Macroscopic aerogels with retained nanoscopic plasmonic properties

Aerogels can bridge the nanoscopic to the macroscopic world. One physical phenomenon typically limited to the nanoscopic world is the occurrence of localized surface plasmon resonances (LSPRs), which are observed in conductive nanoparticles. Once brought into close contact, assemblies or superstructures of these nanoparticles often lose their plasmonic properties in the transition stage towards the bulk material. Therefore, LSPRs are typically not observed in macroscopic objects. The present work aims at voluminous nanoparticle-based aerogels with optical properties close to that of the initial colloidal solution and the possibility to manipulate the final plasmonic properties by bringing the particles into defined distances. In detail, Ag nanocrystals with silica shells ranging from 0 to 12 nm are employed as building blocks, which are assembled from their solution into macroscopic three-dimensional superstructures by freezing and subsequent lyophilization. These cryogelated aerogels are synthesized as monoliths and thin films in which the Ag nanocrystals are arranged in defined distances according to their silica shell. The resulting aerogels exhibit plasmonic properties ranging from a behavior similar to that of the building blocks for the thickest shell to a heavily distorted behavior for bare Ag nanocrystals.