Colloidal quasicrystals engineered with DNA.

In principle, designing and synthesizing almost any class of colloidal crystal is possible. Nonetheless, the deliberate and rational formation of colloidal quasicrystals has been difficult to achieve. Here we describe the assembly of colloidal quasicrystals by exploiting the geometry of nanoscale decahedra and the programmable bonding characteristics of DNA immobilized on their facets. This process is enthalpy-driven, works over a range of particle sizes and DNA lengths, and is made possible by the energetic preference of the system to maximize DNA duplex formation and favour facet alignment, generating local five- and six-coordinated motifs. This class of axial structures is defined by a square-triangle tiling with rhombus defects and successive on-average quasiperiodic layers exhibiting stacking disorder which provides the entropy necessary for thermodynamic stability. Taken together, these results establish an engineering milestone in the deliberate design of programmable matter.

Temperature-Modulated Reversible Clustering of Gold Nanorods Driven by Small Surface Ligands.

Temperature-modulated colloidal phase of plasmonic nanoparticles is a convenient playground for resettable soft-actuators or colorimetric sensors. To render reversible clustering under temperature change, bulky ligands are required, especially if anisotropic morphologies are of interest. This study showcases thermoresponsive gold nanorods by employing small surface ligands, bis (p-sulfonatophenyl) phenyl-phosphine dihydrate dipotassium salt (BSPP) and native cationic surfactant. Temperature-dependent analysis in real-time allowed to describe the structural features (interparticle distance and cluster size) as well as thermal parameters, melting and freezing temperatures. These findings suggest that neither covalent Au-S bonds nor bulky ligands are required to obtain a robust thermoresponsive system based on anisotropic gold nanoparticles, paving the way to stimuli-responsive nanoparticles with a wide range of sizes and geometries.

The Influence of Size, Shape, and Twin Boundaries on Heat-Induced Alloying in Individual Au@Ag Core-Shell Nanoparticles.

Environmental conditions during real-world application of bimetallic core-shell nanoparticles (NPs) often include the use of elevated temperatures, which are known to cause elemental redistribution, in turn significantly altering the properties of these nanomaterials. Therefore, a thorough understanding of such processes is of great importance. The recently developed combination of fast electron tomography with in situ heating holders is a powerful approach to investigate heat-induced processes at the single NP level, with high spatial resolution in 3D. In combination with 3D finite-difference diffusion simulations, this method can be used to disclose the influence of various NP parameters on the diffusion dynamics in Au@Ag core-shell systems. A detailed study of the influence of heating on atomic diffusion and alloying for Au@Ag NPs with varying core morphology and crystallographic details is carried out. Whereas the core shape and aspect ratio of the NPs play a minor role, twin boundaries are found to have a strong influence on the elemental diffusion.

Three-Dimensional Quantification of the Facet Evolution of Pt Nanoparticles in a Variable Gaseous Environment.

Pt nanoparticles play an essential role in a wide variety of catalytic reactions. The activity of the particles strongly depends on their three-dimensional (3D) structure and exposed facets, as well as on the reactive environment. High-resolution electron microscopy has often been used to characterize nanoparticle catalysts but unfortunately most observations so far have been either performed in vacuum and/or using conventional (2D) in situ microscopy. The latter however does not provide direct 3D morphological information. We have implemented a quantitative methodology to measure variations of the 3D atomic structure of nanoparticles under the flow of a selected gas. We were thereby able to quantify refaceting of Pt nanoparticles with atomic resolution during various oxidation-reduction cycles. In a H2 environment, a more faceted surface morphology of the particles was observed with {100} and {111} planes being dominant. On the other hand, in O2 the percentage of {100} and {111} facets decreased and a significant increase of higher order facets was found, resulting in a more rounded morphology. This methodology opens up new opportunities toward in situ characterization of catalytic nanoparticles because for the first time it enables one to directly measure 3D morphology variations at the atomic scale in a specific gaseous reaction environment.

Strong Magneto-Optical Response of Nonmagnetic Organic Materials Coupled to Plasmonic Nanostructures.

Plasmonic nanoparticles (PNPs) can significantly modify the optical properties of nearby organic molecules and thus present an attractive opportunity for sensing applications. However, the utilization of PNPs in conventional absorption, fluorescence, or Raman spectroscopy techniques is often ineffective due to strong absorption background and light scattering, particularly in the case of turbid solutions, cell suspensions, and biological tissues. Here we show that nonmagnetic organic molecules may exhibit magneto-optical response due to binding to a PNP. Specifically, we detect strong magnetic circular dichroism signal from supramolecular J-aggregates, a representative organic dye, upon binding to silver-coated gold nanorods. We explain this effect by strong coupling between the J-aggregate exciton and the nanoparticle plasmon, leading to the formation of a hybrid state in which the exciton effectively acquires magnetic properties from the plasmon. Our findings are fully corroborated by theoretical modeling and constitute a novel magnetic method for chemo- and biosensing, which (upon adequate PNP functionalization) is intrinsically insensitive to the organic background and thus offers a significant advantage over conventional spectroscopy techniques.

Reversible Clustering of Gold Nanoparticles under Confinement.

A limiting factor of solvent-induced nanoparticle self-assembly is the need for constant sample dilution in assembly/disassembly cycles. Changes in the nanoparticle concentration alter the kinetics of the subsequent assembly process, limiting optical signal recovery. Herein, we show that upon confining hydrophobic nanoparticles in permeable silica nanocapsules, the number of nanoparticles participating in cyclic aggregation remains constant despite bulk changes in solution, leading to highly reproducible plasmon band shifts at different solvent compositions.

High-Yield Seeded Growth of Monodisperse Pentatwinned Gold Nanoparticles through Thermally Induced Seed Twinning.

We show that thermal treatment of small Au seeds results in extensive twinning and a subsequent drastic improvement in the yield (>85%) of formation of pentatwinned nanoparticles (NPs), with preselected morphology (nanorods, bipyramids, and decahedra) and aspect ratio. The "quality" of the seeds thus defines the yield of the obtained NPs, which in the case of nanorods avoids the need for additives such as Ag+ ions. This modified seeded growth method also improves reproducibility, as the seeds can be stored for extended periods of time without compromising the quality of the final NPs. Additionally, minor modification of the seeds with Pd allows their localization within the final particles, which opens new avenues toward mechanistic studies. Together, these results represent a paradigm shift in anisotropic gold NP synthesis.

Measuring Lattice Strain in Three Dimensions through Electron Microscopy.

The three-dimensional (3D) atomic structure of nanomaterials, including strain, is crucial to understand their properties. Here, we investigate lattice strain in Au nanodecahedra using electron tomography. Although different electron tomography techniques enabled 3D characterizations of nanostructures at the atomic level, a reliable determination of lattice strain is not straightforward. We therefore propose a novel model-based approach from which atomic coordinates are measured. Our findings demonstrate the importance of investigating lattice strain in 3D.

Glycans as biofunctional ligands for gold nanorods: stability and targeting in protein-rich media.

Poly(ethylene glycol) (PEG) has become the gold standard for stabilization of plasmonic nanoparticles (NPs) in biofluids, because it prevents aggregation while minimizing unspecific interactions with proteins. Application of Au NPs in biological environments requires the use of ligands that can target selected receptors, even in the presence of protein-rich media. We demonstrate here the stabilizing effect of low-molecular-weight glycans on both spherical and rod-like plasmonic NPs under physiological conditions, as bench-marked against the well-established PEG ligands. Glycan-coated NPs are resistant to adsorption of proteins from serum-containing media and avoid phagocytosis by macrophage-like cells, but retain selectivity toward carbohydrate-binding proteins in protein-rich biological media. These results open the way toward the design of efficient therapeutic/diagnostic glycan-decorated plasmonic nanotools for specific biological applications.

Quantum dot thermometry evaluation of geometry dependent heating efficiency in gold nanoparticles.

Quantum dot based thermometry, in combination with double beam confocal microscopy, was used to investigate the absorption/heating efficiency of gold nanoparticles with different morphologies (nanorods, nanocages, nanoshells, and nanostars), all of them with an intense localized surface plasmon resonance within the first biological window, at around 808 nm. The heating efficiency was found to be strongly dependent on the geometry of the nanostructure, with the largest values found for gold nanorods and long-edge gold nanostars, both of them with heating efficiencies close to 100%. Gold nanorods and nanocages were found to have the largest absorption cross section per unit mass among all the studied geometries, emerging as optimum photothermal agents with minimum metal loading for biosystems.

Quantifying Shape Transition in Anisotropic Plasmonic Nanoparticles through Geometric Inversion. Application to Gold Bipyramids.

Unraveling the nuanced interplay between the morphology and the optical properties of plasmonic nanoparticles is crucial for targeted applications. Managing the relationship becomes significantly complex when dealing with anisotropic nanoparticles that defy a simple description using parameters like length, width, or aspect ratio. This complexity requires computationally intensive numerical modeling and advanced imaging techniques. To address these challenges, we propose a detailed structural parameter determination of gold nanoparticles using their two-dimensional projections (e.g., micrographs). Employing gold bipyramids (AuBPs) as a model morphology, we can determine their three-dimensional geometry and extract optical features computationally for comparison with the experimental data. To validate our inversion model's effectiveness, we apply it to derive the structural parameters of AuBPs undergoing shape modification through oxidative etching. In summary, our findings allow for the precise characterization of structural parameters for plasmonic nanoparticles during shape transitions, potentially enhancing the comprehension of nanocrystal growth and optimizing plasmonic material design for various applications.

Direct visualization of ligands on gold nanoparticles in a liquid environment.

The interactions between gold nanoparticles, their surface ligands and the solvent critically influence the properties of these nanoparticles. Although spectroscopic and scattering techniques have been used to investigate their ensemble structure, a comprehensive understanding of these processes at the nanoscale remains challenging. Electron microscopy makes it possible to characterize the local structure and composition but is limited by insufficient contrast, electron beam sensitivity and the requirement for ultrahigh-vacuum conditions, which prevent the investigation of dynamic aspects. Here we show that, by exploiting high-quality graphene liquid cells, we can overcome these limitations and investigate the structure of the ligand shell around gold nanoparticles and at the ligand-gold interface in a liquid environment. Using this graphene liquid cell, we visualize the anisotropy, composition and dynamics of ligand distribution on gold nanorod surfaces. Our results indicate a micellar model for surfactant organization. This work provides a reliable and direct visualization of ligand distribution around colloidal nanoparticles.

Enhanced Photocurrent and Electrically Pumped Quantum Dot Emission from Single Plasmonic Nanoantennas.

Integrating cavity-enhanced colloidal quantum dots (QDs) into photonic chip devices would be transformative for advancing room-temperature optoelectronic and quantum photonic technologies. However, issues with efficiency, stability, and cost remain formidable challenges to reach the single antenna limit. Here, we present a bottom-up approach that delivers single QD-plasmonic nanoantennas with electrical addressability. These QD nanojunctions exhibit robust photoresponse characteristics, with plasmonically enhanced photocurrent spectra matching the QD solution absorption. We demonstrate electroluminescence from individual plasmonic nanoantennas, extending the device lifetime beyond 40 min by utilizing a 3 nm electron-blocking polymer layer. In addition, we reveal a giant voltage-dependent redshift of up to 62 meV due to the quantum-confined Stark effect and determine the exciton polarizability of the CdSe QD monolayer to be 4 × 10-5 meV/(kV/cm)2. These developments provide a foundation for accessing scalable quantum light sources and high-speed, tunable optoelectronic systems operating under ambient conditions.

Highly transparent and conductive films of densely aligned ultrathin Au nanowire monolayers.

The combination of low electrical resistance and high optical transparency in a single material is very uncommon. Developing these systems is a scientific challenge and a technological need, to replace ITO in flexible electronic components and other highly demanding applications. Here we report a facile method to prepare single layers of densely aligned ultrathin Au-nanowires, homogeneous over cm(2) areas. The as-deposited films show an electrical/optical performance competitive with ITO and graphene-based electrodes. Moreover, the Au-films show a good stability under ambient conditions, and the large aspect ratio of the ultrathin nanowires makes them perfect for deposition in flexible substrates.

Steric hindrance induces crosslike self-assembly of gold nanodumbbells.

In the formation of colloidal molecules, directional interactions are crucial for controlling the spatial distribution of the building blocks. Anisotropic nanoparticles facilitate directional clustering via steric constraints imposed by each specific shape, thereby restricting assembly along certain directions. We show in this Letter that the combination of patchiness (attraction) and shape (steric hindrance) allows assembling gold nanodumbbell building blocks into crosslike dimers with well-controlled interparticle distance and relative orientation. Steric hindrance between interacting dumbbell-like particles opens up a new synthetic approach toward low-symmetry plasmonic clusters, which may significantly contribute to understand complex plasmonic phenomena.

Behavior of Au Nanoparticles under Pressure Observed by In Situ Small-Angle X-ray Scattering.

The mechanical properties and stability of metal nanoparticle colloids under high-pressure conditions are investigated by means of optical extinction spectroscopy and small-angle X-ray scattering (SAXS), for colloidal dispersions of gold nanorods and gold nanospheres. SAXS allows us to follow in situ the structural evolution of the nanoparticles induced by pressure, regarding both nanoparticle size and shape (form factor) and their aggregation through the interparticle correlation function S(q) (structure factor). The observed behavior changes under hydrostatic and nonhydrostatic conditions are discussed in terms of liquid solidification processes yielding nanoparticle aggregation. We show that pressure-induced diffusion and aggregation of gold nanorods take place after solidification of the solvent. The effect of nanoparticle shape on the aggregation process is additionally discussed.

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.

Photoluminescence upconversion in monolayer WSe2 activated by plasmonic cavities through resonant excitation of dark excitons.

Anti-Stokes photoluminescence (PL) is light emission at a higher photon energy than the excitation, with applications in optical cooling, bioimaging, lasing, and quantum optics. Here, we show how plasmonic nano-cavities activate anti-Stokes PL in WSe2 monolayers through resonant excitation of a dark exciton at room temperature. The optical near-fields of the plasmonic cavities excite the out-of-plane transition dipole of the dark exciton, leading to light emission from the bright exciton at higher energy. Through statistical measurements on hundreds of plasmonic cavities, we show that coupling to the dark exciton leads to a near hundred-fold enhancement of the upconverted PL intensity. This is further corroborated by experiments in which the laser excitation wavelength is tuned across the dark exciton. We show that a precise nanoparticle geometry is key for a consistent enhancement, with decahedral nanoparticle shapes providing an efficient PL upconversion. Finally, we demonstrate a selective and reversible switching of the upconverted PL via electrochemical gating. Our work introduces the dark exciton as an excitation channel for anti-Stokes PL in WSe2 and paves the way for large-area substrates providing nanoscale optical cooling, anti-Stokes lasing, and radiative engineering of excitons.

Determination of 2D Particle Size Distributions in Plasmonic Nanoparticle Colloids via Analytical Ultracentrifugation: Application to Gold Bipyramids.

Multidimensional particle properties determine the product properties in numerous advanced applications. Accurate and statistically meaningful measurements of complex particles and their multidimensional distributions are highly challenging but strongly needed. 2D particle size distributions of plasmonic nanoparticles of complex regular shape can be obtained from analytical ultracentrifugation experiments via the optical back coupling method. A workflow for the calculation of frictional properties of arbitrarily shaped nanoparticles was developed based on bead shell models and applied to gold bipyramids with a pentagonal cross-section. The obtained 2D particle length-diameter distributions and the reduced cumulative 1D length and diameter distributions were compared to transmission electron microscopy measurements. While we find very good agreement for most measurements, the obtained length and diameter distributions were shifted by a few nanometers for some samples. Transmission electron microscopy, energy-dispersive X-ray spectroscopy, electron tomography, and finite element modeling indicate that the shift originated from a slight mismatch between the assumed shape of the simulated perfect bipyramids and the real particle shape and composition due to the presence of silver in the particles. This study demonstrates the feasibility of the applied techniques for complex shape analysis of nanoparticle ensembles with unmatched particle count numbers.