Surface Energy‐Controlled SERS Substrates for Molecular Concentration at Plasmonic Nanogaps

Positioning probe molecules at electromagnetic hot spots with nanometer precision is required to achieve highly sensitive and reproducible surface‐enhanced Raman spectroscopy (SERS) analysis. In this article, molecular positioning at plasmonic nanogaps is reported using a high aspect ratio (HAR) plasmonic nanopillar array with a controlled surface energy. A large‐area HAR plasmonic nanopillar array is generated using a nanolithography‐free simple process involving Ar plasma treatment applied to a smooth polymer surface and the subsequent evaporation of metal onto the polymer nanopillars. The surface energy can be precisely controlled through the selective removal of an adsorbed self‐assembled monolayer of low surface‐energy molecules prepared on the plasmonic nanopillars. This process can be used to tune the surface energy and provide a superhydrophobic surface with a water contact angle of 165.8° on the one hand or a hydrophilic surface with a water contact angle of 40.0° on the other. The highly tunable surface wettability is employed to systematically investigate the effects of the surface energy on the capillary‐force‐induced clustering among the HAR plasmonic nanopillars as well as on molecular concentration at the collapsed nanogaps present at the tops of the clustered nanopillars.     

Plasmonic Nanoneedle Arrays with Enhanced Hot Electron Photodetection for Near-IR Imaging

Hot electron photodetection based on metallic nanostructures is attracting significant attention due to its potential to overcome the limitation of the traditional semiconductor bandgap. To enable efficient hot electron photodetection for practical applications, it is necessary to achieve broadband and perfect light absorption within extremely thin plasmonic nanostructures using cost-effective fabrication techniques. In this study, an ultrahigh optical absorption (up to 97.3% in average across the spectral range of 1200−2400 nm) is demonstrated in the ultrathin plasmonic nanoneedle arrays (NNs) with thickness of 10 nm, based on an all-wet metal-assisted chemical etching process. The efficient hot electron generation, transport, and injection at the nanoscale apex of the nanoneedles facilitate the photodetector to achieve a record low noise equivalent power (NEP) of 4.4 × 10⁻¹² W Hz^−0.5 at the wavelength of 1300 nm. The hot-electron generation and injection process are elucidated through a transport model based on a Monte Carlo approach, which quantitatively matches the experimental data. The photodetector is further integrated into a light imaging system, as a demonstration of the exceptional imaging capabilities at the near-IR regime. The study presents a lithography-free, scalable, and cost-effective approach to enhance hot electron photodetection, with promising prospects for future imaging systems.     

3D Aluminum Hybrid Plasmonic Nanostructures with Large Areas of Dense Hot Spots and Long‐Term Stability

Plasmonic materials possessing dense hot spots with high field enhancement over a large area are highly desirable for ultrasensitive biochemical sensing and efficient solar energy conversion; particularly those based on low‐cost noncoinage metals with high natural abundance are of considerable practical significance. Here, 3D aluminum hybrid nanostructures (3D‐Al‐HNSs) with high density of plasmonic hot spots across a large scale are fabricated via a highly efficient and scalable nonlithographic method, i.e., millisecond‐laser‐direct‐writing in liquid nitrogen. The nanosized alumina interlayer induces intense and dual plasmonic resonance couplings between adjacent Al nanoparticles with bimodal size distribution within each of the hybrid assemblies, leading to remarkably elevated localized electric fields (or hot spots) accessible to the analytes or reactants. The 3D‐stacked nanostructure substantially raises the hot spot density, giving rise to plasmon‐enhanced light harvesting from deep UV to the visible, strong enhancement of Raman signals, and a very low limit of detection outperforming reported Al nanostructures, and even comparable to the noble metals. Combined with the long‐term stability and good reproducibility, the 3D‐Al‐HNSs hold promise as a robust low‐cost plasmonic material for applications in plasmon‐enhanced spectroscopic sensing and light harvesting.     

Thermosensitive Plasmonic Color Enabled by Sodium Metasurface

Active plasmonic nanostructures have attracted tremendous interest in nanophotonics and metamaterials owing to the dynamically switchable capabilities of plasmonic resonances. In this study, tunable hybrid plasmon resonances (HPR) of sodium metasurfaces through heat-initiated structural transformation is experimentally demonstrated. A HPR is formed by coupling surface plasmon polaritons (SPP) and gap plasmon resonances (GPR), whose resonant wavelengths are highly sensitive to gaseous nanogaps. By carefully manipulating the thermo-assisted spin-coating process and post-thermal treatment, tuning of the HPR is achieved because of the phase transition between the antidome and nanodome structural profiles of liquid sodium inside the patterned fused silica substrates. Furthermore, the figure of merit of the heat initiated variable structure-spectrum is demonstrated that is highly dependent on the size of the substrate patterns, based on which temperature-sensitive plasmonic color and “invisible ink” of sodium metasurfaces are demonstrated. These findings can lead to new solutions for manipulating low-cost and high-performance active plasmonic devices.     

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.     

Multilayer Graphene with a Rippled Structure as a Spacer for Improving Plasmonic Coupling

The plasmonic coupling, the enhanced electromagnetic field occurring through a uniform and small separation between metallic particles, is required for better application to localized surface plasmon resonance. Graphene has been studied as a good spacer candidate because of its precise controllability at subnanoscale. Here, the enhancement of plasmonic coupling among metallic nanoparticles (NPs) uniformly spread out on both sides of a graphene spacer is experimentally and simulatively investigated. Additionally, the post‐evaporated flat structure is rippled along one direction to reduce the separation between nanoparticles. As the amount of rippling increases, the enhancement factor (EF) of the plasmonic coupling increases almost linearly or quadratically depending on the size of nanoparticles. Such a highly rippled nanostructure is believed to not only increase the plasmonic coupling in either side of the spacer but lead to a higher density of “hot spots” through the spacer gap also. The observed EFs of a structure with the MLG spacer are consistent with the simulation results obtained from the classical electrodynamics. On the other hand, the SLG case appears to be inconsistent with such a classical approach, indicating that the plasmon tunneling through the thin barrier is prevalent in the case of the SLG spacer.     

叠层圆柱台表面等离激元器件的共振特性

基于金属纳米结构增强光与物质的相互作用,调控光学响应是光学前沿研究。金属纳米结构能显著增强电磁场和热点空间位置调控,是表面等离激元器件应用的关键。借鉴衍射光学元件设计思想,文中提出一种简单的多尺度叠层圆柱台（double stacked nanocone,DSC）金属纳米结构,实现近/远场深度调控。在给定激发条件下,DSC纳米结构中腔模与局域表面等离激元模式间产生杂化,实现多尺度级联场增强,远场响应也得到有效调制,且热点能有效地定位到纳米结构的上表面。进一步,提出并研究了掩模重构的纳米加工方法,低成本、可控地制备了DSC纳米结构,工艺控制是三台阶DSC器件特性的关键,实验结果与理论设计一致。     

Nanogap Plasmonic Structures Fabricated by Switchable Capillary‐Force Driven Self‐Assembly for Localized Sensing of Anticancer Medicines with Microfluidic SERS

Nanogap plasmonic structures, which can strongly enhance electromagnetic fields, enable widespread applications in surface‐enhanced Raman spectroscopy (SERS) sensing. Although the directed self‐assembly strategy has been adopted for the fabrication of micro/nanostructures on open surfaces, fabrication of nanogap plasmonic structures on complex substrates or at designated locations still remains a grand challenge. Here, a switchable self‐assembly method is developed to manufacture 3D nanogap plasmonic structures by combining supercritical drying and capillary‐force driven self‐assembly (CFSA) of micropillars fabricated by laser printing. The polymer pillars can stay upright during solvent development via supercritical drying, and then can form the nanogap after metal coating and subsequent CFSA. Due to the excellent flexibility of this method, diverse patterned plasmonic nanogap structures can be fabricated on planar or nonplanar substrates for SERS. The measured SERS signals of different patterned nanogaps in fluidic environment show a maximum enhancement factor ≈8 × 10⁷. Such nanostructures in microchannels also allow localized sensing for anticancer drugs (doxorubicin). Resulting from the marriage of top‐down and self‐assembly techniques, this method provides a facile, effective, and controllable approach for creating nanogap enabled SERS devices in fluidic channels, and hence can advance applications in precision medicine.     

Facile Fabrication of High‐Density Sub‐1‐nm Gaps from Au Nanoparticle Monolayers as Reproducible SERS Substrates

The fabrication of ultrasmall nanogaps (sub‐1 nm) with high density is of significant interest and importance in physics, chemistry, life science, materials science, surface science, nanotechnology, and environmental engineering. However, it remains a challenge to generate uncovered and clean sub‐1‐nm gaps with high density and uniform reproducibility. Here, a facile and low‐cost approach is demonstrated for the fabrication of high‐density sub‐1‐nm gaps from Au nanoparticle monolayers as reproducible surface‐enhanced Raman scattering (SERS) substrates. Au nanoparticles with larger diameters possess lower surface charge, thus the obtained large‐area nanoparticle monolayer generates a high‐density of sub‐1‐nm gaps. In addition, a remarkable SERS performance with a 10¹¹ magnitude for the Raman enhancement is achieved for 120 nm Au nanoparticle monolayers due to the dramatic increase in the electromagnetic field enhancement when the obtained gap is smaller than 0.5 nm. The Au nanoparticle monolayer is also transferred onto a stretchable PDMS substrate and the structural stability and reproducibility of the high‐density sub‐1‐nm gaps in Au monolayer films are illustrated. The resultant Au nanoparticle monolayer substrates with an increasing particle diameter exhibit tunable plasmonic properties, which control the plasmon‐enhanced photocatalytic efficiency for the dimerization of p‐aminothiophenol. The findings reported here offer a new opportunity for expanding the SERS application.     

Illuminating Dark Plasmons of Silver Nanoantenna Rings to Enhance Exciton–Plasmon Interactions

The chemical growth of silver nanorings that possess singly twinned crystals and a circular cross section via a reductive reaction solution is reported. The wire and ring diameters of the synthesized nanorings are in the ranges 80–200 nm and 4.5–18.0 μm, respectively. By lighting up the multipolar dark plasmons with slanted illumination, the silver nanoring exhibits unique focused scattering and large local‐field enhancement. We also demonstrate strong exciton–plasmon interactions between a monolayer of CdSe/ZnS semiconductor quantum dots and a single silver antenna‐like nanoring (nanoantenna) at the “hot spots” located at the cross points of the incident plane and nanoring; the position of these spots are tunable by adjusting the incidence angle of illumination. The tunable plasmonic behavior of the silver nanorings could find applications as optical nanoantennae or plasmonic nanocavities.     

3D Visible-Light-Driven Plasmonic Oxide Frameworks Deviated from Liquid Metal Nanodroplets

Eutectic gallium-indium (EGaIn) liquid metal droplets have been considered as a suitable platform for producing customized 3D composites with functional nanomaterials owing to their soft and highly reductive surface. Herein, the synthesis of a 3D plasmonic oxide framework (POF) is reported by incorporating the ultra-thin angstrom-scale-porous hexagonal molybdenum oxide (h-MoO₃) onto the spherical EGaIn nanodroplets through ultrasonication. Simultaneously, a large number of oxygen vacancies form in h-MoO₃, boosting its free charge carrier concentration and therefore generating a broad surface plasmon resonance across the whole visible light spectrum. The plasmonic chemical sensing properties of the POF is investigated by the surface-enhanced Raman scattering detection of rhodamine 6G (R6G) at 532 nm, in which the minimum detectable concentration is 10⁻⁸ m and the enhancement factor reached up to 6.14 × 10⁶. The extended optical absorption of the POF also allowed the efficient degradation of the R6G dye under the excitation of ultraviolet-filtered simulated solar light. Furthermore, the POF exhibits remarkable photocurrent responses towards the entire visible light region with the maximum response of ≈ 1588 A W⁻¹ at 455 nm. This work demonstrates the great potential of the liquid metal-based POFs for high-performance sensing, catalytic, and optoelectronic devices.     

Electrically Sensitive Plasmonic Photonic Crystals for Dynamic Upconversion Manipulation

Local optical field modulation using plasmonic materials or photonic crystals provides a powerful strategy for enhancing upconversion emission of lanthanide-doped upconversion nanocrystals (UCNPs). However, it is restricted to static UC enhancement and the corresponding dynamic modulation of UC is yet to be reported, limiting its practical applications in information devices. Here, a dynamic UC modulation system is reported through electric stimulation by integrating UCNPs with electrically sensitive WO_3−x plasmonic photonic crystals (PPCs). The tunable emission enhancement of UCNPs varying from five to 26 folds is achieved in WO_3−x PPCs/UCNPs hybrids through external electric stimulation within +1.6 and −1.6 V. It stems from the reversible control of the photonic bandgaps and localized surface plasmon resonance of WO_3−x PPCs, ascribed to the variation of refractive index and oxygen vacancy of WO_3−x, induced by the reversible change of atomic ratio of W⁵⁺ to W⁶⁺ under different applied voltages. Moreover, the electrically triggered information encryption devices are developed, employing a programmable logic gate array based on WO_3−x PPCs/UCNPs with the ability to convert information-encrypted electrical signals into visible patterns. These observations offer a new attempt to manipulate the UC and will simulate the new applications in the display and optical storage devices.     

Distributed database design methodologies

This paper surveys methodological approaches for distributed database design. The design of distribution can be performed top-down or bottom-up; the first approach is typical of a distributed database developed from scratch, while the second approach is typical of the development of a multi-database as the aggregation of existing databases. We review the design problems and methodologies along both directions, and we describe DATAID-D, a top-down methodology for distribution design. We indicate how the methodology is part of a global approach to database design; how to collect the requirements about the distribution of data and applications; and how to progressively build the distribution of a schema. Our approach is exemplified through one case study.     

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.     

Laser-Printed Plasmonic Metasurface Supporting Bound States in the Continuum Enhances and Shapes Infrared Spontaneous Emission of Coupled HgTe Quantum Dots

In order to advance the development of quantum emitter-based devices, it is essential to enhance light-matter interactions through coupling between semiconductor quantum dots with high quality factor resonators. Here, efficient tuning of the emission properties of HgTe quantum dots in the infrared spectral region is demonstrated by coupling them to a plasmonic metasurface that supports bound states in the continuum. The plasmonic metasurface, composed of an array of gold nanobumps, is fabricated using single-step direct laser printing, opening up new opportunities for creating exclusive 3D plasmonic nanostructures and advanced photonic devices in the infrared region. A 12-fold enhancement of the photoluminescence in the 900–1700 nm range is observed under optimal coupling conditions. By tuning the geometry of the plasmonic arrays, controllable shaping of the emission spectra is achieved, selectively enhancing specific wavelength ranges across the emission spectrum. The observed enhancement and shaping of the emission are attributed to the Purcell effect, as corroborated by systematic measurements of radiative lifetimes and optical simulations based on the numerical solution of Maxwell's equations. Moreover, coupling of the HgTe photoluminescence to high quality factor modes of the metasurface improves emission directivity, concentrating output within an ≈20° angle.     

Multi-level attention model for tracking and segmentation of objects under complex occlusion

A multi-level attention framework for tracking and segmentation of humans and objects under complex occlusions is investigated, featuring an effective probabilistic appearance-based technique for pixel reclassification during object grouping and splitting. A novel ’spatial-depth affinity metric’ is introduced in the conventional likelihood function, utilising information of both spatial locations of pixels and dynamic depth ordering of the component objects in grouping. Depth ordering estimation is achieved through a combination of top-down and bottom-up approach. Experiments on some realworld difficult scenarios of low quality and highly compressed videos demonstrate the very promising results achieved.     

Efficient multilevel brain tumor segmentation with integrated bayesian model classification

We present a new method for automatic segmentation of heterogeneous image data that takes a step toward bridging the gap between bottom-up affinity-based segmentation methods and top-down generative model based approaches. The main contribution of the paper is a Bayesian formulation for incorporating soft model assignments into the calculation of affinities, which are conventionally model free. We integrate the resulting model-aware affinities into the multilevel segmentation by weighted aggregation algorithm, and apply the technique to the task of detecting and segmenting brain tumor and edema in multichannel magnetic resonance (MR) volumes. The computationally efficient method runs orders of magnitude faster than current state-of-the-art techniques giving comparable or improved results. Our quantitative results indicate the benefit of incorporating model-aware affinities into the segmentation process for the difficult case of glioblastoma multiforme brain tumor.     

Tunable Enhancement of Raman Scattering in Graphene‐Nanoparticle Hybrids

The realization of graphene‐gold‐nanoparticle (G‐AuNP) hybrids is presented here through a versatile electrochemical approach, which allows the continuous tuning of the size and density of the particles obtainable on the graphene surface. Raman scattering from graphene, which is significantly enhanced in such hybrids, is systematically investigated as a function of the size and density of particles at the same location. In agreement with theory, it is shown that the Raman enhancement is tunable by varying predominantly the density of the nanoparticles. Furthermore, it is observed that the increase in Raman cross‐section and the strength of Raman enhancement varies as a function of the frequency of the vibrational mode, which may be correlated with the plasmonic fingerprint of the deposited AuNPs. In addition to this electromagnetic enhancement, support is found for a chemical contribution through the occurrence of charge transfer from the AuNPs onto graphene. Finally, G‐AuNP hybrids can be efficiently utilized as SERS substrates for the detection of specifically bound non‐resonant molecules, whose vibrational modes can be unambiguously identified. With the possibility to tune the degree of Raman enhancement, this is a platform to design and engineer SERS substrates to optimize the detection of trace levels of analyte molecules.     

Selective Pd Deposition on Au Nanobipyramids and Pd Site‐Dependent Plasmonic Photocatalytic Activity

The synthesis of anisotropic metal nanostructures is strongly desired for exploring plasmon‐enabled applications. Herein, the preparation of anisotropic Au/SiO₂ and Au/SiO₂/Pd nanostructures is realized through selective silica coating on Au nanobipyramids. For silica coating at the ends of Au nanobipyramids, the amount of coated silica and the overall shape of the coated nanostructures exhibit a bell‐shaped dependence on the cationic surfactant concentration. For both end and side silica coating on Au nanobipyramids, the size of the silica component can be varied by changing the silica precursor amount. Silica can also be selectively deposited on the corners or facets of Au nanocubes, suggesting the generality of this method. The blockage of the predeposited silica component on Au nanobipyramids enables further selective Pd deposition. Suzuki coupling reactions carried out with the different bimetallic nanostructures functioning as plasmonic photocatalysts indicate that the plasmonic photocatalytic activity is dependent on the site of Pd nanoparticles on Au nanobipyramids. Taken together, these results suggest that plasmonic hot spots play an important role in hot‐electron‐driven plasmonic photocatalysis. This study opens up a promising route to the construction of anisotropic bimetallic nanostructures as well as to the design of bimetallic plasmonic‐catalytic nanostructures as efficient plasmonic photocatalysts.     

Interfacial Modulation with Aluminum Oxide for Efficient Plasmon-Induced Water Oxidation

Plasmon-induced photocatalysts hold great promise for solar energy conversion owing to their strong light-harvesting ability and tunable optical properties. However, the complex process of interfacial extraction of hot carriers and the roles of metal/semiconductor interfaces in plasmonic photocatalysts are still not clearly understood. Herein, the manipulation of the interface between a plasmon metal (Au) and a semiconductor (rutile TiO₂) by introducing an interfacial metal oxide (Al₂O₃) is reported. The resulting Au/Al₂O₃/TiO₂ exhibits remarkable enhancement in photocatalytic water oxidation activity compared with Au/TiO₂, giving an apparent quantum efficiency exceeding 1.3% at 520 nm for photocatalytic water oxidation. Such an interfacial modulation approach significantly prolongs the lifetime of hot carriers in the Au/TiO₂ system, which conclusively improves the utilization of hot carriers for plasmon-induced water oxidation reaction upon irradiation. This work emphasizes the essential role of the interfacial structure in plasmonic devices and provides an alternative method for designing efficient plasmonic photocatalysts for solar energy conversion.