title: Degree of functionalisation dependence of individual Raman intensities in covalent graphene derivatives.
abstract: Covalent functionalisation of graphene is a continuously progressing field of research. The optical properties of such derivatives attract particular attention. In virtually all optical responses, however, an enhancement in peak intensity with increase of sp3carbon content, and a vanishing of the peak position shift in monolayer compared to few-layer systems, is observed. The understanding of these seemingly connected phenomena is lacking. Here we demonstrate, using Raman spectroscopy and in situ electrostatic doping techniques, that the intensity is directly modulated by an additional contribution from photoluminescent π-conjugated domains surrounded by sp3carbon regions in graphene monolayers. The findings are further underpinned by a model which correlates the individual Raman mode intensities to the degree of functionalisation. We also show that the position shift in the spectra of solvent-based and powdered functionalised graphene derivatives originates predominantly from the presence of edge-to-edge and edge-to-basal plane interactions and is by large functionalisation independent.
authors.affiliation: Department of Chemistry and Pharmacy and Joint Institute of Advanced Materials and Processes (ZMP), Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Henkestrasse 42, 91054 Erlangen, Germany.
authors.forename: Philipp
authors.initials: P
authors.lastname: Vecera
authors.affiliation: Department of Chemistry and Pharmacy and Joint Institute of Advanced Materials and Processes (ZMP), Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Henkestrasse 42, 91054 Erlangen, Germany.
authors.forename: Siegfried
authors.initials: S
authors.lastname: Eigler
authors.affiliation: Chair for Applied Physics, Department of Physics, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Staudtstraße 7, 91058 Erlangen, Germany.
authors.forename: Maria
authors.initials: M
authors.lastname: Koleśnik-Gray
authors.affiliation: Chair for Applied Physics, Department of Physics, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Staudtstraße 7, 91058 Erlangen, Germany.
authors.forename: Vojislav
authors.initials: V
authors.lastname: Krstić
authors.affiliation: Institut für Festkörperphysik, Technische Universität Berlin, Eugene-Wigner-Building EW 5-4, Hardenbergstrasse 36, 10623 Berlin, Germany.
authors.forename: Asmus
authors.initials: A
authors.lastname: Vierck
authors.affiliation: Institut für Festkörperphysik, Technische Universität Berlin, Eugene-Wigner-Building EW 5-4, Hardenbergstrasse 36, 10623 Berlin, Germany.
authors.forename: Janina
authors.initials: J
authors.lastname: Maultzsch
authors.affiliation: Department of Chemistry and Pharmacy and Joint Institute of Advanced Materials and Processes (ZMP), Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Henkestrasse 42, 91054 Erlangen, Germany.
authors.forename: Ricarda A
authors.initials: RA
authors.lastname: Schäfer
authors.affiliation: Department of Chemistry and Pharmacy and Joint Institute of Advanced Materials and Processes (ZMP), Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Henkestrasse 42, 91054 Erlangen, Germany.
authors.forename: Frank
authors.initials: F
authors.lastname: Hauke
authors.affiliation: Department of Chemistry and Pharmacy and Joint Institute of Advanced Materials and Processes (ZMP), Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Henkestrasse 42, 91054 Erlangen, Germany.
authors.forename: Andreas
authors.initials: A
authors.lastname: Hirsch