Modulating the Charge-Transfer Enhancement in GERS using an Electrical Field under Vacuum and an n/p-Doping Atmosphere

The modulation of charger-transfer (CT) enhancement in graphene-enhanced Raman scattering (GERS) by an electric field under different atmospheres is reported. The GERS spectra of cobalt phthalocyanine (CoPc) molecules were collected by in situ Raman measurements under ambient air, vacuum, NH3 atmosphere, and O-2 atmosphere, in which the Fermi level of graphene was modulated by an electrical field effect (EFE). The Raman scattering intensities of adsorbed molecules can be tuned to be stronger or weaker as the graphene Fermi level down-shifts or up-shifts under electrical field modulation. However, the Raman intensity modulation in GERS is seriously influenced by the hysteresis effect in graphene EFE, which makes the modulation ability small and shows strong gate voltage sweep rate dependence in ambient air. Fortunately, the hysteresis effect in graphene EFE can be decreased by performing the measurement under vacuum conditions, and thus the Raman modulation ability in GERS can be increased. Furthermore, compared with the vacuum condition, the Raman modulation ability shows an increase under an NH3 atmosphere, while it shows a decrease under an O-2 atmosphere, which is due to the different Fermi level modulation region in different atmospheres. More interestingly, this Raman intensity modulation in GERS shows a hysteresis-like behavior that is the same as the graphene Fermi level modulation under the EFE in a different atmosphere. All these observations suggest that the Raman enhancement in GERS occurs through a charge-transfer (CT) enhancement mechanism and the CT process can be modulated by the graphene EFE. This technique will benefit the study of the basic properties of both graphene and chemical enhancement mechanism in surface-enhanced Raman spectroscopy (SERS).