Colloidal Self-Assembly of Silver Nanoparticle Clusters for Optical Metasurfaces

Optical metasurfaces are two-dimensional assemblies of nanoscale optical resonators and could constitute the next generation of ultrathin optical components. The development of methods to manufacture these nanostructures on a large scale is still a challenge, while most performance demonstrations were obtained with lithographically fabricated metasurfaces that are restricted to small scales. Self-assembly fabrication routes are promising alternatives and have been used to produce original nanoresonators. Reports of self-assembled metasurface fabrication, however, are still scarce. Here, we show that an emulsion-based formulation approach can be used both for the fabrication of complex colloidal resonators, presenting a strong interaction with light, in particular due to simultaneous magnetic and electric modes of resonance, and for their deposition in homogeneous films. This fabrication technique involves emulsification of an aqueous suspension of silver nanoparticles in an oil phase, followed by controlled drying of the emulsion, and produces silver colloidal clusters. We show that the drying process can be controlled in a liquid emulsion, producing a metafluid, as well as in a sedimented emulsion, producing a metasurface. The structural control of the synthesized colloidal clusters is demonstrated with electron microscopy and X-ray scattering techniques. Using a polarization-resolved multiangle light scattering setup in the visible wavelength range, we conduct a comprehensive angular and spectroscopic study of the optical resonant scattering of the nanoresonators in a metafluid and show that they present strong optical magnetic resonances and directional forward-scattering patterns, with scattering efficiencies of up to 4. The metasurfaces consist of homogeneous films, of variable surface density, of colloidal clusters that have the same extinction properties on the surface and in the fluid. This experimental approach allows for large-scale production of metasurfaces.