Prismatic Confinement Induces Tunable Orientation in Plasmonic Supercrystals.

Throughout history scientists have looked to Nature for inspiration and attempted to replicate intricate complex structures formed by self-assembly. In the context of synthetic supercrystals, achieving such complexity remains a challenge due to the highly symmetric nature of most nanoparticles (NPs). Previous works have shown intricate coupling between the self-assembly of NPs and confinement in templates, such as emulsion droplets (spherical confinement) or tubes (cylindrical confinement). This study focuses on the interplay between anisotropic NP shape and tunable "prismatic confinement" leading to the self-assembly of supercrystals in cavities featuring polygonal cross sections. A multiscale characterization strategy is employed to investigate the orientation and structure of the supercrystals locally and at the ensemble level. Our findings highlight the role of the mold interface in guiding the growth of distinct crystal domains: each side of the mold directs the formation of a monodomain that extends until it encounters another, leading to the creation of grain boundaries. Computer simulations in smaller prismatic cavities were conducted to predict the effect of an increased confinement. Comparison between prismatic and cylindrical confinements shows that flat interfaces are key to orienting the growth of supercrystals. This work shows a method of inducing orientation in plasmonic supercrystals and controlling their textural defects, thus offering insight into the design of functional metasurfaces and hierarchically structured devices.

Confinement Effects on the Structure of Entropy-Induced Supercrystals.

Depletion-induced self-assembly is routinely used to separate plasmonic nanoparticles (NPs) of different shapes, but less often for its ability to create supercrystals (SCs) in suspension. Therefore, these plasmonic assemblies have not yet reached a high level of maturity and their in-depth characterization by a combination of in situ techniques is still very much needed. In this work, gold triangles (AuNTs) and silver nanorods (AgNRs) are assembled by depletion-induced self-assembly. Small Angle X-ray Scattering (SAXS) and scanning electron microscopy (SEM) analysis shows that the AuNTs and AgNRs form 3D and 2D hexagonal lattices in bulk, respectively. The colloidal crystals are also imaged by in situ Liquid-Cell Transmission Electron Microscopy. Under confinement, the affinity of the NPs for the liquid cell windows reduces their ability to stack perpendicularly to the membrane and lead to SCs with a lower dimensionality than their bulk counterparts. Moreover, extended beam irradiation leads to disassembly of the lattices, which is well described by a model accounting for the desorption kinetics highlighting the key role of the NP-membrane interaction in the structural properties of SCs in the liquid-cell. The results shed light on the reconfigurability of NP superlattices obtained by depletion-induced self-assembly, which can rearrange under confinement.

Extracting the morphology of gold bipyramids from small-angle X-ray scattering experiments via form factor modelling.

Accurate shape description is a challenge in materials science. Small-angle X-ray scattering (SAXS) can provide the shape, size and polydispersity of nanoparticles by form factor modelling. However, simple geometric models such as the ellipsoid may not be enough to describe objects with complex shapes. This work shows that the form factor of gold nanobipyramids is accurately described by a truncated bicone model, which is validated by comparison with transmission electron microscopy (TEM) data for nine different synthesis batches; the average shape parameters (width, height and truncation) and the sample polydispersity are obtained. In contrast, the ellipsoid model yields worse fits of the SAXS data and exhibits systematic discrepancies with the TEM results.

Polymorphous Packing of Pentagonal Nanoprisms.

Packing solid shapes into regular lattices can yield very complex assemblies, not all of which achieve the highest packing fraction. In two dimensions, the regular pentagon is paradigmatic, being the simplest shape that does not pave the plane completely. In this work, we demonstrate the packing of plasmonic nanoprisms with pentagonal cross section, which form extended supercrystals. We do encounter the long-predicted ice-ray and Dürer packings (with packing fractions of 0.921 and 0.854, respectively) but also a variety of novel polymorphs that can be obtained from these two configurations by a continuous sliding transformation and exhibit an intermediate packing fraction. Beyond the fundamental interest of this result, fine control over the density and symmetry of such plasmonic assemblies opens the perspective of tuning their optical properties, with potential applications in metamaterial fabrication, catalysis, or molecular detection.

Formation of kinetically trapped small clusters of PEGylated gold nanoparticles revealed by the combination of small-angle X-ray scattering and visible light spectroscopy.

Gold nanoparticles coated with polyethylene glycol (PEG) are able to form clusters due to the collapse of the surface-grafted polymer chains when the temperature and ion concentration of the aqueous medium are increased. The chain collapse reduces the steric repulsion, leading to particle aggregation. In this work, we combine small angle X-ray scattering (SAXS) and visible light spectroscopy to elucidate the structure of the developing clusters. The structure derived from the SAXS measurements reveals a decrease in interparticle distance and drastic narrowing of its distribution in the cluster, indicating restricted particle mobility and displacement within the cluster. Surprisingly, instead of forming a large crystalline phase, the evolving clusters are composed of about a dozen particles. The experimental optical extinction spectra measured during cluster formation can be very well reproduced by optical simulations based on the SAXS-derived structural data.

Double-Lattice Packing of Pentagonal Gold Bipyramids in Supercrystals with Triclinic Symmetry.

Pentagonal packing is a long-standing issue and a rich mathematical topic, brought to the fore by recent progress in nanoparticle design. Gold pentagonal bipyramids combine fivefold symmetry and anisotropy and their section varies along the length. In this work, colloidal supercrystals of pentagonal gold bipyramids are obtained in a compact arrangement that generalizes the optimal packing of regular pentagons in the plane. Multimodal investigations reveal a two-particle unit cell with triclinic symmetry, a lower symmetry than that of the building blocks. Monte Carlo computer simulations show that this lattice achieves the densest possible packing. Going beyond pentagons, further simulations show an odd-even effect of the number of sides on the packing: odd-sided bipyramids are non-centrosymmetric and require the double-lattice arrangement to recover inversion symmetry. The supercrystals display a facet-dependent optical response that is promising for sensing, metamaterials applications, and for fundamental studies of self-assembly processes.

Unveiling the Coupling of Single Metallic Nanoparticles to Whispering-Gallery Microcavities.

Whispering-gallery mode resonators host multiple trapped narrow-band circulating optical resonances that find applications in quantum electrodynamics, optomechanics, and sensing. However, the spherical symmetry and low field leakage of dielectric microspheres make it difficult to probe their high-quality optical modes using far-field radiation. Even so, local field enhancement from metallic nanoparticles (MNPs) coupled to the resonators can interface the optical far field and the bounded cavity modes. In this work, we study the interaction between whispering-gallery modes and MNP surface plasmons with nanometric spatial resolution by using electron-beam spectroscopy with a scanning transmission electron microscope. We show that gallery modes are induced over a selective spectral range of the nanoparticle plasmons, and additionally, their polarization can be controlled by the induced dipole moment of the MNP. Our study demonstrates a viable mechanism to effectively excite high-quality-factor whispering-gallery modes and holds potential for applications in optical sensing and light manipulation.

Gold-clay nanocomposite colloids with liquid-crystalline and plasmonic properties.

Imparting liquid-crystal (LC) materials with the plasmonic properties of metal nanoparticles is actively pursued for applications. We achieved this goal by synthetizing gold nanoparticles onto clay nanosheets, leading to nematic nanocomposite suspensions. Optical observations and structural analysis show the growth of the gold nanoparticles without altering the LC properties of the nanosheets. These colloids display plasmonic structural colours and they can be aligned by an electric field, which is relevant for fundamental and materials chemistry of colloidal LC.

Doping Liquid Crystals of Colloidal Inorganic Nanotubes by Additive-Free Metal Nanoparticles.

Doping liquid-crystal phases with nanoparticles is a fast-growing field with potential breakthroughs due to the combination of the properties brought by the two components. One of the main challenges remains the long-term stability of the hybrid system, requiring complex functionalization of the nanoparticles at the expense of their self-assembly properties. Here we demonstrate the successful synthesis of additive-free noble-metal nanoparticles at the surface of charged inorganic nanotubes. Transmission electron microscopy and UV-visible spectroscopy confirm the stabilization of metallic nanoparticles on nanotubes. Meanwhile, the spontaneous formation of liquid-crystals phases induced by the nanotubes is observed, even after surface modification with metallic nanoparticles. Small-angle X-ray scattering experiments reveal that the average interparticle distance in the resulting hybrids can be easily modulated by controlling electrostatic interactions. As a proof-of-concept, we demonstrate the effectiveness of our method for the preparation of homogeneous transparent hybrid films with a high degree of alignment.

Real-Time In Situ Observations Reveal a Double Role for Ascorbic Acid in the Anisotropic Growth of Silver on Gold.

Rational nanoparticle design is one of the main goals of materials science, but it can only be achieved via a thorough understanding of the growth process and of the respective roles of the molecular species involved. We demonstrate that a combination of complementary techniques can yield novel information with respect to their individual contributions. We monitored the growth of long aspect ratio silver rods from gold pentatwinned seeds by three in situ techniques (small-angle X-ray scattering, optical extinction spectroscopy and liquid-cell transmission electron microscopy). Exploiting the difference in reaction speed between the bulk synthesis and the nanoparticle formation in the TEM cell, we show that the anisotropic growth is thermodynamically controlled (rather than kinetically) and that ascorbic acid, widely used for its mild reductive properties, plays a shape-directing role, by stabilizing the {100} facets of the silver cubic lattice, in synergy with the halide ions. This approach can easily be applied to a wide variety of synthesis strategies.

Determining the morphology and concentration of core-shell Au/Ag nanoparticles.

Accurately measuring the shape, structure and concentration of nanoparticles (NPs) is a crucial step towards understanding their formation and a prerequisite for any applications. While determining these parameters for single-metal NPs is by now rather routine, reliably characterizing bimetallic NPs is still a challenge. Using four complementary techniques: transmission electron microscopy (TEM), light absorbance spectroscopy (AS), small-angle X-ray scattering (SAXS) and inductively coupled plasma mass spectrometry (ICP-MS) we study bimetallic nanoparticles obtained by growing a silver shell on top of a gold seed. The initial quasi-spherical objects become faceted and grow into a rounded cube as the molar silver-to-gold ratio K increases. The shape evolution is well described by SAXS and TEM. The shell thickness, overall size polydispersity and number particle concentration obtained by the various methods are in good agreement, validating the use of non-invasive in situ techniques such as AS and SAXS for the study of bimetallic NPs.

Plasmonic Oligomers with Tunable Conductive Nanojunctions.

Engineering plasmonic hot spots is essential for applications of plasmonic nanoparticles. A particularly appealing route is to weld plasmonic nanoparticles together to form more complex structures sustaining plasmons with symmetries targeted to given applications. However, control of the welding and subsequent hot spot characteristics is still challenging. Herein, we demonstrate an original method that connects gold particles to their neighbors by another metal of choice. We first assemble gold bipyramids in a tip-to-tip configuration, yielding short chains of variable length, and grow metallic junctions in a second step. We follow the chain formation and the deposition of the second metal (i.e., silver or palladium) via UV/vis spectroscopy, and we map the plasmonic properties using electron energy loss spectroscopy. The formation of silver bridges leads to a huge red shift of the longitudinal plasmon modes into the mid-infrared region, while the addition of palladium results in a red shift accompanied by significant plasmon damping.

Controlling the symmetry of supercrystals formed by plasmonic core-shell nanorods with tunable cross-section.

Tailoring the crystal structure of plasmonic nanoparticle superlattices is a crucial step in controlling the collective physical response of these nanostructured materials. Various strategies can achieve this goal for isotropic nanoparticles, but few of them have been successful with anisotropic building blocks. In this work we use hybrid particles, consisting of gold nanorods encased in silver shells with a thickness that can be controlled from a few atomic layers to tens of nanometers. The particles were synthesized, characterized by a combination of techniques and assembled into supercrystals with a smectic B configuration, i.e. a 2D in-plane periodic order without interplane lateral correlations. We showed that, by tuning the silver shell thickness, the in-plane order can be changed from hexagonal to square and the lattice parameters can be adjusted. The spatial distribution of the supercrystal was systematically studied by optical and electron microscopy and by small-angle X-ray scattering. Through optimized surface chemistry, we obtain homogeneous, millimeter-size films of standing nanoparticles, which hold promise for all applications using plasmon-enhanced technologies.

Colloidal design of plasmonic sensors based on surface enhanced Raman scattering.

This feature article focuses on the use of colloid chemistry to engineer metallic nanostructures toward application in surface enhanced Raman scattering (SERS) sensing, in particular for 'real-life' applications, where the analyte may be present in complex mixtures. We present a broad summary of the field, including recent advances that have been developed during the past 10 years. Real-life applications require a rational design and we aimed at identifying the key elements involved in it. The discussion is centered around colloidal plasmonic nanoparticles and therefore we start from the library of morphologies that have been reported in the literature. To complete the picture, colloidal self-assembly, surface chemistry and the combination with materials science techniques are highlighted. Considering the progress in the field, SERS may ultimately realize its full potential as an ultrasensitive tool for routine analytical applications.

Detection and imaging of quorum sensing in Pseudomonas aeruginosa biofilm communities by surface-enhanced resonance Raman scattering.

Most bacteria in nature exist as biofilms, which support intercellular signalling processes such as quorum sensing (QS), a cell-to-cell communication mechanism that allows bacteria to monitor and respond to cell density and changes in the environment. As QS and biofilms are involved in the ability of bacteria to cause disease, there is a need for the development of methods for the non-invasive analysis of QS in natural bacterial populations. Here, by using surface-enhanced resonance Raman scattering spectroscopy, we report rationally designed nanostructured plasmonic substrates for the in situ, label-free detection of a QS signalling metabolite in growing Pseudomonas aeruginosa biofilms and microcolonies. The in situ, non-invasive plasmonic imaging of QS in biofilms provides a powerful analytical approach for studying intercellular communication on the basis of secreted molecules as signals.

Hierarchical organization and molecular diffusion in gold nanorod/silica supercrystal nanocomposites.

Hierarchical organization of gold nanorods was previously obtained on a substrate, allowing precise control over the morphology of the assemblies and macroscale spatial arrangement. Herein, a thorough description of these gold nanorod assemblies and their orientation within supercrystals is presented together with a sol-gel technique to protect the supercrystals with mesoporous silica films. The internal organization of the nanorods in the supercrystals was characterized by combining focused ion beam ablation and scanning electron microscopy. A mesoporous silica layer is grown both over the supercrystals and between the individual lamellae of gold nanorods inside the structure. This not only prevented the detachment of the supercrystal from the substrate in water, but also allowed small molecule analytes to infiltrate the structure. These nanocomposite substrates show superior Raman enhancement in comparison with gold supercrystals without silica owing to improved accessibility of the plasmonic hot spots to analytes. The patterned supercrystal arrays with enhanced optical and mechanical properties obtained in this work show potential for the practical implementation of nanostructured devices in spatially resolved ultradetection of biomarkers and other analytes.

Hierarchical Assembly of Plasmonic Nanoparticles.

In this Minireview, we summarize recent advances in the ordering of plasmonic nanoparticles over extended areas on solid substrates. The spotlight is thus focused on examples showing one-, two-, and three-dimensional assemblies, with a particular attention on assemblies displaying hierarchical order. Throughout the manuscript we identify the main parameters and methods that can be tuned to achieve long range organization.

Collective Plasmonic Properties in Few-Layer Gold Nanorod Supercrystals.

Gold nanorod supercrystals have been widely employed for the detection of relevant bioanalytes with detection limits ranging from nano- to picomolar levels, confirming the promising nature of these structures for biosensing. Even though a relationship between the height of the supercrystal (i.e., the number of stacked nanorod layers) and the enhancement factor has been proposed, no systematic study has been reported. In order to tackle this problem, we prepared gold nanorod supercrystals with varying numbers of stacked layers and analyzed them extensively by atomic force microscopy, electron microscopy and surface enhanced Raman scattering. The experimental results were compared to numerical simulations performed on real-size supercrystals composed of thousands of nanorod building blocks. Analysis of the hot spot distribution in the simulated supercrystals showed the presence of standing waves that were distributed at different depths, depending on the number of layers in each supercrystal. On the basis of these theoretical results, we interpreted the experimental data in terms of analyte penetration into the topmost layer only, which indicates that diffusion to the interior of the supercrystals would be crucial if the complete field enhancement produced by the stacked nanorods is to be exploited. We propose that our conclusions will be of high relevance in the design of next generation plasmonic devices.

Hierarchical self-assembly of gold nanoparticles into patterned plasmonic nanostructures.

The integration of nanoparticle superstructures into daily life applications faces major challenges including the simplification of the self-assembly process, reduced cost, and scalability. It is, however, often difficult to improve on one aspect without losing on another. We present in this paper a benchtop method that allows patterning a macroscopic substrate with gold nanoparticle supercrystals in a one-step process. The method allows parallelization, and patterned substrates can be made with high-throughput. The self-assembly of a variety of building blocks into crystalline superstructures takes place upon solvent evaporation, and their precise placement over millimeter scale areas is induced by confinement of the colloidal suspension in micron-sized cavities. We mainly focus on gold nanorods and demonstrate their hierarchical organization up to the device scale. The height of the formed nanorod supercrystals can be tuned by simply varying nanorod concentration, so that the topography of the substrate and the resulting optical properties can be readily modulated. The crystalline order of the nanorods results in homogeneous and high electric field enhancements over the assemblies, which is demonstrated by surface-enhanced Raman scattering spectroscopy.

Peptidic ligands to control the three-dimensional self-assembly of quantum rods in aqueous media.

The use of peptidic ligands is validated as a generic chemical platform allowing one to finely control the organization in solid phase of semiconductor nanorods originally dispersed in an aqueous media. An original method to generate, on a macroscopic scale and with the desired geometry, three-dimensional supracrystals composed of quantum rods is introduced. In a first step, nanorods are transferred in an aqueous phase thanks to the substitution of the original capping layer by peptidic ligands. Infrared and nuclear magnetic resonance spectroscopy data prove that the exchange is complete; fluorescence spectroscopy demonstrates that the emitter optical properties are not significantly altered; electrophoresis and dynamic light scattering experiments assess the good colloidal stability of the resulting aqueous suspension. In a second step, water evaporation in a microstructured environment yields superstructures with a chosen geometry and in which nanorods obey a smectic B arrangement, as shown by electron microscopy. Incidentally, bulk drying in a capillary tube generates a similar local order, as evidenced by small angle X-ray scattering.