Shedding Light on the Growth of Gold Nanoshells

Nanostructured particles containing noble metals can have highly tunable localized surface plasmon resonances and are therefore of particular interest for numerous applications. Nanoshells comprising a dielectric core and gold or silver shell are a widely researched systems because of the strong dependence of their optical properties on the ratio of core diameter to shell thickness. Although seeded-growth procedures have been developed to produce these particles, the many reported studies show significant variation in the nanoshell morphologies and hence optical properties. In order to establish processes that reproducibly synthesize nanoshells with high optical quality, it is necessary to develop techniques that monitor changes at the core particle surface during shell growth. For that purpose, we have carried out in situ nonlinear second-harmonic scattering (SHS) and linear vis-NIR extinction spectroscopy simultaneously during the seeded growth of gold nanoshells on silica core particles. Our SHS measurements show a striking variation in the nonlinear optical properties of the growing gold nanoshells. In comparison with linear optical measurements and with scanning electron microscopy (SEM) images made of gold nanoshells produced with varying shell completenesses, the SHS signal was observed to reach a peak intensity at a stage prior to shell closure. We attribute this high sensitivity of the SHS signal to the incomplete nanoshell surface morphology to the generation and subsequent degeneration of regions of electric field enhancement at gaps between isolated gold islands, which grow and coalesce. This conclusion is corroborated by finite-difference time-domain simulations of incomplete nanoshells. We suggest that the in situ analytical approach demonstrated here offers significant promise for future activities regarding the in-process optimization of the morphology and optical properties of metal nanoshells and other nanostructured plasmonic particles.