Sensitive Raman Probe of Electronic Interactions between Monolayer Graphene and Substrate under Electrochemical Potential Control

Abstract

In situ electrochemical Raman spectroscopic measurements of defect-free monolayer graphene on various substrates were performed under electrochemical potential control. The G and 2D Raman band wavenumbers (ωG, ω2D) of graphene were found to depend upon the electrochemical potential, i.e., the charge density of graphene. The values of ωG and ω2D also varied depending on the choice of substrates. On metal substrates where graphene was synthesized by chemical vapor deposition, a strong blue shift of ω2D was induced, which could not account for the strain and charge doping. We attributed the blue shift of ω2D to a change in the electronic properties of graphene induced by distinct electronic interactions with the metal substrates. To explain the unique characteristics in the Raman spectrum of graphene on various substrates, a novel mechanism is proposed considering reduction of the Fermi velocity in graphene owing to dielectric screening from the metal substrates.