Abstract

We combine the fabrication of Au and Au/Ag core/shell nanorods (NRs), as well as experimental measurements of vis-NIR extinction, unpolarized, and cross-polarized light scattering spectra, with T-matrix and separation-of-variables simulations, to gain insight into the relation between the morphology/composition of nanoparticles and their isotropic and anisotropic optical responses. Using several Au and Au/Ag core/shell NR samples, we present unambiguous experimental evidence of a tunable correlation between the longitudinal plasmon resonances of NRs and their spectral depolarization maxima. For gold NRs, the depolarization maxima follow the extinction plasmon resonances blue-shifted from 80 to 270 nm. In contrast, the depolarization maximum of Au/Ag NRs is located just near the longitudinal resonance, and the spectral shift of the depolarization maximum is about 10 to 20 nm. The experimental extinction and depolarization spectra of gold NRs are in good agreement with T-matrix simulations based on TEM-fitted models that account for the aspect ratio polydispersity and byproduct contributions. For composite Au/Ag NRs, the separation-of-variables simulations provide a calibration curve that correlates the relative spectral shift of the extinction resonance with the silver shell thicknesses and generates experimental data that are in good agreement with estimations based on the Ag/Au mass ratio.

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