Surface Lattice Resonances in Self-Assembled Gold Nanoparticle Arrays: Impact of Lattice Period, Structural Disorder, and Refractive Index on Resonance Quality.

Surface lattice resonances are optical resonances composed of hybridized plasmonic and diffractive modes. These collective resonances occur in periodic arrays of plasmonic nanoparticles with wavelength-scale interparticle distances. The appearance and strength of surface lattice resonances strongly depend on the single particle localized surface plasmon resonance and its spectral overlap with the diffractive modes of the array. Coupling to in-plane orders of diffraction is also strongly affected by the refractive index environment and its symmetry. In this work, we address the impact of the interparticle distance, the symmetry of the refractive index environment, and structural imperfections in self-assembled colloidal monolayers on the plasmonic-diffractive coupling. For this purpose, we prepared hexagonally ordered, nonclose packed monolayers of gold nanoparticles using a fast and efficient, interface-mediated, colloidal self-assembly approach. By tuning the thickness and deformability of the polymer shells, we were able to prepare monolayers with a broad range of interparticle distances. The optical properties of the samples were studied experimentally by UV-Vis spectroscopy and theoretically by finite difference time domain simulations. The measured and simulated spectra allow a comprehensive analysis of the details of electromagnetic coupling in periodic plasmonic arrays. In particular, we identify relevant criteria required for surface lattice resonances in the visible wavelength range with optimized quality factors in self-assembled monolayers.

Chiral Surface Lattice Resonances.

Collective excitation of periodic arrays of metallic nanoparticles by coupling localized surface plasmon resonances to grazing diffraction orders leads to surface lattice resonances with narrow line width. These resonances may find numerous applications in optical sensing and information processing. Here, a new degree of freedom of surface lattice resonances is experimentally investigated by demonstrating handedness-dependent excitation of surface lattice resonances in arrays of chiral plasmonic crescents. The self-assembly of particles used as mask and modified colloidal lithography is applied to produce arrays of planar and 3D gold crescents over large areas. The excitation of surface lattice resonances as a function of the interparticle distance and the degree of order within the arrays is investigated. The chirality of the individual 3D crescents leads to the formation of chiral lattice modes, that is, surface lattice resonances that exhibit optical activity.

Moiré and honeycomb lattices through self-assembly of hard-core/soft-shell microgels: experiment and simulation.

Control over microstructure and interparticle spacing in substrate-supported colloidal arrangements is a key challenge in colloidal self-assembly. We demonstrate here the preparation of Moiré and honeycomb monolayer lattices from core/shell microgels with rigid inorganic cores and soft, deformable hydrogel shells. These structures were realized by the sequential double deposition of freely floating monolayers from the air/water interface onto the same, centimetre-scale substrate. Due to the soft and deformable character of the hydrogel shells, the second applied monolayer fully settles into the same plane as the first monolayer. The resulting structural motif is determined by the drying conditions applied to the second deposition step. We support our experimental findings by Brownian dynamics simulations and provide insights into the structure formation process.

Silver Nanoparticle Gradient Arrays: Fluorescence Enhancement of Organic Dyes.

Noble metal nanoparticles show pronounced extinction peaks in the visible wavelength range due to their localized surface plasmon resonances. The excitation of these resonances leads to strong confinement of electromagnetic energy at nanometer scales, which is critical for ultrasensitive, fluorescence-based detection of analytes. The strength and spatial distribution of this near-field zone depend on particle size, shape, and composition. To determine how these near-field effects depend on the particle size, we have prepared nanoparticle gradients on centimeter-scale substrates using a colloid-based approach. This plasmonic gradient is used to study the steady-state emission and fluorescence lifetime of a common organic dye that was embedded into the monolayer.

In-Plane Surface Lattice and Higher Order Resonances in Self-Assembled Plasmonic Monolayers: From Substrate-Supported to Free-Standing Thin Films.

Periodic arrays of plasmonic nanostructures are able to strongly confine light at the nanometer scale because of surface lattice resonances. These resonances are the result of electromagnetic coupling between single-particle localized surface plasmon resonances and Bragg resonances of the periodic lattice. Here, we investigate the effect of a finite size refractive index environment on the formation of surface lattice resonances by increasing the thickness of a polymer coating in nanometer-scale increments. Wet-chemically synthesized, spherical silver and gold nanoparticles with soft hydrogel shells are self-assembled into macroscopic, hexagonally ordered arrays on glass substrates using an interface-assisted approach. The resulting periodic plasmonic monolayers are subsequently coated by a polymer matching closely the refractive index of the glass support. The optical response of the plasmonic arrays is studied using far-field extinction spectroscopy and supported by numerical simulations. We show the formation of surface lattice resonances as well as higher order resonances in finite thickness polymer coatings. The resonance positions are determined by the interparticle spacing as well as the plasmonic material. Additionally, we demonstrate that a coating thickness of 450 nm is sufficient to support strong in-plane surface lattice resonances. This enables us to prepare macroscopic, free-standing polymer films with embedded plasmonic nanoparticle arrays, which feature strong surface lattice resonances.

Plasmonic and colloidal stability behaviours of Au-acrylic core-shell nanoparticles with thin pH-responsive shells.

The localised surface plasmon resonance (LSPR) of Au nanoparticles (NPs) as well as its interaction with nearby entities provides a wealth of fundamental and practical information at the nanometre scale. A number of studies have investigated core-shell NPs with Au cores and polymer shells that are temperature-responsive. However, there are very few studies of pH-responsive Au-polymer NP shells. Precipitation polymerisation is a scalable method and here we establish such a method to synthesise pH-responsive Au-poly(methyl methacrylate) copolymer core-shell NPs without the need for pre-functionalisation. The comonomers used were methacrylic acid (MAA) or 2-carboxyethyl acrylate (CEA) and the shells were crosslinked with ethylene glycol dimethacrylate. A series of five core-shell systems with collapsed shell thicknesses less than 30 nm are studied. The shell-thicknesses for the CEA-based core-shell NPs are relatively thin (≤5 nm) compared to related Au-polymer core-shell NPs prepared using precipitation polymerisation. The LSPR properties of the core-shell NPs were dependent on the shell thickness and were successfully simulated using finite difference time domain (FDTD) calculations. Two systems are considered further as exemplars. The MAA-based core-shell system with the thickest shell exhibited enhanced colloidal stability to added electrolyte. The CEA-based core-shell dispersion with the thinnest shells displayed reversible pH-triggered aggregation and was cytocompatible for HeLa cells. Proof-of-concept data are presented that demonstrate intracellular pH reporting.

Bottom-Up Meets Top-Down: Patchy Hybrid Nonwovens as an Efficient Catalysis Platform.

Heterogeneous catalysis with supported nanoparticles (NPs) is a highly active field of research. However, the efficient stabilization of NPs without deteriorating their catalytic activity is challenging. By combining top-down (coaxial electrospinning) and bottom-up (crystallization-driven self-assembly) approaches, we prepared patchy nonwovens with functional, nanometer-sized patches on the surface. These patches can selectively bind and efficiently stabilize gold nanoparticles (AuNPs). The use of these AuNP-loaded patchy nonwovens in the alcoholysis of dimethylphenylsilane led to full conversion under comparably mild conditions and in short reaction times. The absence of gold leaching or a slowing down of the reaction even after ten subsequent cycles manifests the excellent reusability of this catalyst system. The flexibility of the presented approach allows for easy transfer to other nonwoven supports and catalytically active NPs, which promises broad applicability.

Time-Controlled Colloidal Superstructures: Long-Range Plasmon Resonance Coupling in Particle Monolayers.

Particle interactions, from pronounced dipolar plasmon coupling to noncoupling in colloidal monolayers with interparticle distances of hundreds of nanometers, are demonstrated. Macroscopically sized, hexagonal monolayers with exceptionally high degrees of order are fabricated in one step. Time controls the interparticle spacing and no further processing is required.