Unexpected large nanoparticle size of single dimer hotspot systems for broadband SERS enhancement.

We have numerically demonstrated the feasibility and possibility to achieve broadband surface-enhanced Raman scattering (SERS) enhancement in the visible and near-infrared wavelength range using single nanoparticle (NP) dimer hotspot systems. Instead of the conventionally reported sub-100 nm, we find that the optimal NP size is as large as 200 nm in diameter for both Ag and Au. The key lies in the continuous arising of the bonding dipole plasmon mode and higher-order resonances at shorter wavelengths. Further, it is revealed that the near- and far-field optical responses of these hotspot systems correlate well with each other, despite the intrinsic enormous near- to far-field redshift for individual large NPs. The physical principles demonstrated here benefit significantly the fundamental understanding and engineering optimization of broadband SERS substrates.

Reducing the loss of electric field enhancement for plasmonic core-shell nanoparticle dimers by high refractive index dielectric coating.

Plasmonic nanoparticle (NP) dimers, generating highly intense areas of electric field enhancement named hot spots, have been playing a vital role in various applications like surface enhanced Raman scattering. For stabilization and functionalization, such metallic NPs are often coated with dielectric shells, yet suffer from a rapid degeneration of the hot spot with the increase of the shell thickness. Herein, it is demonstrated that the use of appropriately high refractive dielectric coatings can greatly reduce the loss of local electric field enhancement, maintaining usable hot spots. Two mechianisms work synergistically. Firstly, the high refractive index dielectric coating enables a great leap of the local electric fields reaching the gap, which follows the boundary conditions at the interface within electrodynamics. Secondly, owing to its strong Mie resonances that can participate in the plasmon hybridization, the high refractive index dielectric coating contributes to a strong light coupling effect in terms of improving the light absorption. Taking advantage of the proposed physical process decomposition, both the resonance shift and local electric field enhancement can be elaborated. These findings should be of significant importance in extended applications of surface enhanced spectroscopies and related plasmonic devices based on hot spots.