Core-satellite-satellite hierarchical nanostructures: assembly, plasmon coupling, and gap-selective surface-enhanced Raman scattering.

Abstract

The plasmonic properties of gold nanoparticles (AuNPs), such as color tunability, electric field generation, hot carrier generation, and localized heating, are significantly enhanced in the nanogaps between AuNPs. Therefore, the creation and control of nanogaps are key to developing advanced plasmonic nanomaterials. Most AuNP nanoassemblies, including dimers, trimers, and core-satellites, have a single type of nanogap within the assembly. In this study, we construct core-satellite-satellite (CSS) hierarchical, fractal-like nanostructures featuring two types of nanogaps, namely first generation nanogaps (Gap1) between the core and first satellite (Sat1) AuNPs and second generation nanogaps (Gap2) between Sat1 and second satellite (Sat2) AuNPs. The sequential and alternating immersion of glass slides in different-sized AuNPs and linkers forms CSS with perfect yield. The UV-vis spectroscopy, combined with charge density distribution calculations, reveals the nature of the plasmon coupling between the AuNPs that constitute CSS nanoassemblies. The plasmon coupling can be tuned by independently varying Gap1 and Gap2. Furthermore, we explore the electric field amplification in Gap1 and Gap2 by comparing the surface-enhanced Raman scattering signal intensity selectively from each nanogap. This new type of nanostructure provides a great flexibility to control and enhance the plasmonic properties of noble metal nanoparticles.