Effect of Size, Shape, Composition, and Support Film on Localized Surface Plasmon Resonance Frequency: A Single Particle Approach Applied to Silver Bipyramids and Gold and Silver Nanocubes

Localized surface plasmon resonances (LSPR), collective electron oscillations in nanoparticles, are being heavily scrutinized for applications in chemical and biological sensing, as well as in prototype nanophotonic devices. This phenomenon exhibits an acute dependence on the particle’s size, shape, composition, and environment. The detailed characterization of the structure-function relationship of nanoparticles is obscured by ensemble averaging. Consequently, single-particle data must be obtained to extract useful information from polydisperse reaction mixtures. Recently, a correlated high resolution transmission electron microscopy (HRTEM) LSPR technique has been developed and applied to silver nanocubes. We report here a second generation of experiments using this correlation technique, in which statistical analysis is performed on a large number of single particles. The LSPR dependence on size, shape, material, and environment was probed using silver right bipyramids, silver cubes, and gold cubes. It was found that the slope of the dependence of LSPR peak on size for silver bipyramids increases as the edges become sharper. Also, a plasmon shift of 96 nm was observed between similar silver and gold cubes, while a shift of 26 nm was observed, for gold cubes, between substrates of refractive index (RI) of 1.5 and 2.05.