Sensitivity of Localized Surface Plasmon Resonances to Bulk and Local Changes in the Optical Environment

Single rod-shaped and disk-shaped gold nanoparticles with sizes ranging from 60 to 162 nm were analyzed using dark-field scattering spectroscopy. The sensitivity of the localized surface plasmon resonance (LSPR) of each nanoparticle to both a bulk and a local change in the refractive index of the environment was obtained by monitoring the change in the spectral position of the LSPR. It was found that the rods were more sensitive to changes in both the local environment and the bulk environment, in particular rods with a length > 110 nm. This behavior was confirmed by finite element modeling of the structures that clearly indicated a saturation of the relative wavelength shift for the disks as the diameter increased whereas the sensitivity of the rods continued to increase linearly with increasing length. This disparity in the behavior of the two types of nanoparticle may in part be attributed to two principal effects associated with the presence of the substrate: first, that the proportion of the surface area of the nanoparticle in contact with the substrate is larger for the disk than for the rod; second, that the LSPR electromagnetic field is more concentrated within the superstrate for the rod compared to the disk. Further analysis of data obtained from modeling a changing local environment indicates that, although the rods are more sensitive, both rods and disks exhibit a similar field confinement.