A combined size sorting strategy for monodisperse plasmonic nanostructures

Abstract

The fabrication of highly monodisperse silica coated Au NPs by the microemulsion approach and the selection of the nanostructure morphology have been described. Several experimental conditions, synthetic parameters and post-preparative strategies such as reaction time, precursor concentration, size selection techniques and NP surface treatments have been suitably investigated in order to fabricate Au and Au@SiO₂ NPs with peculiar and tuneable plasmonic properties that strongly depend on the specific size distribution and nanostructure morphology. In particular, size selected precipitation of oleylamine-capped Au NPs by antisolvent titration has successfully offered a strategy to discriminate and collect monodisperse fractions with different average size and narrow size distribution. Moreover, for the first time, a deep insight into the microemulsion mechanism for the silica shell growth has been provided, highlighting the critical role played by the density of oleylamine at the Au NP surface. Specifically the capping agent has been demonstrated to strongly determine the multiplicity of the core in the final Au@SiO₂ nanostructures. Density gradient centrifugation has been finally performed to sort the achieved Au@SiO₂ NPs with different morphologies, which was ultimately able to recover a significant fraction formed of two Au NPs in one silica shell. A systematic characterization of the Au and Au@SiO₂ NPs has been carried out by complementary morphological and spectroscopic techniques. These deeply investigated materials, with tuneable plasmonic properties, have been proposed as versatile building blocks useful for the design and fabrication of plasmonic and photonic structures as well as metamaterials for device applications.