The ability to precisely tune plasmon resonances is critical for advancing nanophotonic and sensing technologies. In this work, we exploit the photothermal effect to achieve picometer-level tunability of plasmon resonances in nanorod-on-mirror nanocavities, using polyelectrolyte (PE) layers as dielectric spacers. The plasmon-induced thermal response of these soft materials allows real-time adjustment of the nanocavity, unlike stable inorganic spacers like aluminum oxide. Under continuous laser illumination, the PE spacers undergo thickness reduction and phase transitions, leading to significant shifts in plasmon resonances. These shifts are influenced by laser power and initial spacer thickness, which govern near-field enhancement and photothermal effects. It is shown that this precise tuning capability enables the exploration of various photophysical processes, including the excitation of higher-order plasmon modes, optomechanical enhancement of surface-enhanced Raman scattering signals, electron tunneling, molecular diffusion from the nanocavities, and the transition to charge transfer plasmons.
Keywords: gold nanorods; layer-by-layer assembly; photothermal; plasmonic nanocavity; polyelectrolytes; thermoplasmonic.