Second-Harmonic Generation from Sub‑5 nm Gaps by Directed Self-Assembly of Nanoparticles onto Template-Stripped Gold Substrates

Strong field enhancement and confinement in plasmonic nanostructures provide suitable conditions for nonlinear optics in ultracompact dimensions. Despite these enhancements, second-harmonic generation (SHG) is still inefficient due to the centrosymmetric crystal structure of the bulk metals used, e.g., Au and Ag. Taking advantage of symmetry breaking at the metal surface, one could greatly enhance SHG by engineering these metal surfaces in regions where the strong electric fields are localized. Here, we combine top-down lithography and bottom-up self-assembly to lodge single rows of 8 nm diameter Au nanoparticles into trenches in a Au film. The resultant “double gap” structures increase the surface-to-volume ratio of Au colocated with the strong fields in ∼2 nm gaps to fully exploit the surface SHG of Au. Compared to a densely packed arrangement of AuNPs on a smooth Au film, the double gaps enhance SHG emission by 4200-fold to achieve an effective second-order susceptibility χ(2) of 6.1 pm/V, making it comparable with typical nonlinear crystals. This patterning approach also allows for the scalable fabrication of smooth gold surfaces with sub-5 nm gaps and presents opportunities for optical frequency up-conversion in applications that require extreme miniaturization.