Hollow Porous Gold Nanoshells with Controlled Nanojunctions for Highly Tunable Plasmon Resonances and Intense Field Enhancements for Surface-Enhanced Raman Scattering.

Plasmonic metal nanostructures with nanogaps have attracted great interest owing to their controllable optical properties and intense electromagnetic fields that can be useful for a variety of applications, but precise and reliable control of nanogaps in three-dimensional nanostructures remains a great challenge. Here, we report the control of nanojunctions of hollow porous gold nanoshell (HPAuNS) structures by a facile oxygen plasma-etching process and the influence of changes in nanocrevices of the interparticle junction on the optical and sensing characteristics of HPAuNSs. We demonstrate a high tunability of the localized surface plasmon resonance (LSPR) peaks and surface-enhanced Raman scattering (SERS) detection of rhodamine 6G (R6G) using HPAuNS structures with different nanojunctions by varying the degree of gold sintering. As the neck region of the nanojunction is further sintered, the main LSPR peak shifts from 785 to 1350 nm with broadening because the charge transfer plasmon mode becomes more dominant than the dipolar plasmon mode, resulting from the increase of conductance at the interparticle junctions. In addition, it is demonstrated that an increase in the sharpness of the nanojunction neck can enhance the SERS enhancement factor of the HPAuNS by up to 4.8-fold. This enhancement can be ascribed to the more intense local electromagnetic fields at the sharper nanocrevices of interparticle junctions. The delicate change of nanojunction structures in HPAuNSs can significantly affect their optical spectrum and electromagnetic field intensity, which are critical for their practical use in a SERS-based analytical sensor as well as multiple-wavelength compatible applications.