Spectral Tuning of a Nanoparticle-on-Mirror System by Graphene Doping and Gap Control with Nitric Acid

[Image: see text] Nanoparticle-on-mirror systems are a stable, robust, and reproducible method of squeezing light into sub-nanometer volumes. Graphene is a particularly interesting material to use as a spacer in such systems as it is the thinnest possible 2D material and can be doped both chemically and electrically to modulate the plasmonic modes. We investigate a simple nanoparticle-on-mirror system, consisting of a Au nanosphere on top of an Au mirror, separated by a monolayer of graphene. With this system, we demonstrate, with both experiments and numerical simulations, how the doping of the graphene and the control of the gap size can be controlled to tune the plasmonic response of the coupled nanosphere using nitric acid. The coupling of the Au nanosphere and Au thin film reveals multipolar modes which can be tuned by adjusting the gap size or doping an intermediate graphene monolayer. At high doping levels, the interaction between the charge-transfer plasmon and gap plasmon leads to splitting of the plasmon energies. The study provides evidence for the unification of theories proposed by previous works investigating similar systems.