Luisa D’Urso

Noble metal nanostructures provide versatile platforms for light manipulation through localized surface plasmon resonances (LSPRs). Among them, triangular silver nanoplates (AgNPTs) exhibit strong field-enhancement and spectral tunability, yet assembling them reproducibly on solids is challenging. We report a two-step functionalization strategy for constructing ordered AgNPT dimers on silica substrates, combining 3-aminopropyltriethoxysilane (APTES) anchoring with 1,4-butanedithiol bridging. AFM reveals face-to-face dimers with well-defined sub-nanometer gaps. Large-area AFM statistics collected over multiple regions (N = 80 nanoplates per condition) confirm reproducible and selective vertical dimerization. Extinction spectroscopy reveals sequential dielectric and coupling effects: thiol adsorption red-shifts the main resonance from 700 to 780 nm because of increased local refractive index and near-field damping, whereas dimerization partially restores it to ≈750 nm, consistent with plasmon hybridization within rigid ∼0.7 nm molecular gaps, where nonclassical moderation may occur but classical hybridization fully explains the observed shifts. Concomitantly, the extinction intensity doubles, following an exponential growth toward saturation during assembly. Surface-enhanced Raman scattering (SERS) measurements using 4-mercaptobenzoic acid (4-MBA) confirm a fourfold increase in the SERS enhancement factor from monolayer to bilayer, consistent with near-field coupling and hotspot formation at interplate junctions. Quantitative plasmon sensitivity analysis yields comparable results between experiments and finite-difference-time-domain simulations, confirming that the observed spectral shifts arise from near-field coupling and dielectric modulation rather than ensemble effects. This reproducible methodology enables precise tuning of NPT orientation, spacing, and optical response, providing a robust platform for enhanced sensing, SERS, and nanophotonic device engineering.