Metal colloids are of great interest in the field of nanophotonics, mainly due to their morphology-dependent optical properties, but also because they are high-quality building blocks for complex plasmonic architectures. Close-packed colloidal supercrystals not only serve for investigating the rich plasmonic resonances arising in strongly coupled arrangements but also enable tailoring the optical response, on both the nano- and the macroscale. Bridging these vastly different length scales at reasonable fabrication costs has remained fundamentally challenging, but is essential for applications in sensing, photovoltaics or optoelectronics, among other fields. We present here a scalable approach to engineer plasmonic supercrystal arrays, based on the template-assisted assembly of gold nanospheres with topographically patterned polydimethylsiloxane molds. Regular square arrays of hexagonally packed supercrystals were achieved, reaching periodicities down to 400 nm and feature sizes around 200 nm, over areas up to 0.5 cm. These two-dimensional supercrystals exhibit well-defined collective plasmon modes that can be tuned from the visible through the near-infrared by simple variation of the lattice parameter. We present electromagnetic modeling of the physical origin of the underlying hybrid modes and demonstrate the application of superlattice arrays as surface-enhanced Raman scattering (SERS) spectroscopy substrates which can be tailored for a specific probe laser. We therefore investigated the influence of the lattice parameter, local degree of order, and cluster architecture to identify the optimal configuration for highly efficient SERS of a nonresonant Raman probe with 785 nm excitation.

Negative-index metamaterials (NIMs) are engineered structures with optical properties that cannot be obtained in naturally occurring materials. Recent work has demonstrated that focused ion beam and layer-by-layer electron-beam lithography can be used to pattern the necessary nanoscale features over small areas (hundreds of µm(2)) for metamaterials with three-dimensional layouts and interesting characteristics, including negative-index behaviour in the optical regime. A key challenge is in the fabrication of such three-dimensional NIMs with sizes and at throughputs necessary for many realistic applications (including lenses, resonators and other photonic components). We report a simple printing approach capable of forming large-area, high-quality NIMs with three-dimensional, multilayer formats. Here, a silicon wafer with deep, nanoscale patterns of surface relief serves as a reusable stamp. Blanket deposition of alternating layers of silver and magnesium fluoride onto such a stamp represents a process for 'inking' it with thick, multilayer assemblies. Transfer printing this ink material onto rigid or flexible substrates completes the fabrication in a high-throughput manner. Experimental measurements and simulation results show that macroscale, three-dimensional NIMs (>75 cm(2)) nano-manufactured in this way exhibit a strong, negative index of refraction in the near-infrared spectral range, with excellent figures of merit.

A simple, reproducible, and reliable method to crystallize sub‐micrometer‐size spherical colloids using a mixture of volatile solvents as dispersion media is presented. Strongly diffracting direct opal structures of high uniformity are attainable over large areas within minutes and without further processing. Thickness and orientation control is also possible through this technique. In the figure, both [111] (left) and [100] (right) oriented lattices deposited on glass slides are shown.