Reducing Effective System Dimensionality with Long-Range Collective Dipole-Dipole Interactions.

Dimensionality plays a crucial role in long-range dipole-dipole interactions (DDIs). We demonstrate that a resonant nanophotonic structure modifies the apparent dimensionality in an interacting ensemble of emitters, as revealed by population decay dynamics. Our measurements on a dense ensemble of interacting quantum emitters in a resonant nanophotonic structure with long-range DDIs reveal an effective dimensionality reduction to d[over ¯]=2.20(12), despite the emitters being distributed in 3D. This contrasts with the homogeneous environment, where the apparent dimension is d[over ¯]=3.00. Our work presents a promising avenue to manipulate dimensionality in an ensemble of interacting emitters.

Nanoparticle Anisotropy Increases Targeting Interactions on Live-Cell Membranes.

This paper describes how branch lengths of anisotropic nanoparticles can affect interactions between grafted ligands and cell-membrane receptors. Using live-cell, single-particle tracking, we found that DNA aptamer-gold nanostar nanoconstructs with longer branches showed improved binding efficacy to human epidermal growth factor receptor 2 (HER2) on cancer cell membranes. Inhibiting nanoconstruct-HER2 binding promoted nonspecific interactions, which increased the rotational speed of long-branched nanoconstructs but did not affect that of short-branched constructs. Bivariate analysis of the rotational and translational dynamics showed that longer branch lengths increased the ratio of targeting to nontargeting interactions. We also found that longer branches increased the nanoconstruct-cell interaction times before internalization and decreased intracellular trafficking velocities. Differences in binding efficacy revealed by single-particle dynamics can be attributed to the distinct protein corona distributions on short- and long-branched nanoconstructs, as validated by transmission electron microscopy. Minimal protein adsorption at the high positive curvature tips of long-branched nanoconstructs facilitated binding of DNA aptamer ligands to HER2. Our study reveals the significance of nanoparticle branch length in regulating local chemical environment and interactions with live cells at the single-particle level.

Liquid lasing from solutions of ligand-engineered semiconductor nanocrystals.

Semiconductor nanocrystals (NCs) can function as efficient gain materials with chemical versatility because of their surface ligands. Because the properties of NCs in solution are sensitive to ligand-environment interactions, local chemical changes can result in changes in the optical response. However, amplification of the optical response is technically challenging because of colloidal instability at NC concentrations needed for sufficient gain to overcome losses. This paper demonstrates liquid lasing from plasmonic lattice cavities integrated with ligand-engineered CdZnS/ZnS NCs dispersed in toluene and water. By taking advantage of calcium ion-induced aggregation of NCs in aqueous solutions, we show how lasing threshold can be used as a transduction signal for ion detection. Our work highlights how NC solutions and plasmonic lattices with open cavity architectures can serve as a biosensing platform for lab-on-chip devices.

Ligand Separation on Nanoconstructs Affects Targeting Selectivity to Protein Dimers on Cell Membranes.

This work demonstrates that targeting ligand density on nanoparticles can affect interactions between the nanoconstructs and cell membrane receptors. We discovered that when the separation between covalently grafted DNA aptamers on gold nanostars was comparable to the distance between binding sites on a receptor dimer (matched density; MD), nanoconstructs exhibited a higher selectivity for binding to the dimeric form of the protein. Single-particle dynamics of MD nanoconstructs showed slower rotational rates and larger translational footprints on cancer cells expressing more dimeric forms of receptors (dimer+) compared with cells having more monomeric forms (dimer-). In contrast, nanoconstructs with either increased (nonmatched density; NDlow) or decreased ligand spacing (NDhigh) had minimal changes in dynamics on either dimer+ or dimer- cells. Real-time, single-particle analyses can reveal the importance of nanoconstruct ligand density for the selective targeting of membrane receptors in live cells.

Spike Growth on Patterned Gold Nanoparticle Scaffolds.

This work reports a scaffold-templated, bottom-up synthesis of 3D anisotropic nanofeatures on periodic arrays of gold nanoparticles (AuNPs). Our method relies on substrate-bound AuNPs as large seeds with hemispherical shapes and smooth surfaces after the thermal annealing of as-fabricated particles. Spiky features were grown by immersing the patterned AuNPs into a growth solution consisting of a gold salt and Good's buffer; the number and length of spikes could be tuned by changing the solution pH and buffer concentration. Intermediate structures that informed the growth mechanism were characterized as a function of time by correlating the optical properties and spike features. Large-area (cm2) spiky AuNP arrays exhibited surface-enhanced Raman spectroscopy enhancement that was associated with increased numbers of high-aspect-ratio spikes formed on the AuNP seeds.

Quasi-Random Multimetallic Nanoparticle Arrays.

This paper describes a nanofabrication procedure that can generate multiscale substrates with quasi-random microregions of nanoparticle arrays having different periodicities and metals. We combine cycles of large-area nanoparticle array fabrication with solvent-assisted wrinkle lithography to mask and etch quasi-random areas of prefabricated nanoparticles to control the fill factors of the arrays. The approach is highly flexible, and parameters, including nanoparticle size and material, array geometry, and fill factor, can be tailored independently. Multimetallic nanoparticle arrays can support surface lattice resonances at fill factors as low as 20% and can function as nanoscale cavities for lasing action with as few as 10% of the nanoparticles in an array. We demonstrated that multimetallic nanoparticle substrates that combine two or three arrays with different periodicities can exhibit lasing responses over visible and near-infrared wavelengths. Our work showcases the robust optical responses of multimetallic and periodic devices for broadband light manipulation.

Superlattice Surface Lattice Resonances in Plasmonic Nanoparticle Arrays with Patterned Dielectrics.

This paper describes how two-dimensional plasmonic nanoparticle lattices covered with microscale arrays of dielectric patches can show superlattice surface lattice resonances (SLRs). These optical resonances originate from multiscale diffractive coupling that can be controlled by the periodicity and size of the patterned dielectrics. The features in the optical dispersion diagram are similar to those of index-matched microscale arrays of metal nanoparticle lattices, having the same lateral dimensions as the dielectric patches. With an increase in nanoparticle size, superlattice SLRs can also support quadrupole excitations with distinct dispersion diagrams. The tunable optical band structure enabled by patterned dielectrics on plasmonic nanoparticle arrays offers prospects for enhanced nonlinear optics, nanoscale lasing, and engineered parity-time symmetries.

Area-Specific, Hierarchical Nanowrinkling of Two-Dimensional Materials.

This paper describes an approach to generate hierarchical wrinkles in two-dimensional (2D) electronic materials with spatial control over adjacent wavelengths. A rigid fluoropolymer mold was used to pattern a sacrificial polymer skin layer on monolayer graphene, molybdenum disulfide, and hexagonal boron nitride on prestrained thermoplastic sheets. Strain relief and removal of the polymer layer resulted in 2D-material wrinkles whose wavelengths scaled linearly with the local skin thickness. A second generation of wrinkles could be created on top of the first generation by applying a subsequent cycle of polymer skin coating, strain relief, and polymer removal. This area-specific hierarchical wrinkling is general and will facilitate the engineering of the local properties of various 2D materials and their heterostructures.

Far-field coupling between moiré photonic lattices.

Superposing two or more periodic structures to form moiré patterns is emerging as a promising platform to confine and manipulate light. However, moiré-facilitated interactions and phenomena have been constrained to the vicinity of moiré lattices. Here we report on the observation of ultralong-range coupling between photonic lattices in bilayer and multilayer moiré architectures mediated by dark surface lattice resonances in the vertical direction. We show that two-dimensional plasmonic nanoparticle lattices enable twist-angle-controlled directional lasing emission, even when the lattices are spatially separated by distances exceeding three orders of magnitude of lattice periodicity. Our discovery of far-field interlattice coupling opens the possibility of using the out-of-plane dimension for optical manipulation on the nanoscale and microscale.

A soil-inspired dynamically responsive chemical system for microbial modulation.

Interactions between the microbiota and their colonized environments mediate critical pathways from biogeochemical cycles to homeostasis in human health. Here we report a soil-inspired chemical system that consists of nanostructured minerals, starch granules and liquid metals. Fabricated via a bottom-up synthesis, the soil-inspired chemical system can enable chemical redistribution and modulation of microbial communities. We characterize the composite, confirming its structural similarity to the soil, with three-dimensional X-ray fluorescence and ptychographic tomography and electron microscopy imaging. We also demonstrate that post-synthetic modifications formed by laser irradiation led to chemical heterogeneities from the atomic to the macroscopic level. The soil-inspired material possesses chemical, optical and mechanical responsiveness to yield write-erase functions in electrical performance. The composite can also enhance microbial culture/biofilm growth and biofuel production in vitro. Finally, we show that the soil-inspired system enriches gut bacteria diversity, rectifies tetracycline-induced gut microbiome dysbiosis and ameliorates dextran sulfate sodium-induced rodent colitis symptoms within in vivo rodent models.

Plasmonic Nanoparticle Lattice Devices for White-Light Lasing.

A plasmonic nanolaser architecture that can produce white-light emission is reported. A laser device is designed based on a mixed dye solution used as gain material sandwiched between two aluminum nanoparticle (NP) square lattices of different periodicities. The (±1, 0) and (±1, ±1) band-edge surface lattice resonance (SLR) modes of one NP lattice and the (±1, 0) band-edge mode of the other NP lattice function as nanocavity modes for red, blue, and green lasing respectively. From a single aluminum NP lattice, simultaneous red and blue lasing is realized from a binary dye solution, and the relative intensities of the two colors are controlled by the volume ratio of the dyes. Also, a laser device is constructed by sandwiching dye solutions between two Al NP lattices with different periodicities, which enables red-green and blue-green lasing. With a combination of three dyes as liquid gain, red, green, and blue lasing for a white-light emission profile is realized.

Lasing Action from Quasi-Propagating Modes.

Band edges at the high symmetry points in reciprocal space of periodic structures hold special interest in materials engineering for their high density of states. In optical metamaterials, standing waves found at these points have facilitated lasing, bound-states-in-the-continuum, and Bose-Einstein condensation. However, because high symmetry points by definition are localized, properties associated with them are limited to specific energies and wavevectors. Conversely, quasi-propagating modes along the high symmetry directions are predicted to enable similar phenomena over a continuum of energies and wavevectors. Here, quasi-propagating modes in 2D nanoparticle lattices are shown to support lasing action over a continuous range of wavelengths and symmetry-determined directions from a single device. Using lead halide perovskite nanocrystal films as gain materials, lasing is achieved from waveguide-surface lattice resonance (W-SLR) modes that can be decomposed into propagating waves along high symmetry directions, and standing waves in the orthogonal direction that provide optical feedback. The characteristics of the lasing beams are analyzed using an analytical 3D model that describes diffracted light in 2D lattices. Demonstrations of lasing across different wavelengths and lattice designs highlight how quasi-propagating modes offer possibilities to engineer chromatic multibeam emission important in hyperspectral 3D sensing, high-bandwidth Li-Fi communication, and laser projection displays.

Ultraefficient Electrocatalytic Hydrogen Evolution from Strain-Engineered, Multilayer MoS2.

This paper reports an approach to repurpose low-cost, bulk multilayer MoS2 for development of ultraefficient hydrogen evolution reaction (HER) catalysts over large areas (>cm2). We create working electrodes for use in HER by dry transfer of MoS2 nano- and microflakes to gold thin films deposited on prestrained thermoplastic substrates. By relieving the prestrain at a macroscopic scale, a tunable level of tensile strain is developed in the MoS2 and consequently results in a local phase transition as a result of spontaneously formed surface wrinkles. Using electrochemical impedance spectroscopy, we verified that electrochemical activation of the strained MoS2 lowered the charge transfer resistance within the materials system, achieving HER activity comparable to platinum (Pt). Raman and X-ray photoelectron spectroscopy show that desulfurization in the multilayer MoS2 was promoted by the phase transition; the combined effect of desulfurization and the lower charge resistance induced superior HER performance.

Light-Matter Interactions in Hybrid Material Metasurfaces.

This Review focuses on the integration of plasmonic and dielectric metasurfaces with emissive or stimuli-responsive materials for manipulating light-matter interactions at the nanoscale. Metasurfaces, engineered planar structures with rationally designed building blocks, can change the local phase and intensity of electromagnetic waves at the subwavelength unit level and offers more degrees of freedom to control the flow of light. A combination of metasurfaces and nanoscale emitters facilitates access to weak and strong coupling regimes for enhanced photoluminescence, nanoscale lasing, controlled quantum emission, and formation of exciton-polaritons. In addition to emissive materials, functional materials that respond to external stimuli can be combined with metasurfaces to engineer tunable nanophotonic devices. Emerging metasurface designs including surface-functionalized, chemically tunable, and multilayer hybrid metasurfaces open prospects for diverse applications, including photocatalysis, sensing, displays, and quantum information.

Interfacial engineering of plasmonic nanoparticle metasurfaces.

SignificanceMolecules interacting with metallic nanostructures can show tunable exciton-plasmon coupling, ranging from weak to strong. One factor that influences the interactions is the spatial organization of the molecules relative to the localized plasmon-enhanced electromagnetic fields. In this work, we show that the arrangement of aromatic dye molecules can be tuned within plasmonic hotspots by interfacial engineering of nanoparticle surfaces. By controlling the local chemical and physical interactions, we could modulate lasing thresholds. Surface-functionalized plasmonic metasurfaces open prospects for programmable light-matter interactions at the nanoscale.

Delivery Order of Nanoconstructs Affects Intracellular Trafficking by Endosomes.

This paper reports how the endosomal pathways of nanoparticle (NP) constructs with different surface curvatures are affected by their order of delivery. Sequential incubation of cytosine-phosphate-guanine (CpG)-conjugated spiky and spherical gold NPs with macrophages resulted in different nanoconstruct ratios at the interior edges of endosomes. Application of spiky NPs after spherical NPs accelerated the formation of late-stage endosomes and resulted in larger endosomes, and the spherical NPs were enclosed by the spiky NPs. In contrast, the reverse incubation order produced an asymmetric distribution of the two nanoconstruct shapes in smaller endosomes. Macrophages with a higher proportion of the enclosed spherical NPs as well as a larger ratio of spiky to spherical NPs at the endosomal edge showed enhanced toll-like receptor 9 activation and secretion of proinflammatory cytokines and chemokines. Our results indicate that the subcellular trafficking of targeting nanoconstructs by vesicles is affected by both the delivery order and the endosomal distribution. Our study also establishes a new approach for nanoscale monitoring of intracellular therapeutics delivery with conventional electron microscopy.

Investigating Reaction Intermediates during the Seedless Growth of Gold Nanostars Using Electron Tomography.

Good's buffers can act both as nucleating and shape-directing agents during the synthesis of anisotropic gold nanostars (AuNS). Although different Good's buffers can produce AuNS shapes with branches that are oriented along specific crystallographic directions, the mechanism is not fully understood. This paper reports how an analysis of the intermediate structures during AuNS synthesis from HEPES, EPPS, and MOPS Good's buffers can provide insight into the formation of seedless AuNS. Electron tomography of AuNS structures quenched at early times (minutes) was used to characterize the morphology of the incipient seeds, and later times were used to construct the growth maps. Through this approach, we identified how the crystallinity and shape of the first structures synthesized with different Good's buffers determine the final AuNS morphologies.

Polariton Dynamics in Two-Dimensional Ruddlesden-Popper Perovskites Strongly Coupled with Plasmonic Lattices.

Strong coupling between light and matter can produce hybrid eigenstates known as exciton-polaritons. Although polariton dynamics are important photophysical properties, the relaxation pathways of polaritons in different coupling regimes have seen limited attention. This paper reports the dynamics of hybridized states from 2D Ruddlesden-Popper perovskites coupled to plasmonic nanoparticle lattices. The open cavity architecture of Al lattices enables the coupling strength to be modulated by varying either the lead halide perovskite film thickness or the superstrate refractive index. Both experiments and finite-difference time-domain simulations of the optical dispersion diagrams showed avoided crossings that are a signature of strong coupling. Our analytical model also elucidated the correlation between the exciton/plasmon mixing ratio and polariton coupling strength. Using fs-transient absorption spectroscopy, we found that both the upper and lower polaritons have shorter lifetimes than the excitons and that polaritons can show faster excited-state dynamics when they have access to additional energy transfer channels.