Investigation of epitaxial graphene via Raman spectroscopy: Origins of phonon mode asymmetries and line width deviations

In this work a comprehensive study is presented for the analysis of epitaxial graphene layers using Raman spectroscopy. A wide range of graphene types is covered, from defective/polycrystalline single layer graphene to multilayer graphene with low defect density. On this basis the influence of strain type, Fermi level and number of layers on the Raman spectrum of graphene is investigated. A detailed view on the 2 D / G dispersion and the respective slopes of uniaxially and biaxially strained graphene is given and its implications on the asymmetry of the G peak analyzed. A linear dependency of the phonon mode asymmetry on uniaxial strain is presented in addition to the known Fermi level dependence. Additional impacts on the asymmetry are found to be arising from the defect density and transfer doping of adsorbates. The discovered transfer doping mechanism is contrary to pure phonon excitation through excitons and exhibits increasing asymmetry with increasing Fermi level. A new characteristic correlation between the 2 D mode line width and the inverse I(D)/I(G) ratio is introduced that allows the determination of the strain type and layer number and explains the difference between Raman line widths of monolayer graphene on different substrates.