“…By coupling optical fields with collective electronic excitations (i.e., surface plasmons), plasmonic nanoparticles have the ability to confine light down to a deep-subwavelength scale (e.g., 10 nm) and produce enhanced local electromagnetic fields. , However, it is challenging to achieve more tightly confined optical fields (e.g., sub-5 nm) . Recently, nanoparticle-on-mirror (NPoM) plasmonic nanocavities, , formed by placing a metal nanoparticle on a metal film separated with a nanometer-thick dielectric layer, have attracted intensive research interest due to their capability of extreme optical confinement and ease of fabrication. − They have given rise to a series of breakthroughs in state-of-the-art nanophotonic research and applications, − such as spontaneous emission enhancement, ,, strong coupling, ,, optical sensing, ,,, and quantum plasmonics. , Usually, the implementation of NPoM nanocavities uses deposited metal films as the mirror, − ,− ,− which have a polycrystalline structure and a typical surface root-mean-square (RMS) roughness of a few nanometers . Due to the extreme confinement of the optical fields in the nanometer-scale gap, granular polycrystalline metal films can introduce a significant optical loss because of the scattering of electrons by surface roughness and numerous grain boundaries. − This limits th...…”