Reversible charge-transfer doping in graphene due to reaction with polymer residues

Chemical doping in graphene due to polymer molecules adsorption has attracted much recent interest because of the modification of electrical, magnetic, and optical properties of graphene. We show a reversible charge-transfer doping effect in graphene due to the reaction with poly(methyl methacrylate) (PMMA) residues. By helium ion irradiation and vacuum annealing without introducing an external dopant, reversible shifts in Raman G and 2D bands are observed as well as the change in the relative 2D band intensity to the G band. Chemical bonds between functional groups from PMMA residues and graphene could be formed due to He⁺ ion irradiation, and the desorption of functional groups from graphene is dominant during the vacuum annealing process. Meanwhile, PMMA residue on the graphene surface is mostly removed and the surface morphology becomes smooth after irradiation and annealing. Both electrical conductance and Raman band shifts show nonmonotonic dependence on the dose density, which remains after annealing, indicating that the doping also involves an irreversible effect. Our study helps better the understanding of the doping effects in graphene due to polymer adsorption, which is efficient to tune the properties of graphene.