Circular Dichroism Studies on Plasmonic Nanostructures

In recent years, optical chirality of plasmonic nanostructures has aroused great interest because of innovative fundamental understanding as well as promising potential applications in optics, catalysis and sensing. Herein, state‐of‐the‐art studies on circular dichroism (CD) characteristics of plasmonic nanostructures are summarized. The hybrid of achiral plasmonic nanoparticles (NPs) and chiral molecules is explored to generate a new CD response at the plasmon resonance as well as the enhanced CD intensity of chiral molecules in the UV region, owing to the Coulomb static and dynamic dipole interactions between plasmonic NPs and chiral molecules. As for chiral assembly of plasmonic NPs, plasmon–plasmon interactions between the building blocks are found to induce generation of intense CD response at the plasmon resonance. Three‐dimensional periodical arrangement of plasmonic NPs into macroscale chiral metamaterials is further introduced from the perspective of negative refraction and photonic bandgap. A strong CD signal is also discerned in achiral planar plasmonic nanostructures under illumination of circular polarized plane wave at oblique incidence or input vortex beam at normal incidence. Finally perspectives, especially on future investigation of time‐resolved CD responses, are presented.     

Fluorescence Enhancement on Large Area Self‐Assembled Plasmonic‐3D Photonic Crystals

Discontinuous plasmonic‐3D photonic crystal hybrid structures are fabricated in order to evaluate the coupling effect of surface plasmon resonance and the photonic stop band. The nanostructures are prepared by silver sputtering deposition on top of hydrophobic 3D photonic crystals. The localized surface plasmon resonance of the nanostructure has a symbiotic relationship with the 3D photonic stop band, leading to highly tunable characteristics. Fluorescence enhancements of conjugated polymer and quantum dot based on these hybrid structures are studied. The maximum fluorescence enhancement for the conjugated polymer of poly(5‐methoxy‐2‐(3‐sulfopropoxy)‐1,4‐phenylenevinylene) potassium salt by a factor of 87 is achieved as compared with that on a glass substrate due to the enhanced near‐field from the discontinuous plasmonic structures, strong scattering effects from rough metal surface with photonic stop band, and accelerated decay rates from metal‐coupled excited state of the fluorophore. It is demonstrated that the enhancement induced by the hybrid structures has a larger effective distance (optimum thickness ≈130 nm) than conventional plasmonic systems. It is expected that this approach has tremendous potential in the field of sensors, fluorescence‐imaging, and optoelectronic applications.     

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.     

Magnetic plasmon formation and propagation in artificial aromatic molecules

The plasmonic properties of coupled metallic nanostructures are understood through the analogy between their collective plasmon modes and the electronic orbitals of corresponding molecules. Here we expand this analogy to planar arrangements of plasmonic nanostructures whose magnetic plasmons directly resemble the delocalized orbitals of aromatic hydrocarbon molecules. The heptamer structure serves as a benzene-like building block for a family of plasmonic artificial aromatic analogs with fused ring structures. Antiphase magnetic plasmons are excited in adjacent fused heptamer units, which for a linear multiheptamer structure is a behavior controlled by the number of units in the structure. This antiphase coupling gives rise to plasmonic "antiferromagnetic" behavior in multiple repeated heptamer structures, supporting the propagation of low-loss magnetic plasmons in this new waveguide geometry.     

Reproducible Enhancement of Fluorescence by Bimetal Mediated Surface Plasmon Coupled Emission for Highly Sensitive Quantitative Diagnosis of Double‐Stranded DNA

Plasmonic enhancement of fluorescence from SYBR Green I conjugated with a double‐stranded DNA (dsDNA) amplicon is demonstrated on polymerase chain reaction (PCR) products. Theoretical computation leads to use of the bimetallic (Au 2 nm–Ag 50 nm) surface plasmons due to larger local fields (higher quality factors) than monometallic (Ag or Au) ones at both dye excitation and emission wavelengths simultaneously, optimizing fluorescence enhancement with surface plasmon coupled emission (SPCE). Two kinds of reverse Kretschmann configurations are used, which favor, in signal‐to‐noise ratio, a fluorescence assay that uses optically dense buffer such as blood plasma. The fluorescence enhancement (12.9 fold at maximum) with remarkably high reproducibility (coefficient of variation (CV) < 1%) is experimentally demonstrated. This facilitates credible quantitation of enhanced fluorescence, however unlikely to obtain by localized surface plasmons. The plasmon‐induced optical gain of 46 dB due to SPCE‐active dye molecules is also estimated. The fluorescence enhancement technologies with PCR enables LOD of the dsDNA template concentration of ≈400 fg µL^?1 (CV < 1%), the lowest ever reported in DNA fluorescence assay to date. SPCE also reduces photobleaching significantly. These technologies can be extended for a highly reproducible and sufficiently sensitive fluorescence assay with small volumes of analytes in multiplexed diagnostics.     

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.     

Hybrid Plasmonic–Ferroelectric Architectures for Lasing and SHG Processes at the Nanoscale

Coherent light sources providing sub‐wavelength confined modes are in ever more demand to face new challenges in a variety of disciplines. Scalability and cost‐effective production of these systems are also highly desired. The use of ferroelectrics in functional optical platforms, on which plasmonic arrangements can be formed, is revealed as a simple and powerful method to develop coherent light sources with improved and novel functionalities at the nanoscale. Two types of sources with sub‐diffraction spatial confinement and improved performances are presented: i) plasmon‐assisted solid‐state nanolasers based on the interaction between metallic nanostructures and optically active rare earth doped ferroelectric crystals and ii) nonlinear radiation sources based on quadratic frequency mixing processes that are enhanced by means of localized surface plasmon (LSP) resonances. The mechanisms responsible for the intensification of the radiation–matter interaction processes by LSP resonances are discussed in each case. The challenges, potential applications, and future perspectives of the field are highlighted.     

Designable Luminescence with Quantum Dot–Silver Plasmon Coupler

We explore a strongly interacting QDs/Ag plasmonic coupling structure that enables multiple approaches to manipulate light emission from QDs. Group II–VI semiconductor QDs with unique surface states (SSs) impressively modify the plasmonic character of the contiguous Ag nanostructures whereby the localized plasmons (LPs) in the Ag nanostructures can effectively extract the non‐radiative SSs of the QDs to radiatively emit via SS–LP resonance. The SS–LP coupling is demonstrated to be readily tunable through surface‐state engineering both during QD synthesis and in the post‐synthesis stage. The combination of surface‐state engineering and band‐tailoring engineering allows us to precisely control the luminescence color of the QDs and enables the realization of white‐light emission with single‐size QDs. Being a versatile metal, the Ag in our optical device functions in multiple ways: as a support for the LPs, for optical reflection, and for electrical conduction. Two application examples of the QDs/Ag plasmon coupler for optical devices are given, an Ag microcavity + plasmon‐coupling structure and a new QD light‐emitting diode. The new QDs/Ag plasmon coupler opens exciting possibilities in developing novel light sources and biomarker detectors.     

Growth of Silver Nanowires from Controlled Silver Chloride Seeds and Their Application for Fluorescence Enhancement Based on Localized Surface Plasmon Resonance

A “Polyol” method has granted low‐cost and facile process‐controllability for silver‐nanowire (Ag‐NW) synthesis. Although homogenous and heterogeneous nucleation and growth during Ag‐NW synthesis are possible using polyol methods, heterogeneous nucleation and growth of Ag NW guarantees highly selective growth of nanostructures using silver chloride (AgCl) seeds, which provides a stable source of chloride ions (Cl?) and thermodynamic reversibility. In this paper, a microdroplet has been adopted to synthesize uniform AgCl seeds with different diameter that are used for seed‐mediated Ag‐NW synthesis. The concentration of two precursors (AgNO₃ and NaCl) in the droplets is modulated to produce different sizes of AgCl seeds, which determines the diameter and length of Ag NWs. The process of the seed‐mediated growth of Ag NWs has been monitored by observing the peak shift in the time‐resolved UV–vis extinction spectrum. Furthermore, the distinct plasmonic property of Ag NWs for transverse and longitudinal localized‐surface‐plasmon‐resonance (LSPR)‐mediated fluorescence enhancement is utilized. The high aspect ratio and sharp tips work as simple antennas that induce the enhanced fluorescence emission intensity of a fluorophore, which can be applied in the fields of biological tissue imaging and therapy.     

Large‐Scale Plasmonic Hybrid Framework with Built‐In Nanohole Array as Multifunctional Optical Sensing Platforms

Light coupling with patterned subwavelength hole arrays induces enhanced transmission supported by the strong surface plasmon mode. In this work, a nanostructured plasmonic framework with vertically built‐in nanohole arrays at deep‐subwavelength scale (6 nm) is demonstrated using a two‐step fabrication method. The nanohole arrays are formed first by the growth of a high‐quality two‐phase (i.e., Au–TiN) vertically aligned nanocomposite template, followed by selective wet‐etching of the metal (Au). Such a plasmonic nanohole film owns high epitaxial quality with large surface coverage and the structure can be tailored as either fully etched or half‐way etched nanoholes via careful control of the etching process. The chemically inert and plasmonic TiN plays a role in maintaining sharp hole boundary and preventing lattice distortion. Optical properties such as enhanced transmittance and anisotropic dielectric function in the visible regime are demonstrated. Numerical simulation suggests an extended surface plasmon mode and strong field enhancement at the hole edges. Two demonstrations, including the enhanced and modulated photoluminescence by surface coupling with 2D perovskite nanoplates and the refractive index sensing by infiltrating immersion liquids, suggest the great potential of such plasmonic nanohole array for reusable surface plasmon‐enhanced sensing applications.     

Deep‐Ultraviolet Hyperbolic Metacavity Laser

Given the high demand for miniaturized optoelectronic circuits, plasmonic devices with the capability of generating coherent radiation at deep subwavelength scales have attracted great interest for diverse applications such as nanoantennas, single photon sources, and nanosensors. However, the design of such lasing devices remains a challenging issue because of the long structure requirements for producing strong radiation feedback. Here, a plasmonic laser made by using a nanoscale hyperbolic metamaterial cube, called hyperbolic metacavity, on a multiple quantum‐well (MQW), deep‐ultraviolet emitter is presented. The specifically designed metacavity merges plasmon resonant modes within the cube and provides a unique resonant radiation feedback to the MQW. This unique plasmon field allows the dipoles of the MQW with various orientations into radiative emission, achieving enhancement of spontaneous emission rate by a factor of 33 and of quantum efficiency by a factor of 2.5, which is beneficial for coherent laser action. The hyperbolic metacavity laser shows a clear clamping of spontaneous emission above the threshold, which demonstrates a near complete radiation coupling of the MQW with the metacavity. This approach shown here can greatly simplify the requirements of plasmonic nanolaser with a long plasmonic structure, and the metacavity effect can be extended to many other material systems.     

DNA‐Mediated Self‐Assembly of Plasmonic Antennas with a Single Quantum Dot in the Hot Spot

DNA self‐assembly is a powerful tool to arrange optically active components with high accuracy in a large parallel manner. A facile approach to assemble plasmonic antennas consisting of two metallic nanoparticles (40 nm) with a single colloidal quantum dot positioned at the hot spot is presented here. The design approach is based on DNA complementarity, stoichiometry, and steric hindrance principles. Since no intermediate molecules other than short DNA strands are required, the structures possess a very small gap (≈ 5 nm) which is desired to achieve high Purcell factors and plasmonic enhancement. As a proof‐of‐concept, the fluorescence emission from antennas assembled with both conventional and ultrasmooth spherical gold particles is measured. An increase in fluorescence is obtained, up to ≈30‐fold, compared to quantum dots without antenna.     

DNA‐Origami‐Based Assembly of Anisotropic Plasmonic Gold Nanostructures

Precise control over the assembly of anisotropic plasmonic gold nanostructures with relative spatial directionality and sequence asymmetry remains a major challenge and offers great fundamental insight and optical application possibilities. Here, a novel strategy is developed to anisotropically functionalize gold nanorods (AuNRs) by using a DNA‐origami‐based precise machine to transfer essential DNA sequence configurations to the surface of the AuNRs through an intentionally designed toehold‐initiated displacement reaction. Different AuNR products are examined via hybridization with DNA‐AuNPs that display distinct elements of regiospecificity. These assembled anisotropic plasmonic gold nanostructures based on the DNA‐origami precise machine inherit the encoded information from the parent platform with high fidelity and show fixed orientation and bonding anisotropy, thereby generating discrete plasmonic nanostructures with enhanced Raman resonance.     

Ordered Arrangement and Optical Properties of Silica‐Stabilized Gold Nanoparticle–PNIPAM Core–Satellite Clusters for Sensitive Raman Detection

Gold–polymer hybrid nanoparticles attract wide interest as building blocks for the engineering of photonic materials and plasmonic (active) metamaterials with unique optical properties. In particular, the coupling of the localized surface plasmon resonances of individual metal nanostructures in the presence of nanometric gaps can generate highly enhanced and confined electromagnetic fields, which are frequently exploited for metal‐enhanced light–matter interactions. The optical properties of plasmonic structures can be tuned over a wide range of properties by means of their geometry and the size of the inserted nanoparticles as well as by the degree of order upon assembly into 1D, 2D, or 3D structures. Here, the synthesis of silica‐stabilized gold–poly(N‐isopropylacrylamide) (SiO₂‐Au‐PNIPAM) core–satellite superclusters with a narrow size distribution and their incorporation into ordered self‐organized 3D assemblies are reported. Significant alterations of the plasmon resonance are found for different assembled structures as well as strongly enhanced Raman signatures are observed. In a series of experiments, the origin of the highly enhanced signals can be assigned to the interlock areas of adjacent SiO₂‐Au‐PNIPAM core–satellite clusters and their application for highly sensitive nanoparticle‐enhanced Raman spectroscopy is demonstrated.     

Plasmon Modes Induced by Anisotropic Gap Opening in Au@Cu2O Nanorods

Integration of semiconductors with noble metals to form heteronanostructures can give rise to many interesting plasmonic and electronic properties. A number of such heteronanostructures have been demonstrated comprising noble metals and n‐type semiconductors, such as TiO₂, ZnO, SnO₂, Fe₃O₄, and CuO. In contrast, reports on heteronanostructures made of noble metals and p‐type semiconductors are scarce. Cu₂O is an unintentional p‐type semiconductor with unique properties. Here, the uniform coating of Cu₂O on two types of Au nanorods and systematic studies of the plasmonic properties of the resultant core–shell heteronanostructures are reported. One type of Au nanorods is prepared by seed‐mediated growth, and the other is obtained by oxidation of the as‐prepared Au nanorods. The (Au nanorod)@Cu₂O nanostructures produced from the as‐prepared nanorods exhibit two transverse plasmon peaks, whereas those derived from the oxidized nanorods display only one transverse plasmon peak. Through electrodynamic simulations the additional transverse plasmon peak is found to originate from a discontinuous gap formed at the side of the as‐prepared nanorods. The existence of the gap is verified and its formation mechanism is unraveled with additional experiments. The results will be useful for designing metal–semiconductor heteronanostructures with desired plasmonic properties and therefore also for exploring plasmon‐enhanced applications in photocatalysis, solar‐energy harvesting, and biotechnologies.     

Substrate Phonon‐Mediated Plasmon Hybridization in Coplanar Graphene Nanostructures for Broadband Plasmonic Circuits

The mode hybridization between adjacent graphene nanoribbons determines the integration density of graphene‐based plasmonic devices. Here, plasmon hybridization in graphene nanostructures is demonstrated through the characterization of the coupling strength of plasmons in graphene nanoribbons as a function of charge density and inter‐ribbon spacing using Fourier transform infrared microscopy. In combination with numerical simulations, it is shown that the plasmon coupling is strongly mediated by the substrate phonons. For polar substrates, the plasmon coupling strength is limited by the plasmon–phonon interactions. In contrast, a nonpolar substrate affects neither the energy distribution of the original plasmon modes in graphene nanostructures nor their plasmon interactions, which increases exponentially as the inter‐ribbon spacing decreases. To further explore the potential of graphene broadband plasmonics on nonpolar substrates, a scheme is proposed that uses a metal–dielectric heterostructure to prevent the overlap of plasmons between neighboring graphene nanoribbons. The device structures retain the plasmon resonance frequency of the graphene ribbons and maximally isolate the plasmonic components from the surrounding electromagnetic environment, allowing modular design in integrated plasmonic circuits.     

Nanowire‐Intensified Metal‐Enhanced Fluorescence in Hybrid Polymer‐Plasmonic Electrospun Filaments

Hybrid polymer‐plasmonic nanostructures might combine high enhancement of localized fields from metal nanoparticles with light confinement and long‐range transport in subwavelength dielectric structures. Here, the complex behavior of fluorophores coupling to Au nanoparticles within polymer nanowires, which features localized metal‐enhanced fluorescence (MEF) with unique characteristics compared to conventional structures, is reported. The intensification effect when the particle is placed in the organic filaments is remarkably higher with respect to thin films of comparable thickness, thus highlighting a specific, nanowire‐related enhancement of MEF effects. A dependence on the confinement volume in the dielectric nanowire is also indicated, with MEF significantly increasing upon reduction of the wire diameter. These findings are rationalized by finite element simulations, predicting a position‐dependent enhancement of the quantum yield of fluorophores embedded in the fibers. Calculation of the ensemble‐averaged fluorescence enhancement unveils the possibility of strongly enhancing the overall emission intensity for structures with size twice the diameter of the embedded metal particles. These new, hybrid fluorescent systems with localized enhanced emission, and the general nanowire‐enhanced MEF effects associated to them, are highly relevant for developing nanoscale light‐emitting devices with high efficiency and intercoupled through nanofiber networks, highly sensitive optical sensors, and novel laser architectures.     

Polarization-selective plasmon-enhanced silicon quantum-dot luminescence

The photoluminescence intensity of silicon quantum dots is enhanced in a polarization-selective way by coupling to elongated Ag nanoparticles. The observed polarization dependence provides direct proof that the PL enhancement is due to electromagnetic coupling of the silicon quantum-dot emission dipoles with dipolar plasmon modes of the Ag nanoparticles. The polarization selectivity demonstrates the potential of engineered plasmonic nanostructures to optimize and tune the performance of light sources in a way that goes beyond solely enhancing the emission and absorption rates.     

High Efficiency Organic Solar Cells Achieved by the Simultaneous Plasmon‐Optical and Plasmon‐Electrical Effects from Plasmonic Asymmetric Modes of Gold Nanostars

The plasmon‐optical effects have been utilized to optically enhance active layer absorption in organic solar cells (OSCs). The exploited plasmonic resonances of metal nanomaterials are typically from the fundamental dipole/high‐order modes with narrow spectral widths for regional OSC absorption improvement. The conventional broadband absorption enhancement (using plasmonic effects) needs linear‐superposition of plasmonic resonances. In this work, through strategic incorporation of gold nanostars (Au NSs) in between hole transport layer (HTL) and active layer, the excited plasmonic asymmetric modes offer a new approach toward broadband enhancement. Remarkably, the improvement is explained by energy transfer of plasmonic asymmetric modes of Au NS. In more detail, after incorporation of Au NSs, the optical power in electron transport layer transfers to active layer for improving OSC absorption, which otherwise will become dissipation or leakage as the role of carrier transport layer is not for photon‐absorption induced carrier generation. Moreover, Au NSs simultaneously deliver plasmon‐electrical effects which shorten transport path length of the typically low‐mobility holes and lengthen that of high‐mobility electrons for better balanced carrier collection. Meanwhile, the resistance of HTL is reduced by Au NSs. Consequently, power conversion efficiency of 10.5% has been achieved through cooperatively plasmon‐optical and plasmon‐electrical effects of Au NSs.     

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.