Gold nanoparticles with tipped surface structures as substrates for single-particle surface-enhanced Raman spectroscopy: concave nanocubes, nanotrisoctahedra, and nanostars.

Abstract

We demonstrate that Au nanoparticles with tipped surface structures, such as concave nanocubes, nanotrisoctahedra, and nanostars, possess size-dependent tunable plasmon resonances and intense near-field enhancements exploitable for single-particle surface-enhanced Raman spectroscopy (spSERS) under near-infrared excitation. We report a robust seed-mediated growth method for the selective fabrication of Au concave nanocubes, nanotrisoctahedra, and nanostars with fine-controlled particle sizes and narrow size distributions. Through tight control over particle sizes, the plasmon resonances of the nanoparticles can be fine-tuned over a broad spectral range with respect to the excitation laser, allowing us to systematically quantify the SERS enhancements on individual nanoparticles as a function of particle size for each particle geometry. Understanding of the geometry-dependent plasmonic characteristics and SERS activities of the nanoparticles is further enhanced by finite-difference time-domain (FDTD) calculations. Our results clearly show that strong SERS enhancements can be obtained and further optimized on individual Au nanoparticles with nanoengineered "hot spots" on their tipped surfaces when the plasmon resonances of the nanoparticles are tuned to the optimal spectral regions with respect to the excitation laser wavelength. Using tunable plasmonic nanoparticles with tipped surface structures as substrates for spSERS represents a highly promising and feasible approach to the optimization of SERS-based sensing and imaging applications.