Generalization of Self-Assembly Toward Differently Shaped Colloidal Nanoparticles for Plasmonic Superlattices.

Periodic superlattices of noble metal nanoparticles  have demonstrated superior plasmonic properties compared to randomly distributed plasmonic arrangements due to near-field coupling and constructive far-field interference. Here, a chemically driven, templated self-assembly process of colloidal gold nanoparticles is investigated and optimized, and the technology is extended toward a generalized assembly process for variously shaped particles, such as spheres, rods, and triangles. The process yields periodic superlattices of homogenous  nanoparticle clusters on a centimeter scale. Electromagnetically simulated absorption spectra and corresponding experimental extinction measurements demonstrate excellent agreement in the far-field for all particle types and different lattice periods. The electromagnetic simulations reveal the specific nano-cluster near-field behavior, predicting the experimental findings provided by surface-enhanced Raman scattering measurements. It turns out that periodic arrays of spherical nanoparticles produce higher surface-enhanced Raman scattering enhancement factors than particles with less symmetry as a result of very well-defined strong hotspots.