Plasmonic supercrystals and periodically structured arrays comprise a class of materials with unique optical properties that result from the interplay of plasmon resonances, as well as near- and far-field coupling. Controlled synthesis of such hierarchical structures remains a fundamental challenge, as it demands strict control over the assembly morphology, array size, lateral spacing, and macroscale homogeneity. Current fabrication approaches involve complicated multistep procedures lacking scalability and reproducibility, which has hindered the practical application of plasmonic supercrystal arrays. Herein, these challenges are addressed by adding an organic solvent to achieve kinetic control over the template-assisted colloidal assembly of nanoparticles from aqueous dispersion. This method yields highly regular periodic arrays, with feature sizes ranging from less than 200 nm up to tens of microns. A combined experimental/computational approach reveals that the underlying mechanism is a combination of the removal of interfacial surfactant micelles from the particle interface and altered capillary flows. Assessing the efficacy of such square arrays for surface-enhanced Raman scattering spectroscopy, we find that a decrease of the lattice periodicity from 750 nm down to 400 nm boosts the signal by more than an order of magnitude, thereby enabling sensitive detection of analytes, such as the bacterial quorum sensing molecule pyocyanin, even in complex biological media.

Perovskite nanocrystals (NCs) have revolutionized optoelectronic devices because of their versatile optical properties. However, controlling and extending these functionalities often requires a light‐management strategy involving additional processing steps. Herein, we introduce a simple approach to shape perovskite nanocrystals (NC) into photonic architectures that provide light management by directly shaping the active material. Pre‐patterned polydimethylsiloxane (PDMS) templates are used for the template‐induced self‐assembly of 10 nm CsPbBr3 perovskite NC colloids into large area (1 cm2) 2D photonic crystals with tunable lattice spacing, ranging from 400 nm up to several microns. The photonic crystal arrangement facilitates efficient light coupling to the nanocrystal layer, thereby increasing the electric field intensity within the perovskite film. As a result, CsPbBr3 2D photonic crystals show amplified spontaneous emission (ASE) under lower optical excitation fluences in the near‐IR, in contrast to equivalent flat NC films prepared using the same colloidal ink. This improvement is attributed to the enhanced multi‐photon absorption caused by light trapping in the photonic crystal.

Metrics & MoreArticle Recommendations CONSPECTUS: Over the past 30 years, the engineering of plasmonic resonances at the nanoscale has progressed dramatically, with important contributions in a variety of different fields, including chemistry, physics, biology, engineering, and medicine. However, heavy optical losses related to the use of noble metals for the fabrication of plasmonic structures hindered their application in various settings.Recently, an answer to these long-lasting issues emerged in the use of lattice plasmon resonances (LPRs, also called surface lattice resonances), bringing new excitement in the field of plasmonics. Specifically, the organization of plasmonic nanoparticles into ordered arrays enables far-field coupling of the scattered light exploiting the diffraction modes of the array, generating plasmonic resonances with bandwidths as narrow as a few nanometers, corresponding to an increase of over 10-fold in the quality factors compared to localized plasmon resonances. As such, LPRs offer new opportunities to harness light−matter interactions at the nanoscale, while generating renewed interest in the self-assembly of colloidal metal nanoparticles, as a scalable approach to the preparation of such plasmonic arrays. Templated self-assembly emerged as one of the most versatile approaches, being compatible with soft-lithographic techniques such as nanoimprint lithography and amenable to a variety of materials, colloids, and solvents. Templated self-assembly additionally allows the preparation of arrays where the repeating units are composed of multiple self-assembled nanoparticles (i.e., plasmonic clusters). In this system, near-field coupling can be finely tuned, thereby showing promising results in biosensing, catalysis, or plasmonic heating. In this Account, we review the preparation of ordered arrays of clusters of plasmonic nanoparticles. We present various aspects involved in the templated self-assembly of colloidal nanoparticles, with the aim of achieving at the same time close-packed structures within each cavity of the template, and uniform deposition over a large area. We then analyze the optical properties of the prepared substrates. The preparation of hierarchical structures and the possibility of tuning both the internal structure of the cluster and their organization into arrays with different lattice parameters enable control over both near-field and far-field plasmonic coupling. This unique feature of such substrates makes it possible to exploit the interplay between these two types of coupling, for the preparation of versatile functional substrates, expanding the possibilities for the integration of plasmonic arrays into functional devices for various applications. A well-established example is their use for surface-enhanced Raman scattering. On the other hand, optimization of farfield coupling provides access to plasmonic cavities for lasing or refractive index sensing. Despite two decades of fervid scientific research, the preparation and engineering of plasmonic arrays remai...