Controlled Plasmonic Coupling in Silver Nanoplate Dimers for Enhanced Plasmonic Sensing

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.