Electronic Properties of Cycloaddition-Functionalized Graphene

We have studied the electronic characteristics of covalently functionalized graphene by nitrene chemistry using first-principles density functional calculations. The perfluorophenylazide functionalization leads to a band-gap opening in graphene and transition from a semimetallic to a semiconducting state. The [2 + 1] cycloaddition-induced gap is shown to be attributed to the modification of the π conjugation that depends on the concentration of aziridine adducts. The implications of tailoring the band structure of functionalized graphene for future graphene-based device applications are discussed.