Binary Plasmonic Assembly Films with Hotspot-Type-Dependent Surface-Enhanced Raman Scattering Properties

Tuning and controlling the plasmon coupling of noble metal nanoparticles are significant for enhancing their near-field and far-field responses. In this work, a novel heterogeneous plasmonic assembly with a controllable hot spot model was proposed by the conjugation of Au nanospheres (NSs) and Au@Ag core–shell nanocube (NC) films. Three hotspot configurations including point-to-point type, point-to-facet type, and facet-to-facet type were fabricated and transformed simply by adjusting the doping ratio of nanoparticles in the co-assembly film. Expectedly, the localized surface plasmon resonance (LSPR) property and surface-enhanced Raman scattering (SERS) performance of the binary assembly film exhibit distinct diversity due to the change in the hotspot conformation. Interestingly, the point-to-facet hotspot in hybrid assembly films can provide the most extraordinary enhancement for SERS behavior compared with single-component Au NS and Au@Ag NC plasmonic assemblies, which is further confirmed by the finite-different time-domain simulation results of dimer nanostructures. In addition, the two-dimensional binary assemblies of Au NS doping in Au@Ag NCs with excellent sensitivity and high reproducibility were successfully applied in the identification of ketamine. This work opens a new avenue toward the fabrication of plasmonic metal materials with collective LSPR properties and sensitive SERS behavior.