Carbon Vesicles: A Symmetry‐Breaking Strategy for Wide‐Band and Solvent‐Processable Ultrablack Coating Materials

Solvent‐processable ultrablack materials have obvious application convenience in many situations, such as absorbing coatings on large and complex surfaces. However, developing solvent‐processable ultrablack materials with high light‐absorption performance and wide absorption band remains a great challenge. In this article, carbon vesicles (CVs) are fabricated for solvent‐processable ultrablack coating. The fabrication process involves a templated co‐condensation of silica and resorcinol formaldehyde resin (RF resin), followed by carbonization and template removal. The resultant structure shows a very thin inner layer, a rough outer layer, as well as a nano‐porous interlayer. This structure introduces randomness and breaks the spherical symmetry of the common carbon hollow spheres. As a result, structural color due to inner‐particle interference is avoided. In addition, the as‐fabricated CVs show a wide‐band low reflectance because of its low carbon filling ratio and nanoscale scatterer size. The lowest reflectance reaches ≈0.10% at 360 nm, making it the darkest solvent‐processable ultrablack material ever reported. The symmetry‐breaking strategy presented here provides an efficient way for the design of solvent‐processable ultrablack materials.     

Lattice‐Symmetry‐Driven Epitaxy of Hierarchical GaN Nanotripods

Lattice‐symmetry‐driven epitaxy of hierarchical GaN nanotripods is demonstrated. The nanotripods emerge on the top of hexagonal GaN nanowires, which are selectively grown on pillar‐patterned GaN templates using molecular beam epitaxy. High‐resolution transmission electron microscopy confirms that two kinds of lattice‐symmetry, wurtzite (wz) and zinc‐blende (zb), coexist in the GaN nanotripods. Periodical transformation between wz and zb drives the epitaxy of the hierarchical nanotripods with N‐polarity. The zb‐GaN is formed by the poor diffusion of adatoms, and it can be suppressed by improving the ability of the Ga adatoms to migrate as the growth temperature increased. This controllable epitaxy of hierarchical GaN nanotripods allows quantum dots to be located at the phase junctions of the nanotripods and nanowires, suggesting a new recipe for multichannel quantum devices.     

Symmetry‐Breaking Response of Azo Molecular Glass Microspheres to Interfering Circularly Polarized Light: From Shape Manipulation to 3D Patterning

This work investigates symmetry‐breaking deformation of azo molecular glass microspheres induced by interfering circularly polarized light, and related particle shape manipulation as well as 3D patterning. The isolated microspheres and microsphere monolayers are obtained from an azo molecular glass (IA‐Chol) by the solution dispersion method and soft‐lithography, respectively. Unique symmetry‐breaking deformation is observed for the microspheres upon exposure to the spatially modulated light field, which is produced by interference of two orthogonally polarized laser beams with the right‐circular polarization (RCP) and left‐circular polarization (LCP). Two distinct deformation modes are developed upon the irradiation with the interfering beams in RCP:LCP and LCP:RCP superposition manners, respectively. The unique morphologies with the symmetry‐breaking characteristics are caused by mass transfer induced by the light irradiation. For the microsphere monolayers, the deformations of the microspheres not only capture and record the polarization states of the light field, but also create various surface patterns combining the symmetry‐breaking deformations and periodic surface modulation. A variety of unique surface patterns are obtained by irradiation with the interfering circularly polarized waves with the orthogonal and also the same‐handed polarizations. The material and methodology developed in this study are promising for applications in sensing, optics, responsive surfaces, and others.     

Symmetry Breaking in Monometallic Nanocrystals toward Broadband and Direct Electron Transfer Enhanced Plasmonic Photocatalysis

Metallic nanocrystals manifest themselves as fascinating light absorbers for applications in plasmon-enhanced photocatalysis and solar energy harvesting. The essential challenges lie in harvesting the full-spectrum solar light and harnessing the plasmon-induced hot carriers at the metal–acceptor interface. To this end, a cooperative overpotential and underpotential deposition strategy is proposed to mitigate both the challenges. Specifically, by utilizing both ionic additive and thiol passivator to introduce symmetry-breaking growth over gold icosahedral nanocrystals, the microscopic origin can be attributed to the site-specific nucleation of stacking faults and dislocations. By adopting asymmetric crystal shape and unique surface facets, such nanocrystals attain high activity toward photocatalytic ammonia borane hydrolysis, arising from combined broadband plasmonic properties and enhanced direct transfer of hot electrons across the metal–adsorbate interface.     

Plasmonic Nanowire‐Enhanced Upconversion Luminescence for Anticounterfeit Devices

A novel, efficient, cost‐effective, and high‐level security performance anticounterfeit device achieved by plasmonic‐enhanced upconversion luminescence (UCL) is demonstrated. The plasmonic architecture consists of the randomly dispersed Ag nanowires (AgNWs) network, upconversion nanoparticles (UCNPs) monolayer, and metal film, in which the UCL is enhanced by a few tens, compared to reference sample, becuase the plasmonic modes lead to the concentration of the incident near infrared (NIR) light in the UCNPs monolayer. In the configuration, both the localized surface plasmons (LSPs) around the metallic nanostructures and gap plasmon polaritons (GPPs) confined in the UCNPs monolayer, significantly contribute to the UCL enhancement. The UCL enhancement mechanism resulting from enhanced NIR absorption, boosted internal quantum process, and formation of strong plasmonic hot spots in the plasmonic architecture is analyzed theoretically and numerically. More interestingly, a proof‐of‐concept anticounterfeit device using the plasmonic‐enhanced UCL is proposed, through which a nonreusable and high‐level cost‐effective security device protecting the genuine products is realized.     

Large‐Area Fabrication of Periodic Arrays of Nanoholes in Metal Films and Their Application in Biosensing and Plasmonic‐Enhanced Photovoltaics

Plasmonics is a fast developing research area with a great potential for practical applications. However, the implementation of plasmonic devices requires low cost methodologies for the fabrication of organized metallic nanostructures that covers a relative large area (～1 cm²). Here the patterning of periodic arrays of nanoholes (PANHs) in gold films by using a combination of interference lithography, metal deposition, and lift off is reported. The setup allows the fabrication of periodic nanostructures with hole diameters ranging from 110 to 1000 nm, for 450 and 1800 nm of periodicity, respectively. The large areas plasmonic substrates consist of 2 cm × 2 cm gold films homogeneously covered by nanoholes and gold films patterned with a regular microarray of 200 μm diameter circular patches of PANHs. The microarray format is used for surface plasmon resonance (SPR) imaging and its potential for applications in multiplex biosensing is demonstrated. The gold films homogeneously covered by nanoholes are useful as electrodes in a thin layer organic photovoltaic. This is first example of a large area plasmonic solar cell with organized nanostructures. The fabrication approach reported here is a good candidate for the industrial‐scale production of metallic substrates for plasmonic applications in photovoltaics and biosensing.     

Periodic Arrays of Diamond‐Shaped Silver Nanoparticles: From Scalable Fabrication by Template‐Assisted Solid‐State Dewetting to Tunable Optical Properties

Periodic arrays of anisotropic silver nanoparticles having peculiar optical properties are fabricated at a macroscopic scale. The proposed scalable method is based on temperature‐assisted solid‐state dewetting of a continuous thin layer deposited on a silica substrate patterned by the nanoimprint technique. The resulting nanoparticles are shaped like diamonds and are half‐embedded into the patterned silica. A period‐dependent optimum in film thickness for the quality of spatial organization is found and discussed in terms of thermodynamics and, for the first time, in terms of the role of grains in the dewetting process. The optical properties of the arrays are driven by not only simply the particle shape but also the lattice period and the degree of order. A surface lattice resonance that disperses with the underlying period is evidenced experimentally and confirmed by optical simulations. The opportunity to fabricate and tune such an assembly of plasmonic particles on transparent substrate opens interesting perspectives for not only fundamental photonics but also potential optical applications.     

Self‐Assembly of Nanoparticle‐Spiked Pillar Arrays for Plasmonic Biosensing

Plasmonic biosensors have demonstrated superior performance in detecting various biomolecules with high sensitivity through simple assays. Scaled‐up, reproducible chip production with a high density of hotspots in a large area has been technically challenging, limiting the commercialization and clinical translation of these biosensors. A new fabrication method for 3D plasmonic nanostructures with a high density, large volume of hotspots and therefore inherently improved detection capabilities is developed. Specifically, Au nanoparticle‐spiked Au nanopillar arrays are prepared by utilizing enhanced surface diffusion of adsorbed Au atoms on a slippery Au nanopillar arrays through a simple vacuum process. This process enables the direct formation of a high density of spherical Au nanoparticles on the 1 nm‐thick dielectric coated Au nanopillar arrays without high‐temperature annealing, which results in multiple plasmonic coupling, and thereby large effective volume of hotspots in 3D spaces. The plasmonic nanostructures show signal enhancements over 8.3 × 10⁸‐fold for surface‐enhanced Raman spectroscopy and over 2.7 × 10²‐fold for plasmon‐enhanced fluorescence. The 3D plasmonic chip is used to detect avian influenza‐associated antibodies at 100 times higher sensitivity compared with unstructured Au substrates for plasmon‐enhanced fluorescence detection. Such a simple and scalable fabrication of highly sensitive 3D plasmonic nanostructures provides new opportunities to broaden plasmon‐enhanced sensing applications.     

Hot Spot‐Localized Artificial Antibodies for Label‐Free Plasmonic Biosensing

The development of biomolecular imprinting over the last decade has raised promising perspectives in replacing natural antibodies with artificial antibodies. A significant number of reports have been dedicated to imprinting of organic and inorganic nanostructures, but very few were performed on nanomaterials with a transduction function. Herein, a relatively fast and efficient plasmonic hot spot‐localized surface imprinting of gold nanorods using reversible template immobilization and siloxane copolymerization is described. The technique enables a fine control of the imprinting process at the nanometer scale and provides a nanobiosensor with high selectivity and reusability. Proof of concept is established by the detection of neutrophil gelatinase‐associated lipocalin (NGAL), a biomarker for acute kidney injury, using localized surface plasmon resonance spectroscopy. The work represents a valuable step towards plasmonic nanobiosensors with synthetic antibodies for label‐free and cost‐efficient diagnostic assays. It is expected that this novel class of surface imprinted plasmonic nanomaterials will open up new possibilities in advancing biomedical applications of plasmonic nanostructures.     

Enhanced Light‐Harvesting by Integrating Synergetic Microcavity and Plasmonic Effects for High‐Performance ITO‐Free Flexible Polymer Solar Cells

In this work, a high‐performance ITO‐free flexible polymer solar cell (PSC) is successfully described by integrating the plasmonic effect into the ITO‐free microcavity architecture. By carefully controlling the sizes of embedded Ag nanoprisms and their doping positons in the stratified device, a significant enhancement in power conversion efficiency (PCE) is shown from 8.5% (reference microcavity architecture) to 9.4% on flexible substrates. The well‐manipulated plasmonic resonances introduced by the embedded Ag nanoprisms with different LSPR peaks allow the complementary light‐harvesting with microcavity resonance in the regions of 400–500 nm and 600–700 nm, resulting in the substantially increased photocurrent. This result not only signifies that the spectral matching between the LSPR peaks of Ag nanoprisms and the relatively low absorption response of photoactive layer in the microcavity architecture is an effective strategy to enhance light‐harvesting across its absorption region, but also demonstrates the promise of tailoring two different resonance bands in a synergistic manner at desired wavelength region to enhance the efficiency of PSCs.     

Manipulable and Hybridized,Ultralow‐Threshold Lasing in a Plasmonic Laser Using Elliptical InGaN/GaN Nanorods

Manipulating stimulated‐emission light in nanophotonic devices on scales smaller than their emission wavelengths to meet the requirements for optoelectronic integrations is a challenging but important step. Surface plasmon polaritons (SPPs) are one of the most promising candidates for sub‐wavelength optical confinement. In this study, based on the principle of surface plasmon amplification by the stimulated emission of radiation (SPASER), III‐Nitride‐based plasmonic nanolaser with hybrid metal–oxide–semiconductor (MOS) structures is designed. Using geometrically elliptical nanostructures fabricated by nanoimprint lithography, elliptical nanolasers able to demonstrate single‐mode and multimode lasing with an optical pumping power density as low as 0.3 kW cm^?2 at room temperature and a quality Q factor of up to 123 at a wavelength of ≈490 nm are achieved. The ultralow lasing threshold is attributed to the SPP‐coupling‐induced strong electric‐field‐confinement in the elliptical MOS structures. In accordance with the theoretical and experimental results, the size and shape of the nanorod are the keys for manipulating hybridization of the plasmonic and photonic lasing modes in the SPASER. This finding provides innovative insight that will contribute to realizing a new generation of optoelectronic and information devices.     

Light‐Induced Plasmon‐Assisted Phase Transformation of Carbon on Metal Nanoparticles

Highly localized light‐induced phase transformation of electron beam induced deposited carbon nanostructures (dots and squares) on noble metal surfaces is reported. The phase transformation from the amorphous phase to the disordered graphitic phase is analyzed using the characteristic Raman signatures for amorphous and graphitized carbon and conductive force microscopy. The extent of the transformation is found to be largely dependent on the plasmon absorption properties of the underlying metal film. It is observed that the amorphous carbon deposits on the silver films consisting of 12 nm particles with the plasmon absorption near the laser excitation wavelength (514 nm), undergo fast graphitization to a nanocrystalline or a disordered graphitic phase. This transformation results in the formation of a highly conductive carbon/metal interface with at least seven orders of magnitude lower electrical resistivity than the initial insulating interface. It is suggested that the fast graphitization of nanoscale carbon deposits might serve as an efficient path for the formation of complex patterned nanoscale metal‐carbon interconnects with high electrical conductivity.     

Plasmon‐Enhanced Blue Upconversion Luminescence by Indium Nanocrystals

Numerous endeavors have been undertaken to gain enhanced upconversion luminescence via surface plasmon resonance (SPR) generated by specially designed nanostructures of noble metals (e.g., Au, Ag). However, the SPR response of these metals is usually weak in the ultraviolet (UV) region because of their intrinsic electronic configurations; thus, only green and red upconversion emissions can undergo significant plasmonic enhancement yet without selectivity, while an efficient approach to selectively enhancing the blue upconversion luminescence has been lacking. Herein, by integrating the pronounced UV SPR of silica‐coated indium nanocrystals (InNCs) with blue‐emission upconversion nanoparticles (UCNPs) of NaYbF₄:Tm, an up to tenfold selective luminescence enhancement at 450 nm is obtained upon 980 nm laser excitation. Precise manipulation of the silica shell thickness suggests an optimal working distance of 3 nm between InNCs and UCNPs. This study has, for the first time, realized selective blue upconversion luminescence enhancement by using an inexpensive, non‐noble metal material, which will not only enrich the fundamental investigations of SPR‐enhanced upconversion emission, but also widen the applications of blue light‐emitting nanomaterials, for example, in therapeutics.     

Plasmon‐Enhanced Photodetection in Ferromagnet/Nonmagnet Spin Thermoelectric Structures

The photothermoelectric (PTE) effect that originates from the temperature difference within thermoelectric materials induced by light absorption can be used as the mechanism for a light sensor in optoelectronic applications. In this work, a PTE‐based photodetector is reported using a spin thermoelectric structure consisting of CoFeB/Pt metallic bilayers and its signal enhancement achieved by incorporating a plasmonic structure consisting of Au nanorod arrays. The thermoelectric voltage of the bilayers markedly increases by 60 ± 10% when the plasmon resonance condition of the Au nanorods is matched to the wavelength of the incident laser. Full‐wave electromagnetic simulations reveal that the signal enhancement is due to the increase in light absorption and consequential local heating. Moreover, the alignment of the Au nanorods makes the thermoelectric voltages sensitive to the polarization state of the laser, thereby enabling the detection of light polarization. These results demonstrate the feasibility of a hybrid device utilizing plasmonic and spin‐thermoelectric effects as an efficient PTE‐based photodetector.     

Ultrasonication‐Induced Self‐Assembled Fixed Nanogap Arrays of Monomeric Plasmonic Nanoparticles inside Nanopores

Monomeric gold (Au) and silver (Ag) nanoparticle (NP) arrays are self‐assembled uniformly into anodized aluminium oxide (AAO) nanopores with a high homogeneity of greater than 95%, using ultrasonication. The monomeric metal NP array exhibits asymmetric plasmonic absorption due to Fano‐like resonance as interpreted by finite‐difference time‐domain (FDTD) simulation for the numbers up to 127 AuNPs. To examine gap distance‐dependent collective‐plasmonic resonance, the different dimensions of S, M, and L arrays of the AuNP diameters/the gap distances of ≈36 nm/≈66 nm, ≈45 nm/≈56 nm, and ≈77 nm/≈12 nm, respectively, are prepared. Metal NP arrays with an invariable nanogap of ≈50 nm can provide consistent surface‐enhanced Raman scattering (SERS) intensities for Rhodamine 6G (Rh6G) with a relative standard deviation (RSD) of 3.8–5.4%. Monomeric arrays can provide an effective platform for 2D hot‐electron excitation, as evidenced by the SERS peak‐changes of 4‐nitrobenzenethiol (4‐NBT) adsorbed on AgNP arrays with a power density of ≈0.25 mW µm^‐2 at 514 and 633 nm. For practical purposes, the bacteria captured by 4‐mercaptophenylboronic acid are found to be easily destroyed under visible laser excitation at 514 nm with a power density of ≈14 mW µm^‐2 for 60 min using Ag due to efficient plasmonic‐electron transfer.     

Engineering Sensor Arrays Using Aggregation‐Induced Emission Luminogens for Pathogen Identification

Lacking rapid and reliable pathogen diagnostic platforms, inadequate or delayed antimicrobial therapy could be made, which greatly threatens human life and accelerates the emergence of antibiotic‐resistant pathogens. In this contribution, a series of simple and reliable sensor arrays based on tetraphenylethylene (TPE) derivatives are successfully developed for detection and discrimination of pathogens. Each sensor array consists of three TPE‐based aggregation‐induced emission luminogens (AIEgens) that bear cationic ammonium group and different hydrophobic substitutions, providing tunable logP (n‐octanol/water partition coefficient) values to enable the different multivalent interactions with pathogens. On the basis of the distinctive fluorescence response produced by the diverse interaction of AIEgens with pathogens, these sensor arrays can identify different kinds of pathogens, even normal and drug‐resistant bacteria, with nearly 100% accuracy. Furthermore, blends of pathogens can also be identified accurately. The sensor arrays exhibit rapid response (about 0.5 h), high‐throughput, and easy‐to‐operate without washing steps.     

Linewidth‐Optimized Extraordinary Optical Transmission in Water with Template‐Stripped Metallic Nanohole Arrays

The experimental observation of unusually sharp plasmon resonance peaks in periodic Ag nanohole arrays made using template stripping is reported. The extraordinary optical transmission (EOT) peak associated with the surface plasmon polaritons at the smooth Ag‐water interface shows a well‐defined Fano‐type profile with a linewidth below 10 nm at a wavelength of around 700 nm. Notably, this sharp and intense radiant peak (Q factor of 71) is obtained at visible frequencies in water and at normally incident illumination. This is accomplished by obtaining high‐quality Ag surfaces with a roughness below 1 nm, which reduces the imaginary component of the Ag dielectric function that is associated with material damping, as well as shrinking the nanohole radius to decrease radiative damping of plasmons. The localized spectral response of the radiant plasmon peak is characterized using the nanohole array in water in a layer‐by‐layer fashion via sequential atomic layer deposition of Al₂O₃. Because the ultrasharp EOT peak is obtained with excellent uniformity over a centimeter‐sized area from the metallic nanohole array in water, these template‐stripped nanohole arrays will benefit many practical applications based on EOT.     

Biologically Enabled Syntheses of Freestanding Metallic Structures Possessing Subwavelength Pore Arrays for Extraordinary (Surface Plasmon‐Mediated) Infrared Transmission

A scalable wet chemical process has been used to convert the intricate silica microshells (frustules) of diatoms into gold structures that retained the three‐dimensional (3‐D) frustule shapes and fine patterned features. Combined use of an amine‐enriching surface functionalization protocol and electroless deposition yielded thin (<100 nm) conformal nanocrystalline gold coatings that, upon selective silica dissolution, were converted into freestanding gold structures with frustule‐derived 3‐D morphologies. By selecting a diatom frustule template with a quasi‐regular hexagonal pore pattern (Coscinodiscus asteromphalus, CA), gold replica structures possessing such pore patterns were produced that exhibited infrared transmission maxima/reflection minima that were not observed for the starting silica diatom frustules or for flat nonporous gold films; that is, such extraordinary optical transmission (EOT) resulted from the combined effects of the quasi‐periodic hexagonal hole structure (inherited from the CA diatom frustules) and the gold chemistry. Calculated and measured IR transmission spectra obtained from planar gold films with quasi‐periodic hexagonal CA‐derived hole patterns, or with short‐range periodic hexagonal hole patterns, indicated that the enhanced IR transmission exhibited by the gold CA frustule replicas was enabled by the generation and transmission of surface plasmons. This scalable bio‐enabled process provides a new and attractive capability for fabricating self‐supporting, responsive, 3‐D metallic structures for use as dispersible/harvestable microparticles tailored for EOT‐based applications.