An Investigation on the Use of Au@SiO2@Au Nanomatryoshkas as Gap-Enhanced Raman Tags.

Gap-enhanced Raman tags are a new type of optical probe that have wide applications in sensing and detection. A gap-enhanced Raman tag is prepared by embedding Raman molecules inside a gap between two plasmonic metals such as an Au core and Au shell. Even though placing Raman molecules beneath an Au shell seems counter-intuitive, it has been shown that such systems produce a stronger surface-enhanced Raman scattering response due to the strong electric field inside the gap. While the theoretical support of the stronger electric field inside the gap was provided in the literature, a comprehensive understanding of how the electric field inside the gap compares with that of the outer surface of the particle was not readily available. We investigated Au@SiO2@Au nanoparticles with diameters ranging from 35 nm to 70 nm with varying shell (2.5-10 nm) and gap (2.5-15 nm) thicknesses and obtained both far-field and near-field spectra. The extinction spectra from these particles always have two peaks. The low-energy peak redshifts with the decreasing shell thickness. However, when the gap thickness decreases, the low-energy peaks first blueshift and then redshift, producing a C-shape in the peak position. For every system we investigated, the near-field enhancement spectra were stronger inside the gap than on the outer surface of the nanoparticle. We find that a thin shell combined with a thin gap will produce the greatest near-field enhancement inside the gap. Our work fills the knowledge gap between the exciting potential applications of gap-enhanced Raman tags and the fundamental knowledge of enhancement provided by the gap.

Impact of core dielectric properties on the localized surface plasmonic spectra of gold-coated magnetic core-shell nanoparticles.

Gold-coated iron oxide core-shell nanoparticles (IO-Au NPs) are of interest for use in numerous biomedical applications because of their unique combined magnetic-plasmonic properties. Although the effects of the core-dielectric constant on the localized surface plasmon resonance (LSPR) peak position of Au-shell particles have been previously investigated, the impact that light-absorbing core materials with complex dielectric functions have on the LSPR peak is not well established. In this study, we use extended Mie theory for multilayer particles to examine the individual effects of the real and imaginary components of core refractive indices on Au-shell NP plasmonic peaks. We find that the imaginary component dampens the intensity of the cavity plasmon and results in a decrease of surface plasmon coupling. For core materials with large imaginary refractive indices, the coupled mode LSPR peak disappears, and only the anticoupled mode remains. Our findings show that the addition of a nonabsorbing polymer layer to the core surface decreases the dampening of the cavity plasmon and increases LSPR spectral intensity. Additionally, we address apparent discrepancies in the literature regarding the effects of Au-shell thickness on LSPR peak shifts.