Abstract
Nanoscale nonlinear optics is limited by the inherently weak nonlinear response of conventional materials and the small light-matter interaction volumes available in nanostructures. Plasmonic excitations can alleviate these limitations through subwavelength light focusing, boosting optical near fields that drive the nonlinear response, but also suffering from large inelastic losses that are further aggravated by fabrication imperfections. Here, we theoretically explore the enhanced nonlinear response arising from extremely confined plasmon polaritons in few-atom-thick crystalline noble metal films. Our results are based on quantum-mechanical simulations of the nonlinear optical response in atomically thin metal films that incorporate crucial electronic band structure features associated with vertical quantum confinement, electron spill-out, and surface states. We predict an overall enhancement in plasmon-mediated nonlinear optical phenomena with decreasing film thickness, underscoring the importance of surface and electronic structure in the response of ultrathin metal films.