Improved monodispersity of plasmonic nanoantennas via centrifugal processing

Noble metal nanoparticle clusters underlie a variety of plasmonic devices and measurements including surface-enhanced Raman spectroscopy (SERS). Because of the strong dependence of plasmonic properties on nanoparticle cluster aggregation state, the elimination of non-SERS-active structures and the refinement of the nanoparticle cluster population are critical to realizing uniform and reproducible structures for plasmonic nanoantenna applications such as SERS-based sensors. In this Letter, we report a centrifugal sorting technique for gold core/silica shell nanoparticles that host SERS reporter molecules at the gold/silica interface. The relatively massive nanoparticle clusters are sorted by sedimentation coefficient via centrifugation in a high-viscosity density gradient medium, iodixanol, which yields solutions that contain a preponderance of one aggregation state and a diminished monomer population, as determined by transmission electron microscopy, extinction spectroscopy, and SERS. A quantitative analysis of the nanoparticle sedimentation coefficients is presented, thus allowing this approach to be predictably generalized to other nanoparticle systems.