Colloidal Gold Nanorings and Their Plasmon Coupling with Gold Nanospheres

Gold nanorings are attractive as plasmonic metal nanocrystals because they have a hollow inner cavity. Their enhanced electric field inside the ring cavity is accessible, which is highly desirable for assembling with other optical components and studying their plasmon‐coupling behaviors. However, the lack of robust methods for synthesizing size‐controllable and uniform Au nanorings severely impedes the study of their attractive plasmonic properties and plasmon‐driven applications. Herein, an improved wet‐chemistry method is reported for the synthesis of monodisperse colloidal Au nanorings. Using circular Au nanodisks with different thicknesses and diameters as templates, Au nanorings are synthesized with thicknesses varied from ≈30 to ≈50 nm and cavity sizes varied from ≈90 to ≈40 nm. The produced Au nanorings are assembled with colloidal Au nanospheres to yield Au nanoring–nanosphere heterodimers in sphere‐in‐ring and sphere‐on‐ring configurations on substrates. The sphere‐in‐ring heterodimers exhibit the interesting feature of plasmonic Fano resonance upon the excitation of the dark quadrupolar plasmon mode of the Au nanorings. The open cavity in a nanoring holds a great promise for studying plasmon‐coupled systems, which will facilitate the construction of advanced metamaterials and high‐performance Fano‐based devices.     

Tetrakis(4‐sulfonatophenyl)porphyrin‐Directed Assembly of Gold Nanocrystals: Tailoring the Plasmon Coupling Through Controllable Gap Distances

It is known that universality and controllability over nanocrystal orientation must be accomplished to facilitate the potential applications of metal nanocrystals in the areas of photonics, electronics, and optics. The facile fabrication of linear chains of Au nanorods and bifurcated junctions of nanorods/nanospheres is achieved via the crosslinking of H‐type tetrakis(4‐sulfonatophenyl)porphyrin aggregates in solution. The tuning of the plasmon coupling between the Au nanocrystals is demonstrated by varying the porphyrin concentration and thus the interparticle gap distances. Finite‐difference time‐domain calculations show that the red shift of the plasmon band exhibits a nearly exponential decay with increasing interparticle gap distances, thus giving rise to a “plasmon ruler equation.” The gap distances determined according to this equation agree well with the experimental observations and further confirm the porphyrin‐directed assembly process. The interaction mechanism between the Au nanorods and porphyrins is further investigated by a biological procedure using the dark‐field light scattering technique.     

Colloid‐Interface‐Assisted Laser Irradiation of Nanocrystals Superlattices to be Scalable Plasmonic Superstructures with Novel Activities

High‐efficient charge and energy transfer between nanocrystals (NCs) in a bottom‐up assembly are hard to achieve, resulting in an obstacle in application. Instead of the ligands exchange strategies, the advantage of a continuous laser is taken with optimal wavelength and power to irradiate the film‐scale NCs superlattices at solid–liquid interfaces. Owing to the Au‐based NCs' surface plasmon resonance (SPR) effect, the gentle laser irradiation leads the Au NCs or Au@CdS core/shell NCs to attach each other with controlled pattern at the interfaces between solid NCs phase and liquid ethanol/ethylene glycol. A continuous wave 532 nm laser (6.68–13.37 W cm^?2), to control Au‐based superlattices, is used to form the monolayer with uniformly reduced interparticle distance followed by welded superstructures. Considering the size effect to Au NCs' melting, when decreasing the Au NCs size to ≈5 nm, stronger welding nanostructures are obtained with diverse unprecedented shapes which cannot be achieved by normal colloidal synthesis. With the help of facile scale‐up and formation at solid–liquid interfaces, and a good connection of crystalline between NCs, the obtained plasmonic superstructured films that could be facilely transferred onto different substrates exhibit broad SPR absorption in the visible and near‐infrared regime, enhanced electric conductivities, and wide applications as surface enhanced Raman scattering (SERS)‐active substrates.     

High-fidelity optofluidic on-chip sensors using well-defined gold nanowell crystals

Recent advances in nanofabrication techniques have enabled the creation of various metallic nanostructures in order to engineer the location and properties of electromagnetic hot spots in a controlled manner. However, most previous methods usually require complicated and time-consuming techniques, and the integration of metallic nanostructures into simple, low-cost devices for chemical or biological sensing is still challenging. Here, we report a promising new strategy for the fabrication of large-area gold nanowell arrays with novel geometric features that makes use of the trapping of self-assembled colloidal particles on a polymer surface. Through both systematic experimental and theoretical analysis, we confirm that the strong plasmon resonances of the proposed nanowell structures are associated with localized surface plasmon resonance (LSPR) on the brims of the nanoholes in the top gold films as well as in the bottom gold disks. In addition, we demonstrate a novel optofluidic platform with built-in subwavelength nanowell arrays that exhibits strong plasmon resonances within microfluidic chips. In our optofluidic systems, the plasmon coupling between the brims and the disks of nanowells makes the plasmon resonance more sensitive to surrounding materials. The dependence of the plasmon resonance on the refractive index of the surrounding medium is found to be as high as 570 nm RIU(-1) (refractive index units). These data lead to a figure of merit (FOM), the slope of refractive index sensitivity in eV RIU(-1)/line width (eV), as high as 4.1.     

Fabricating a Homogeneously Alloyed AuAg Shell on Au Nanorods to Achieve Strong,Stable, and Tunable Surface Plasmon Resonances

Colloidal metal nanocrystals with strong, stable, and tunable localized surface plasmon resonances (SPRs) can be useful in a corrosive environment for many applications including field‐enhanced spectroscopies, plasmon‐mediated catalysis, etc. Here, a new synthetic strategy is reported that enables the epitaxial growth of a homogeneously alloyed AuAg shell on Au nanorod seeds, circumventing the phase segregation of Au and Ag encountered in conventional synthesis. The resulting core–shell structured bimetallic nanorods (AuNR@AuAg) have well‐mixed Au and Ag atoms in their shell without discernible domains. This degree of mixing allows AuNR@AuAg to combine the high stability of Au with the superior plasmonic activity of Ag, thus outperforming seemingly similar nanostructures with monometallic shells (e.g., Ag‐coated Au NRs (AuNR@Ag) and Au‐coated Au NRs (AuNR@Au)). AuNR@AuAg is comparable to AuNR@Ag in plasmonic activity, but that it is markedly more stable toward oxidative treatment. Specifically, AuNR@AuAg and AuNR@Ag exhibit similarly strong signals in surface‐enhanced Raman spectroscopy that are some 30‐fold higher than that of AuNR@Au. When incubated with a H₂O₂ solution (0.5 m ), the plasmonic activity of AuNR@Ag immediately and severely decayed, whereas AuNR@AuAg retained its activity intact. Moreover, the longitudinal SPR frequency of AuNR@AuAg can be tuned throughout the red wavelengths (≈620–690 nm) by controlling the thickness of the AuAg alloy shell. The synthetic strategy is versatile to fabricate AuAg alloyed shells on different shaped Au, with prospects for new possibilities in the synthesis and application of plasmonic nanocrystals.     

Reconfigurable core-satellite nanoassemblies as molecularly-driven plasmonic switches

Molecular control of plasmon coupling is investigated in sub-100 nm assemblies composed of 13 nm gold "satellite" particles tethered by reconfigurable DNA nanostructures to a 50 nm gold "core" particle. Reconfiguration of the DNA nanostructures from a compact to an extended state results in blue shifting of the assembly plasmon resonance, indicating reduced interparticle coupling and lengthening of the core-satellite tether. Scattering spectra of the core-satellite assemblies before and after reconfiguration are compared with spectra calculated using a structural model that incorporates the core/satellite ratio determined by TEM imaging and estimates of tether length based upon prior measurements of interparticle separation in DNA linked nanoparticle networks. A strong correspondence between measured and simulated difference spectra validates the structural models that link the observed plasmon modulation with DNA nanostructure reconfiguration.     

Optical properties of porous anodic alumina membrane uniformly decorated with ultra-thin porous gold nanoparticles arrays

In this paper, we directly develop a facile method to decorate a modified porous anodic alumina membrane (PAA) with an ultrathin porous film of gold nanoparticles with sub-gaps less than 25 nm and particle size less than 40 nm on the top surface and Au nanoparticles uniformly attached to the pore walls as well as the bottom of the pores, utilizing radio-frequency magnetron sputtering. The size as well as the interparticle distance of the gold nanostructures is adjusted by changing the structural properties of PAA membrane and the sputtering time. According to the measured reflection spectra, the saturation of interference color is significantly enhanced. As a result, the Au-coated PAA membrane exhibits a brilliant and tunable color. Field enhancement can be achieved in these structures through the excitation and constructive interference of surface plasmon waves. In addition, the role of localized surface plasmon and propagating surface plasmon was discussed. A four-layered model is presented to describe the reflectance data that show excellent agreement with the experimental data. The brilliant Au-coated PAA membrane is useful for decorative purposes and holds promise as an effective surface enhanced Raman scattering (SERS) substrate.     

Distance dependent spectral tuning of two coupled metal nanoparticles

The spectral properties of two spherical metallic nanoparticles of 80 nm in diameter are examined with regard to the interparticle distance and relative polarization of the excitation light. One Au nanoparticle is attached to a scanning fiber probe and the second to a scanning substrate. This configuration allows three-dimensional and arbitrary manipulation of both distance and relative orientation with respect to the incident light polarization. As supported by numerical simulations, a periodic modulation of the coupled plasmon resonance is observed for separations smaller than 1.5 microm. This interparticle coupling affects the scattering cross section in terms of spectral position and spectral width as well as the integral intensity of the Mie-scattered light.     

Native MicroRNA Targets Trigger Self‐Assembly of Nanozyme‐Patterned Hollowed Nanocuboids with Optimal Interparticle Gaps for Plasmonic‐Activated Cancer Detection

The modernized use of nucleic acid (NA) sequences to drive nanostructure self‐assembly has given rise to a new class of designed nanomaterials with controllable plasmonic functionalities for broad surface‐enhanced Raman scattering (SERS)‐based bioanalysis applications. Herein, dual usage of microRNAs (miRNAs) as both valuable cancer biomarkers and direct self‐assembly triggers is identified and capitalized upon for custom‐designed plasmonic nanostructures. Through strict NA hybridization of miRNA targets, Au nanospheres selectively self‐assemble onto hollowed Au/Ag alloy nanocuboids with ideal interparticle distances (≈2.3 nm) for optimal SERS signaling. The intrinsic material properties of the self‐assembled nanostructures further elevate miRNA detection performance via nanozyme catalytic SERS signaling cascades. This enables fM‐level miR‐107 detection limit within a clinically‐relevant range without any molecular target amplification. The miRNA‐triggered nanostructure self‐assembly approach is further applied in clinical patient samples, and showcases the potential of miR‐107 as a non‐invasive prostate cancer diagnostic biomarker. The use of miRNA targets to drive nanostructure self‐assembly holds great promise as a practical tool for miRNA detection in disease applications.     

Palladium bridged gold nanocylinder dimer: plasmonic properties and hydrogen sensitivity

Plasmonic nanodimers facilitate electromagnetic hotspots at their gap junction. By loading these gap junctions with nanomaterials, the plasmonic properties of nanodimer can be varied. In this study, we bridged the gap junction of gold (Au) nanocylinder dimer with palladium (Pd), and numerically evaluated the plasmonic properties of the designed nanostructure. We simulated the far-field extinction spectra of Pd bridged Au nanocylinder dimer, and identified the dipole and quadrupole plasmon modes at 839 and 578 nm, respectively. By varying the geometrical parameters of the Pd bridge, we revealed the ability to tune the dipolar plasmon resonance of the bridged dimer. Further, we exploited the hydrogen sensitivity of Pd bridge to harness the bridged-Au dimer as nanoplasmonic hydrogen sensor. Such nano-optical detection platforms have minimal spatial footprint and can be further harnessed for chip-based plasmonic sensing.     

Influence of the interaction between two Ag nanoparticles on optical properties of Ag/PGMEA nanocomposite materials

We report local electric field calculations in Ag/PGMEA nanocomposite materials using the dipole discrete approximation. We employ calculation and simulation to show that the nanoparticle radius and the interparticle distance could control and tune the surface plasmon resonances, which influence the extinction spectra and the near-field enhancement of Ag/PGMEA nanostructures. With decreasing interparticle distance, the near-field coupling between particles will induce the shift of surface plasmon resonance peak and improve the near-field intensity. With increasing radius (r), the resonance wavelength peak is red-shifted because of the interaction between two Ag nanoparticles. At 449 nm, the highest near-field enhancement factor obtained in the center of the gap was 30.5 for two interacting Ag nanoparticles of r = 11 nm with a gap of 5 nm.     

One-dimensional nanorod arrays: independent control of composition, length, and interparticle spacing with nanometer precision

We report the synthesis of solution dispersible, one-dimensional metal nanostructure arrays as small as 35 nm in diameter using on-wire lithography, wherein feature thickness and spacing in the arrays is tailorable down to approximately 6 and 1 nm, respectively. Using this unique level of control, we present solution-averaged extinction spectra of 35 nm diameter Au nanorod dimers with varying gap sizes to illustrate the effect of gap size on plasmon coupling between nanorods. Additionally, we demonstrate control over the composition of the arrays with Au, Ni, and Pt segments, representing important advances in controlling the ordering of sub-100 nm nanostructures that are not available with current synthesis or assembly methods.     

Tuning the Intensity of Metal‐Enhanced Fluorescence by Engineering Silver Nanoparticle Arrays

It is demonstrated that silver nanoparticle (SNP) arrays fabricated by combining nanoimprint lithography and electrochemical deposition methods can be used as substrates for metal‐enhanced fluorescence, which is widely used in optics, sensitive detection, and bioimaging. The method presented here is simple and efficient at controlling the nanoparticle density and interparticle distance within one array. Furthermore, it is found that the fluorescence intensity can be tuned by engineering the feature size of the SNP arrays. This is due to the different coupling efficiency between the emission of the fluorophores and surface plasmon resonance band of the metallic nanostructures.     

Hybrid nanostructures of Au nanocrystals and ZnO nanorods: Layer-by-layer assembly and tunable blue-shift band gap emission

A layer-by-layer assembly technique was developed to synthesize the hybrid nanostructures of Au nanocrystals with diameter of about 5 nm and ZnO nanorods via the electrostatic interaction. In comparison with ZnO nanorods, the Au-ZnO hybrid nanostructures exhibited the broadened and red-shifted surface plasmon band, enhanced band gap emission, and suppressed defect emission due to the strong interfacial coupling between Au and ZnO. Moreover, the band gap emission of the Au-ZnO hybrid nanostructures is controllably blue-shifted with decreasing distance between the Au nanocrystals and ZnO nanorods tuned by the amount of the polyelectrolyte layers due to the exciton and plasmon interactions.     

Thermally Driven Self‐Assembly of Nanomicelles: A Facile Route to Functional Monodisperse Mesoporous Colloidal Nanocomposites of Inorganic Nature and Mesoscale Size

Thermally driven self‐assembly of nanomicelles can be a feasible route to produce monodisperse porous colloidal nanocomposites of inorganic nature and sizes around the mesoscale (below 100 nm). Success relies on extending the lifetime of intermediate droplets (size below about 100 nm) that are obtained under particular conditions. Herein, the conditions for the long‐term stabilization of these unique templates are studied and a model proposed to produce monodisperse porous colloidal nanocomposites. As an example of the potential applications of this methodology, functional colloidal nanocomposites with a high loading of the doping material (30 mol%) are obtained. In particular, superparamagnetic nanomagnets of metallic nature encapsulated in porous oxide colloidal matrixes of mesoscale size that easily respond to an external magnetic field are prepared and characterized in terms of structure and textural and magnetic properties.     

Exploitation of Localized Surface Plasmon Resonance

Recent advances in the exploitation of localized surface plasmons (charge density oscillations confined to metallic nanoparticles and nanostructures) in nanoscale optics and photonics, as well as in the construction of sensors and biosensors, are reviewed here. In particular, subsequent to brief surveys of the most‐commonly used methods of preparation and arraying of materials with localized surface plasmon resonance (LSPR), and of the optical manifestations of LSPR, attention will be focused on the exploitation of metallic nanostructures as waveguides; as optical transmission, information storage, and nanophotonic devices; as switches; as resonant light scatterers (employed in the different near‐field scanning optical microscopies); and finally as sensors and biosensors.     

Target‐Triggered Assembly of Nanogap Antennas to Enhance the Fluorescence of Single Molecules and Their Application in MicroRNA Detection

Nanogap antennas are plasmonic nanostructures with a strong electromagnetic field generated at the gap region of two neighboring particles owing to the coupling of the collective surface plasmon resonance. They have great potential for improving the optical properties of fluorophores. Herein, nanogap antennas are constructed using an aqueous solution‐based method to overcome the defects of weak fluorescence and photobleaching associated with traditional organic dyes, and a highly sensitive nanogap antenna‐based sensing strategy is presented for the detection of low‐abundance nucleic acid biomarkers via a target‐triggered strand displacement amplification (SDA) reaction between two DNA hairpins that are tagged to the tips of gold nanorods (Au NRs). In the presence of targets, end‐to‐end Au NR dimers gradually form, and the fluorophores quenched by the Au NRs exhibit a dramatic fluorescence enhancement due to the plasmon‐enhanced fluorescence effect of nanogap antennas. Meanwhile, the SDA reaction results in secondary amplification of fluorescence signals. Combined with single‐molecule counting, this method applied in miRNA‐21 detection can achieve a low detection limit of 97.2 × 10^?18 m . Moreover, accurate discrimination between different cells through miRNA‐21 imaging demonstrates the potential of this method in monitoring the expression level of low‐abundance nucleic acid biomarkers.     

Self‐Aligned Anisotropic Plasmonic Nanostructures

Great opportunities emerge not only in the generation of anisotropic plasmonic nanostructures but also in controlling their orientation relative to incident light. Herein, a stepwise seeded growth method is reported for the synthesis of rod‐shaped plasmon nanostructures which are vertically self‐aligned with respect to the surface of colloidal substrates. Anisotropic growth of metal nanostructure is achieved by depositing metal seeds onto the surface of colloidal substrates and then selectively passivating the seed surface to induce symmetry breaking in the subsequent seed‐mediated growth process. The versatility of this method is demonstrated by producing nanoparticle dimers and linear trimers of Au, Au–Ag, Au–Pd, and Au–Cu₂O. Further, this unique method enables the automatic vertical alignment of the resulting plasmonic nanostructures to the surface of the colloidal substrate, thereby making it possible to design magnetic/plasmonic nanocomposites that allow the dynamic tuning of the plasmon excitation by controlling their orientation using an external magnetic field. The controlled anisotropic growth of colloidal plasmonic nanostructures and their dynamic modulation of plasmon excitation further allow them to be conveniently fixed in a thin polymer film with a well‐controlled orientation to display polarization‐dependent patterns that may find important applications in information encryption.     

Gold nanolenses generated by laser ablation-efficient enhancing structure for surface enhanced Raman scattering analytics and sensing

Nanoaggregates formed by metal spheres of different radii and interparticle distances represent finite, deterministic, self-similar systems that efficiently concentrate optical fields and act as "nanolenses". Here we verify experimentally the theoretical concept of nanolenses and explore their potential as enhancing nanostructures in surface enhanced Raman scattering (SERS). Self-similar structures formed by gold nanospheres of different sizes are generated by laser ablation from solid gold into water. These nanolenses exhibit SERS enhancement factors on the order of 10(9). The "chemically clean" preparation process provides several advantages over chemically prepared nanoaggregates and makes the stable and biocompatible gold nanolenses potent enhancing structures for various analytical and sensing applications.     

Light guide of Au nanostructures for color-filterness optoelectronic display devices

Au line nanostructures with different pitch distances from 500 nm to 950 nm on ITO coated glass substrates have been fabricated at room temperature for exploring the color light guide in all kinds of display system. The patterned Au line array is used as a light outcoupling and color-selection component due to the emission wavelength changed by the Au line arrays with different pitch distances that could achieve multi-color selections. The ITO coated glass substrates patterned with periodic Au line arrays with controlled line pitches has been demonstrated and used as a color filter in all display devices. Using a proper pitch distance of Au line nanostructures, the basic third colors of red, green, and blue (RGB) can be simply gained and controlled without a traditional color filter for future optoelectronic display devices.