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.

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.

Electrochemical Control of Strong Coupling of CdSe Exciton-Polaritons in Plasmonic Cavities.

This work reports in situ (active) electrochemical control over the coupling strength between semiconducting nanoplatelets and a plasmonic cavity. We found that by applying a reductive bias to an Al nanoparticle lattice working electrode the number of CdSe nanoplatelet emitters that can couple to the cavity is decreased. Strong coupling can be reversibly recovered by discharging the lattice at oxidative potentials relative to the conduction band edge reduction potential of the emitters. By correlating the number of electrons added or removed with the measured coupling strength, we identified that loss and recovery of strong coupling are likely hindered by side processes that trap and/or inhibit electrons from populating the nanoplatelet conduction band. These findings demonstrate tunable, external control of strong coupling and offer prospects to tune selectivity in chemical reactions.

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.

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.

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.

Room-temperature strong coupling between CdSe nanoplatelets and a metal-DBR Fabry-Pérot cavity.

The generation of exciton-polaritons through strong light-matter interactions represents an emerging platform for exploring quantum phenomena. A significant challenge in colloidal nanocrystal-based polaritonic systems is the ability to operate at room temperature with high fidelity. Here, we demonstrate the generation of room-temperature exciton-polaritons through the coupling of CdSe nanoplatelets (NPLs) with a Fabry-Pérot optical cavity, leading to a Rabi splitting of 74.6 meV. Quantum-classical calculations accurately predict the complex dynamics between the many dark state excitons and the optically allowed polariton states, including the experimentally observed lower polariton photoluminescence emission, and the concentration of photoluminescence intensities at higher in-plane momenta as the cavity becomes more negatively detuned. The Rabi splitting measured at 5 K is similar to that at 300 K, validating the feasibility of the temperature-independent operation of this polaritonic system. Overall, these results show that CdSe NPLs are an excellent material to facilitate the development of room-temperature quantum technologies.

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.

Ultranarrow plasmon resonances from annealed nanoparticle lattices.

This paper reports how the spectral linewidths of plasmon resonances can be narrowed down to a few nanometers by optimizing the morphology, surface roughness, and crystallinity of metal nanoparticles (NPs) in two-dimensional (2D) lattices. We developed thermal annealing procedures to achieve ultranarrow surface lattice resonances (SLRs) with full-width at half-maxima linewidths as narrow as 4 nm from arrays of Au, Ag, Al, and Cu NPs. Besides annealing, we developed a chemical vapor deposition process to use Cu NPs as catalytic substrates for graphene growth. Graphene-encapsulated Cu NPs showed the narrowest SLR linewidths (2 nm) and were stable for months. These ultranarrow SLR nanocavity modes supported even narrower lasing emission spectra and high nonlinearity in the input-output light-light curves.

Long-Range Dipole-Dipole Interactions in a Plasmonic Lattice.

Spontaneous emission of quantum emitters can be enhanced by increasing the local density of optical states, whereas engineering dipole-dipole interactions requires modifying the two-point spectral density function. Here, we experimentally demonstrate long-range dipole-dipole interactions (DDIs) mediated by surface lattice resonances in a plasmonic nanoparticle lattice. Using angle-resolved spectral measurements and fluorescence lifetime studies, we show that unique nanophotonic modes mediate long-range DDI between donor and acceptor molecules. We observe significant and persistent DDI strengths for a range of densities that map to ∼800 nm mean nearest-neighbor separation distance between donor and acceptor dipoles, a factor of ∼100 larger than free space. Our results pave the way to engineer and control long-range DDIs between an ensemble of emitters at room temperature.

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.

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.

Programmable Self-Regulation with Wrinkled Hydrogels and Plasmonic Nanoparticle Lattices.

This paper describes a self-regulating system that combines wrinkle-patterned hydrogels with plasmonic nanoparticle (NP) lattices. In the feedback loop, the wrinkle patterns flatten in response to moisture, which then allows light to reach the NP lattice on the bottom layer. Upon light absorption, the NP lattice produces a photothermal effect that dries the hydrogel, and the system then returns to the initial wrinkled configuration. The timescale of this regulatory cycle can be programmed by tuning the degree of photothermal heating by NP size and substrate material. Time-dependent finite element analysis reveals the thermal and mechanical mechanisms of wrinkle formation. This self-regulating system couples morphological, optical, and thermo-mechanical properties of different materials components and offers promising design principles for future smart systems.

Spatially defined molecular emitters coupled to plasmonic nanoparticle arrays.

This paper describes how metal-organic frameworks (MOFs) conformally coated on plasmonic nanoparticle arrays can support exciton-plasmon modes with features resembling strong coupling but that are better understood by a weak coupling model. Thin films of Zn-porphyrin MOFs were assembled by dip coating on arrays of silver nanoparticles (NP@MOF) that sustain surface lattice resonances (SLRs). Coupling of excitons with these lattice plasmons led to an SLR-like mixed mode in both transmission and transient absorption spectra. The spectral position of the mixed mode could be tailored by detuning the SLR in different refractive index environments and by changing the periodicity of the nanoparticle array. Photoluminescence showed mode splitting that can be interpreted as modulation of the exciton line shape by the Fano profile of the surface lattice mode, without requiring Rabi splitting. Compared with pristine Zn-porphyrin, hybrid NP@MOF structures achieved a 16-fold enhancement in emission intensity. Our results establish MOFs as a crystalline molecular emitter material that can couple with plasmonic structures for energy exchange and transfer.

Plasmonic Photoelectrocatalysis in Copper-Platinum Core-Shell Nanoparticle Lattices.

This paper reports that strongly coupled bimetallic core-shell nanoparticle arrays show photoelectrocatalytic activity for hydrogen evolution reactions (HER). We fabricated large-area Cu-Pt nanoparticle lattices by combining top-down lithography and solution-based chemistry. These coupled lattices support two different types of plasmon modes, localized surface plasmons from individual particles and surface lattice resonances (SLRs) from the 2D lattice, that increased HER catalytic activity under white-light illumination up to 60%. Comparing photoelectrocatalytic performances of the two plasmon modes at different wavelength ranges, we found that SLRs had two-fold activity enhancement over that from localized surface plasmons.

Spontaneous Formation of Ordered Magnetic Domains by Patterning Stress.

The formation of ordered magnetic domains in thin films is important for the magnetic microdevices in spin-electronics, magneto-optics, and magnetic microelectromechanical systems. Although inducing anisotropic stress in magnetostrictive materials can achieve the domain assembly, controlling magnetic anisotropy over microscale areas is challenging. In this work, we realized the microscopic patterning of magnetic domains by engineering stress distribution. Deposition of ferromagnetic thin films on nanotrenched polymeric layers induced tensile stress at the interfaces, giving rise to the directional magnetoelastic coupling to form ordered domains spontaneously. By changing the periodicity and shape of nanotrenches, we spatially tuned the geometric configuration of domains by design. Theoretical analysis and micromagnetic characterization confirmed that the local stress distribution by the topographic confinement dominates the forming mechanism of the directed magnetization.

Strong Coupling Between Plasmons and Molecular Excitons in Metal-Organic Frameworks.

This Letter describes strong coupling of densely packed molecular emitters in metal-organic frameworks (MOFs) and plasmonic nanoparticle (NP) lattices. Porphyrin-derived ligands with small transition dipole moments in an ordered MOF film were grown on Ag NP arrays. Angle-resolved optical measurements of the MOF-NP lattice system showed the formation of a polariton that is lower in energy and does not cross the uncoupled MOF Q1 band. Modeling predicted the upper polariton energy and a calculated Rabi splitting of 110 meV. The coupling strength was systematically controlled by detuning the plasmon energy by changing the refractive index of the solvents infiltrating the MOF pores. Through transient absorption spectroscopy, we found that the lower polariton decays quickly at shorter time scales (<500 ps) and slowly at longer times because of energy transfer from the upper polariton. This hybrid system demonstrates how MOFs can function as an accessible excitonic material for polariton chemistry.

Nanoparticle Shape Determines Dynamics of Targeting Nanoconstructs on Cell Membranes.

Nanoparticle carriers are effective drug delivery vehicles. Along with other design parameters including size, composition, and surface charge, particle shape strongly influences cellular uptake. How nanoparticle geometry affects targeted delivery under physiologically relevant conditions, however, is inconclusive. Here, we demonstrate that nanoconstruct core shape influences the dynamics of targeting ligand-receptor interactions on cancer cell membranes. By single-particle tracking of translational and rotational motion, we compared DNA aptamer AS1411 conjugated gold nanostars (AS1411-AuNS) and 50 nm gold spheres (AS1411-50NPs) on cells with and without targeted nucleolin membrane receptors. On nucleolin-expressing cells, AS1411-AuNS exhibited faster velocities under directed diffusion and translated over larger areas during restricted diffusion compared to AS1411-50NPs, despite their similar protein corona profiles. On nucleolin-inhibited cells, AS1411-AuNS showed faster rotation dynamics over smaller translational areas, while AS1411-50NPs did not display significant changes in translation. These differences in translational and rotational motions indicate that nanoparticle shape affects how targeting nanoconstructs bind to cell-membrane receptors.

Light-Mediated Directed Placement of Different DNA Sequences on Single Gold Nanoparticles.

This paper describes the light-directed functionalization of anisotropic gold nanoparticles with different thiolated-DNA oligomer (oligo) sequences. The starting nanoconstructs are gold nanostars (AuNS) uniformly grafted with one oligo sequence that are then exposed to fs-laser pulses at the plasmon resonance of the branches. The excitation selectively cleaves Au-S bonds at the tips of the branches to create vacant areas for functionalization with a different thiolated oligo sequence. Nanoconstructs synthesized by this approach present one oligo sequence on the AuNS body and branches and a different sequence at the tips. This process enables the formation of nanoparticle superstructures consisting of AuNS cores and small Au satellite nanoparticles at controlled locations after DNA hybridization. Our strategy enables selective oligo presentation at the single-particle level and opens prospects for sophisticated design of nanoscale assemblies that are important in a wide range of biological applications.