Tailoring surface plasmons of high-density gold nanostar assemblies on metal films for surface-enhanced Raman spectroscopy

Abstract

Plasmonic systems based on metal nanoparticles on a metal film have generated great interest for surface-enhanced Raman spectroscopy (SERS) chemical sensors. In this study, we describe the fabrication of ultrasensitive SERS substrates based on high-density gold nanostar assemblies on silver films with tailored surface plasmons, where multiple field enhancements from particle-film and interparticle plasmon couplings and lightening rod effects of sharp tips of nanostars contribute to the enormous Raman enhancements. We show that the interplay between interparticle and particle-film plasmon couplings of high-density gold nanostars (GNSs) on metal and dielectric films as a function of interparticle separation can be tailored to provide maximum SERS effects. We observe that the SERS enhancement factor (EF) of GNSs on a metal film as a function of interparticle separation follows a broken power law function, where the EF increases with the interparticle separation for the strong interparticle coupling range below an interparticle separation of ∼0.8 times the GNS size, but decreases for the weak interparticle coupling range (for an interparticle separation of >0.8 times the GNS size). Finally, we demonstrate the use of tailored plasmonic substrates as ultrasensitive SERS chemical sensors with an attomole level of detection capability of 2,4-dinitrotoluene, a model compound of nitroaromatic explosives.