Quantitative Optical and Structural Comparison of 3D and (2+1)D Colloidal Photonic Crystals.

Colloidal crystals are excellent model systems to study self-assembly and structural coloration because their periodicities coincide with the wavelength range of visible light. Different assembly methods inherently introduce characteristic defects and irregularities, even with nearly monodisperse colloidal particles. Here, we investigate how these imperfections influence the structural coloration by comparing two techniques to obtain colloidal crystals. 3D colloidal crystals produced by convective assembly are well-ordered and periodically arranged but show microscopic cracks. (2+1)D colloidal crystals fabricated by stacking individual monolayers show a decreased hexagonal order and limited crystal registration between single monolayers in the z-direction. We investigate the optical properties of both systems by comparing identical numbers of layers using correlative microspectroscopy. These measurements show that the less ordered (2+1)D colloidal crystals exhibit higher reflected light intensities. Macroscopic reflection integrating all angles shows that the reflected light intensity levels out with an increasing number of layers, whereas incoherent scattering increases. Although both types of colloidal crystal show similar angle-dependent color shifts in specular reflection, the less-ordered structure of the (2+1)D colloidal crystal scatters light within a larger angular range under diffusive illumination. Our results suggest that structural coloration is surprisingly robust toward local defects and irregularities.

How Colloidal Lithography Limits the Optical Quality of Plasmonic Nanohole Arrays.

Colloidal lithography utilizes self-assembled particle monolayers as lithographic masks to fabricate arrays of nanostructures by combination of directed evaporation and etching steps. This process provides complex nanostructures over macroscopic areas in a simple, convenient, and parallel fashion without requiring clean-room infrastructure and specialized equipment. The appeal of the method comes at the price of imperfections impairing the optical quality, especially for arrayed nanostructures relying on well-ordered lattices. Imperfections are often generically mentioned to rationalize the discrepancy between experimental and simulated resonances. Yet, little attention is given to detailed structure-property relationships connecting typical defects directly with the optical properties. Here, we use a correlative approach to connect nano- and microscopic defects occurring from the colloidal lithography process with the resulting local optical properties. We use nanohole arrays as a common plasmonic structure known to be sensitive to lattice imperfections. Correlative optical and electron microscopies reveal the individual role of packing order, organic impurities, and solid polymer bridges. Our findings show that simple cleaning processes with solvents and oxygen plasma already improve the optical quality but also highlight how well-controlled self-assembly processes are required for predictable optical properties of such nanostructures.

Coloration in Supraparticles Assembled from Polyhedral Metal-Organic Framework Particles.

Supraparticles are spherical colloidal crystals prepared by confined self-assembly processes. A particularly appealing property of these microscale structures is the structural color arising from interference of light with their building blocks. Here, we assemble supraparticles with high structural order that exhibit coloration from uniform, polyhedral metal-organic framework (MOF) particles. We analyse the structural coloration as a function of the size of these anisotropic building blocks and their internal structure. We attribute the angle-dependent coloration of the MOF supraparticles to the presence of ordered, onion-like layers at the outermost regions. Surprisingly, even though different shapes of the MOF particles have different propensities to form these onion layers, all supraparticle dispersions show well-visible macroscopic coloration, indicating that local ordering is sufficient to generate interference effects.

A Self-Ordered Nanostructured Transparent Electrode of High Structural Quality and Corresponding Functional Performance.

The preparation of a highly ordered nanostructured transparent electrode based on a combination of nanosphere lithography and anodization is presented. The size of perfectly ordered pore domains is improved by an order of magnitude with respect to the state of the art. The concomitantly reduced density of defect pores increases the fraction of pores that are in good electrical contact with the underlying transparent conductive substrate. This improvement in structural quality translates directly and linearly into an improved performance of energy conversion devices built from such electrodes in a linear manner.

Full Control of Plasmonic Nanocavities Using Gold Decahedra-on-Mirror Constructs with Monodisperse Facets.

Bottom-up assembly of nanoparticle-on-mirror (NPoM) nanocavities enables precise inter-metal gap control down to ≈ 0.4 nm for confining light to sub-nanometer scales, thereby opening opportunities for developing innovative nanophotonic devices. However limited understanding, prediction, and optimization of light coupling and the difficulty of controlling nanoparticle facet shapes restricts the use of such building blocks. Here, an ultraprecise symmetry-breaking plasmonic nanocavity based on gold nanodecahedra is presented, to form the nanodecahedron-on-mirror (NDoM) which shows highly consistent cavity modes and fields. By characterizing > 20 000 individual NDoMs, the variability of light in/output coupling is thoroughly explored and a set of robust higher-order plasmonic whispering gallery modes uniquely localized at the edges of the triangular facet in contact with the metallic substrate is found. Assisted by quasinormal mode simulations, systematic elaboration of NDoMs is proposed to give nanocavities with near hundred-fold enhanced radiative efficiencies. Such systematically designed and precisely-assembled metallic nanocavities will find broad application in nanophotonic devices, optomechanics, and surface science.

Chiral Plasmonic Shells: High-Performance Metamaterials for Sensitive Chiral Biomolecule Detection.

Low-cost and large-area chiral metamaterials (CMs) are highly desirable for practical applications in chiral biosensors, nanophotonic chiral emitters, and beyond. A promising fabrication method takes advantage of self-assembled colloidal particles, onto which metal patches with defined orientation are created using glancing angle deposition (GLAD). However, using this method to make uniform and well-defined CMs over macroscopic areas is challenging. Here, we fabricate a uniform large-area colloidal particle array by interface-mediated self-assembly and precisely control the structural handedness of chiral plasmonic shells (CPSs) using GLAD. Strong chiroptical signals arise from twisted currents at the main, corner, and edge of CPSs, allowing a balance between strong chiroptical and high transmittance properties. Our shell-like chiral geometry shows excellent sensor performance in detecting chiral molecules due to the formation of uniform superchiral fields. Systematic investigations optimize the interplay between peak and null point resonances in different CPSs and result in a record consistency chiral sensor parameter U, i.e., 3.77 for null points and 0.0867 for peaks, which are about 54 and 1.257 times larger than the highest value (0.068) of previously reported CMs. The geometrical chirality, surface plasmonic resonance, chiral surface lattice resonance, and chiral sensor performance evidence the chiroptical effect and the excellent chiral sensor performance.

Addressing the plasmonic hotspot region by site-specific functionalization of nanostructures.

Strong electromagnetic fields emerge around resonant plasmonic nanostructures, focusing the light in tiny volumes, usually referred to as hotspots. These hotspots are the key regions governing plasmonic applications since they strongly enhance properties, signals or energies arising from the interaction with light. For a maximum efficiency, target molecules or objects would be exclusively placed within hotspot regions. Here, we propose a reliable, universal and high-throughput method for the site-specific functionalization of hotspot regions over macroscopic areas. We demonstrate the feasibility of the approach using crescent-shaped nanostructures, which can be fabricated using colloidal lithography. These structures feature polarization-dependent resonances and near-field enhancement at their tips, which we use as target regions for the site-selective functionalization. We modify the fabrication process and introduce a defined passivation layer covering the central parts of the gold nanocrescent, which, in turn, selectively uncovers the tips and thus enables a localized functionalization with thiol molecules. We demonstrate and visualize a successful targeting of the hotspot regions by binding small gold nanoparticles and show a targeting efficiency of 90%. Finally, we demonstrate the versatility of the method exemplarily by translating the principle to different nanostructure geometries and architectures.

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.

Spatioselective Deposition of Passivating and Electrocatalytic Layers on Silicon Nanowire Arrays.

Metal-silicon nanowire array photoelectrodes provide a promising architecture for water-splitting because they can afford high catalyst loading and decouple charge separation from the light absorption process. To further improve and understand these hybrid nanowire photoelectrodes, control of the catalyst amount and location within the wire array is required. Such a level of control is currently synthetically challenging to achieve. Here, we report the synthesis of cm2-sized hybrid silicon nanowire arrays with electrocatalytically active Ni-Mo and Pt patches placed at defined vertical locations within the individual nanowires. Our method is based on a modified three-dimensional electrochemical axial lithography (3DEAL), which combines metal-assisted chemical etching (MACE) to produce Si nanowires with spatially defined SiO2 protection layers to selectively cover and uncover specific areas within the nanowire arrays. This spatioselective SiO2 passivation yields nanowire arrays with well-defined exposed Si surfaces, with feature sizes down to 100 nm in the axial direction. Subsequent electrodeposition directs the growth of the metal catalysts at the exposed silicon surfaces. As a proof of concept, we report photoelectrocatalytic activity of the deposited catalysts for the hydrogen evolution reaction on p-type Si nanowire photocathodes. This demonstrates the functionality of these hybrid metal/Si nanowire arrays patterned via 3DEAL, which paves the way for investigations of the influence of three-dimensional geometrical parameters on the conversion efficiency of nanostructured photoelectrodes interfaced with metal catalysts.

Bioinspired Photonic Pigments from Colloidal Self-Assembly.

The natural world is a colorful environment. Stunning displays of coloration have evolved throughout nature to optimize camouflage, warning, and communication. The resulting flamboyant visual effects and remarkable dynamic properties, often caused by an intricate structural design at the nano- and microscale, continue to inspire scientists to unravel the underlying physics and to recreate the observed effects. Here, the methodologies to create bioinspired photonic pigments using colloidal self-assembly approaches are considered. The physics governing the interaction of light with structural features and natural examples of structural coloration are briefly introduced. It is then outlined how the self-assembly of colloidal particles, acting as wavelength-scale building blocks, can be particularly useful to replicate coloration from nature. Different coloration effects that result from the defined structure of the self-assembled colloids are introduced and it is highlighted how these optical properties can be translated into photonic pigments by modifications of the assembly processes. The importance of absorbing elements, as well as the role of surface chemistry and wettability to control structural coloration is discussed. Finally, approaches to integrate dynamic control of coloration into such self-assembled photonic pigments are outlined.

Surface Patterning with SiO2@PNiPAm Core-Shell Particles.

Colloidal lithography is a cost-efficient method to produce large-scale nanostructured arrays on surfaces. Typically, colloidal particles are assembled into hexagonal close-packed monolayers at liquid interfaces and deposited onto a solid substrate. Many applications, however, require non close-packed monolayers, which are more difficult to fabricate. Preassembly at the oil/water interface provides non close-packed colloidal assemblies but these are difficult to transfer to a solid substrate without compromising the ordering due to capillary forces acting upon drying. Alternatively, plasma etching can reduce a close-packed monolayer into a non close-packed arrangement, however, with limited interparticle distance and compromised particle shape. Here, we present a simple alternative approach toward non close-packed colloidal monolayers with tailored interparticle distance, high order, and retained spherical particle shape. We preassemble poly(N-isopropylacrylamide)-silica (SiO2@PNiPAm) core-shell particles at the air/water interface, transfer the interfacial spacer to a solid substrate, and use the polymer shell as a sacrificial layer that can be thermally removed to leave a non close-packed silica monolayer. The shell thickness, cross-linking density, and the phase behavior upon compression of these complex particles at the air/water interface provide parameters to precisely control the lattice spacing in these surface nanostructures. We achieve hexagonal non close-packed arrays of silica spheres with interparticle distances between 400 and 1280 nm, up to 8 times their diameter. The retained spherical shape is advantageous for surface nanostructuring, which we demonstrate by the fabrication of gold nanocrescent arrays via colloidal lithography and silicon nanopillar arrays via metal-assisted chemical etching.