Soft Plasmonic Assemblies Exhibiting Unnaturally High Refractive Index

The increases in refractive indices (n) of materials are crucial for transformative optical technologies. With the progress of monolithic lithography, large advances have been achieved with several semiconductors, including silicon, germanium, and gallium arsenide, which generally provide higher n of ∼4.0 compared to those of other elements. Nevertheless, above this upper limit of naturally available n, the range of light-matter interactions could be unprecedentedly expanded, which in turn enriches the possible applications. Here, we present a soft self-assembly of polyhedral Au colloids as a promising method to achieve unnaturally high n values. The interfacial assembly of Au nanocubes provides n of 6.4 at the resonant wavelength (near-infrared) and 4.5 in the off-resonant regimes (mid-infrared), which have not been previously reached. The soft self-assembly of polyhedral Au colloids can be a versatile and highly effective route for the fabrication of optical metamaterials with unnaturally high n values.