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# Degree of functionalisation dependence of individual Raman intensities in covalent graphene derivatives

Scientific Reports

Nature Publishing Group

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### 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 sp 3 carbon 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 sp 3 carbon 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.

### Most cited references28

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There are few phenomena in condensed matter physics that are defined only by the fundamental constants and do not depend on material parameters. Examples are the resistivity quantum, h/e2 (h is Planck's constant and e the electron charge), that appears in a variety of transport experiments and the magnetic flux quantum, h/e, playing an important role in the physics of superconductivity. By and large, sophisticated facilities and special measurement conditions are required to observe any of these phenomena. We show that the opacity of suspended graphene is defined solely by the fine structure constant, a = e2/hc feminine 1/137 (where c is the speed of light), the parameter that describes coupling between light and relativistic electrons and that is traditionally associated with quantum electrodynamics rather than materials science. Despite being only one atom thick, graphene is found to absorb a significant (pa = 2.3%) fraction of incident white light, a consequence of graphene's unique electronic structure.
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### Raman spectroscopy as a versatile tool for studying the properties of graphene

(2013)
Raman spectroscopy is an integral part of graphene research. It is used to determine the number and orientation of layers, the quality and types of edge, and the effects of perturbations, such as electric and magnetic fields, strain, doping, disorder and functional groups. This, in turn, provides insight into all $$sp^2$$-bonded carbon allotropes, because graphene is their fundamental building block. Here we review the state of the art, future directions and open questions in Raman spectroscopy of graphene. We describe essential physical processes whose importance has only recently been recognized, such as the various types of resonance at play, and the role of quantum interference. We update all basic concepts and notations, and propose a terminology that is able to describe any result in literature. We finally highlight the potential of Raman spectroscopy for layered materials other than graphene.
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### Author and article information

###### Journal
Sci Rep
Sci Rep
Scientific Reports
Nature Publishing Group
2045-2322
27 March 2017
2017
: 7
###### Affiliations
[1 ]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
[2 ]Chair for Applied Physics, Department of Physics, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU) , Staudtstraße 7, 91058 Erlangen, Germany
[3 ]Institut für Festkörperphysik, Technische Universität Berlin, Eugene-Wigner-Building EW 5-4 , Hardenbergstrasse 36, 10623 Berlin, Germany
###### Author notes
[*]

Present Address: Freie Universität Berlin, Institut für Chemie und Biochemie,Takustraße 3, D-14195 Berlin, Germany.

###### Article
srep45165
10.1038/srep45165
5366877