineering of graphene