Graphene is a material of great potential in a broad range of applications, for each of which specific tuning of the material’s properties is required. This can be achieved, for example, by covalent functionalization. We have exploited protocols for surface grafting by diazonium salts, by nucleophilic and electrophilic substitution to perform graphene covalent modification of graphene on substrates. The painstaking analysis problem of monolayered materials was addressed using Raman spectroscopy, SERS, SEIRA, MS, AFM, XPS and SEM/EDX. The covalent grafting was shown to tolerate the transfer process, thus allowing ex post transfer from copper to other substrates. Functional devices often require combination of several materials with specific functions, such as graphene-polymer hybrid heterostructures. We have used the developed methodology of chemical functionalization for preparation of PEDOT:Graphene bilayers by selective in situ polymerization of EDOT on covalently functionalized graphene. The polymerization proceeds exclusively on the grafted graphene, and patterned structures with high spatial resolution down to 3 μm could have been prepared. The composite exhibits enhanced efficiency of electrochemical doping compared to pristine graphene, unsymmetrical transport characteristic with very good hole-transporting properties and efficient electronic communication between the two materials. The covalent functionalization of graphene thus introduces advanced functionality to the material, broadening its scope of applications.Keywords: graphene, covalent functionalization, PEDOT, 2D heterostructures
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