Switching plasmonic nanogaps between classical and quantum regimes with supramolecular interactions

In the realm of extreme nanophotonics, nanogap plasmons support reliable field enhancements up to 1000, which provide unique opportunities to access a single molecule for strong coupling and a single atom for quantum catalysis. The quantum plasmonics are intriguing but difficult to modulate largely because of the lack of proper spacers that can reversibly actuate the sub-1-nm gaps. Here, we demonstrate that supramolecular systems made of oligoamide sequences can reversibly switch the gap plasmons of Au nanoparticles on mirror between classical and quantum tunneling regimes via supramolecular interactions. The results reveal detailed plasmon shift near the quantum tunneling limit, which fits well with both classical- and quantum-corrected models. In the quantum tunneling regime, we demonstrate that plasmonic hot electron tunneling can further blue shift the quantum plasmons because of the increased conductance in the nanogaps, making it a promising prototype of optical tunable quantum plasmonic devices.