Large-Scale Plasmonic Pyramidal Supercrystals via Templated Self-Assembly of Monodisperse Gold Nanospheres

Three-dimensional supercrystals of plasmonic nanoparticles are a novel class of materials with exciting applications in technologies such as light harvesting or metamaterials. However, their realization relies on extraordinarily regular colloidal building blocks and accurate self-assembly methods. We present here a simple and up-scalable protocol for the synthesis of smooth gold nanospheres with high monodispersity in size and sphericity. The synthesis involves rapid growth up to the desired size and subsequent removal of surface roughness via an efficient etching step, so that nanospheres with diameters ranging between 10 and 110 nm can be obtained in large quantities. Upon functionalization with thiolated polyethylene glycol and low surfactant concentration, Au nanospheres were employed as building blocks to produce uniform arrays of micron-sized 3D pyramidal supercrystals over large areas, by means of a template-assisted approach. Focused ion beam cutting and SEM characterization revealed a face-centered cubic lattice within individual pyramidal supercrystals.