Imaging and Controlling Ultrafast Electron Pulses Emitted from Plasmonic Nanostructures.

We experimentally study photoemission from gold nanodisk arrays using space-, time-, and energy-resolved photoemission electron microscopy. When excited by a plasmonic resonant infrared (IR) laser pulse, plasmonic hotspots are generated owing to local surface plasmon resonance. Photoelectrons emitted from each plasmonic hotspot form a nanoscale and ultrashort electron pulse. When the system is excited by an extreme ultraviolet (EUV) laser pulse, a uniformly distributed photoelectron cloud is formed across the sample surface. When excited by the IR and EUV laser pulses together, both the photoemission image and kinetic energy vary significantly for the IR laser-generated electrons depending on the time delay between the two laser pulses. These observations are well explained by the Coulomb interaction with the EUV laser-generated electron cloud. Our study offers a feasible approach to manipulate the energy of electron pulse emitted from a plasmonic nanostructure on an ultrafast time scale.

DNA-Barcoded Plasmonic Nanostructures for Activity-Based Protease Sensing.

We report the development of a new class of protease activity sensors called DNA-barcoded plasmonic nanostructures. These probes are comprised of gold nanoparticles functionalized with peptide-DNA conjugates (GPDs), where the peptide is a substrate of the protease of interest. The DNA acts as a barcode identifying the peptide and facilitates signal amplification. Protease-mediated peptide cleavage frees the DNA from the nanoparticle surface, which is subsequently measured via a CRISPR/Cas12a-based assay as a proxy for protease activity. As proof-of-concept, we show activity-based, multiplexed detection of the SARS-CoV-2-associated protease, 3CL, and the apoptosis marker, caspase 3, with high sensitivity and selectivity. GPDs yield >25-fold turn-on signals, 100-fold improved response compared to commercial probes, and detection limits as low as 58 pM at room temperature. Moreover, nanomolar concentrations of proteases can be detected visually by leveraging the aggregation-dependent color change of the gold nanoparticles. We showcase the clinical potential of GPDs by detecting a colorectal cancer-associated protease, cathepsin B, in three different patient-derived cell lines. Taken together, GPDs detect physiologically relevant concentrations of active proteases in challenging biological samples, require minimal sample processing, and offer unmatched multiplexing capabilities (mediated by DNA), making them powerful chemical tools for biosensing and disease diagnostics.

Plasmonic Resonance Coupling of Nanodisk Array/Thin Film on the Optical Fiber Tip for Integrated and Miniaturized Sensing Detection.

Fiber-optic surface plasmon resonance (FOSPR) sensing technology has become an appealing candidate in biochemical sensing applications due to its distinguished capability of remote and point-of-care detection. However, FOSPR sensing devices with a flat plasmonic film on the optical fiber tip are seldom proposed with most reports concentrating on fiber sidewalls. In this paper, we propose and experimentally demonstrate the plasmonic coupled structure of a gold (Au) nanodisk array and a thin film integrated into the fiber facet, enabling the excitation of the plasmon mode on the planar gold film by strong coupling. This plasmonic fiber sensor is fabricated by the ultraviolet (UV) curing adhesive transferring technology from a planar substrate to a fiber facet. The experimental results demonstrate that the fabricated sensing probe has a bulk refractive index sensitivity of 137.28 nm/RIU and exhibits moderate surface sensitivity by measuring the spatial localization of its excited plasmon mode on Au film by layer-by-layer self-assembly technology. Furthermore, the fabricated plasmonic sensing probe enables the detection of bovine serum albumin (BSA) biomolecule with a detection limit of 19.35 µM. The demonstrated fiber probe here provides a potential strategy to integrate plasmonic nanostructure on the fiber facet with excellent sensing performance, which has a unique application prospect in the detection of remote, in situ, and in vivo invasion.

Plasmonic Nanostructure Biosensors: A Review.

Plasmonic nanostructure biosensors based on metal are a powerful tool in the biosensing field. Surface plasmon resonance (SPR) can be classified into localized surface plasmon resonance (LSPR) and propagating surface plasmon polariton (PSPP), based on the transmission mode. Initially, the physical principles of LSPR and PSPP are elaborated. In what follows, the recent development of the biosensors related to SPR principle is summarized. For clarity, they are categorized into three groups according to the sensing principle: (i) inherent resonance-based biosensors, which are sensitive to the refractive index changes of the surroundings; (ii) plasmon nanoruler biosensors in which the distances of the nanostructure can be changed by biomolecules at the nanoscale; and (iii) surface-enhanced Raman scattering biosensors in which the nanostructure serves as an amplifier for Raman scattering signals. Moreover, the advanced application of single-molecule detection is discussed in terms of metal nanoparticle and nanopore structures. The review concludes by providing perspectives on the future development of plasmonic nanostructure biosensors.

Plasmonic 3D Self-Folding Architectures via Vacuum Microforming.

3D self-folding microarchitectures have been studied enormously since the past decade, because of the potential of utilizing the third dimension to reach a new level of device integration. However, incorporating various functionalities is a great challenge, due to the limited folding force and choice of materials. In particular, self-folding microarchitectures with advanced optical properties have yet to be demonstrated. Here, a unique folding technique is developed, namely vacuum microforming, successfully demonstrating the self-folding of microcubes that can be completed within 30 ms, a few orders of magnitudes faster as compared to various established strategies reported so far. Simultaneously, a metal-insulator-metal (MIM) plasmonic nanostructure is fabricated, invoking strong gap plasmon to obtain a wide and robust angle-independent optical behavior and high environmental sensitivity that is close to the theoretical limit. It is successfully proven that such superb plasmonic properties are well preserved in 3D architectures throughout the folding process. The nanofabrication method together with the self-folding strategy not only provide the fastest folding process so far, compatible for high-volume fabrication, but also create new opportunities in integrating various functionalities, more specifically, optical properties for untethered optical sensing and identification.

Porous Au-Ag Nanoparticles from Galvanic Replacement Applied as Single-Particle SERS Probe for Quantitative Monitoring.

Plasmonic nanostructures have raised the interest of biomedical applications of surface-enhanced Raman scattering (SERS). To improve the enhancement and produce sensitive SERS probes, porous Au-Ag alloy nanoparticles (NPs) are synthesized by dealloying Au-Ag alloy NP-precursors with Au or Ag core in aqueous colloidal environment through galvanic replacement reaction. The novel designed core-shell Au-Ag alloy NP-precursors facilitate controllable synthesis of porous nanostructure, and dealloying degree during the reaction has significant effect on structural and spectral properties of dealloyed porous NPs. Narrow-dispersed dealloyed NPs are obtained using NPs of Au/Ag ratio from 10/90 to 40/60 with Au and Ag core to produce solid core@porous shell and porous nanoshells, having rough surface, hollowness, and porosity around 30-60%. The clean nanostructure from colloidal synthesis exhibits a redshifted plasmon peak up to near-infrared region, and the large accessible surface induces highly localized surface plasmon resonance and generates robust SERS activity. Thus, the porous NPs produce intensely enhanced Raman signal up to 68-fold higher than 100 nm AuNP enhancement at single-particle level, and the estimated Raman enhancement around 7800, showing the potential for highly sensitive SERS probes. The single-particle SERS probes are effectively demonstrated in quantitative monitoring of anticancer drug Doxorubicin release.

Centrifugation-induced assembly of dense hotspots based SERS substrate for enhanced Raman scattering and quenched fluorescence.

Hanging (aggregation stuck to the centrifugal tube) in the centrifugation process is always regarded as an unwanted condition. In this work, we develop a centrifugation-induced assembly of dense hotspots surface-enhanced Raman scattering (SERS) substrates from the hanging phenomenon. We discovered interesting sintering-resistant behavior (maintain the sharp nanotip features) of star-like Au nanoparticles after centrifugation-induced assembly, which is in stark contrast with the sintering phenomenon of sphere-like nanoparticles. We also found that one side of centrifugal-induced Au assemblies is two-dimensional (2D, root mean square (rms) roughness down to ∼10 nm), while the other is three-dimensional (3D, rms roughness more than 100 nm). The close-packed feature of the Au assemblies makes them candidates as dense hotspots based SERS substrates. Through systematic investigation of SERS performance of centrifugation-induced assemblies with different morphology (star-like and sphere-like, 2D and 3D), it was found that the 3D side of star-like Au nanoparticles assembly exhibits the highest SERS enhancement together with quenched fluorescence. The star-like SERS substrate also displays high detection uniformity (with 10-7M Rhodamine 6G) and a low detection limit (down to 10-12M Rhodamine 6G).

Engineering Plasmonic Environments for 2D Materials and 2D-Based Photodetectors.

Two-dimensional layered materials are considered ideal platforms to study novel small-scale optoelectronic devices due to their unique electronic structures and fantastic physical properties. However, it is urgent to further improve the light-matter interaction in these materials because their light absorption efficiency is limited by the atomically thin thickness. One of the promising approaches is to engineer the plasmonic environment around 2D materials for modulating light-matter interaction in 2D materials. This method greatly benefits from the advances in the development of nanofabrication and out-plane van der Waals interaction of 2D materials. In this paper, we review a series of recent works on 2D materials integrated with plasmonic environments, including the plasmonic-enhanced photoluminescence quantum yield, strong coupling between plasmons and excitons, nonlinear optics in plasmonic nanocavities, manipulation of chiral optical signals in hybrid nanostructures, and the improvement of the performance of optoelectronic devices based on composite systems.

Towards realistic modeling of plasmonic nanostructures: a comparative study to determine the impact of optical effects on solar cell improvement.

Plasmonic structures may improve cell performance in a variety of ways. More accurate determining of the optical influence, unlike ideal simulations, requires modeling closer to experimental cases. In this modeling and simulation, irregular nanostructures were chosen and divided into three groups and some modes. For each mode, different sizes of nanoparticles were randomly selected, which could result in pre-determined average particle size and standard deviation. By 3D finite-difference time-domain (3D-FDTD), the optical plasmonic properties of that mode in a solar cell structure were investigated when the nanostructure was added to the buffer/active layer of the organic solar cell. The far- and near-field results were used to compare the plasmonic behavior, relying on the material and geometry. By detailed simulations, Al and Ag nanostructure at the interface of the ZnO/active layer can improve organic solar cell performance optically, especially by the near-field effect. Unlike Au and relative Ag, the Al nanostructured sample showed less parasitic absorption loss. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s10825-021-01829-x.

A DNA-Based Plasmonic Nanodevice for Cascade Signal Amplification.

Here, we describe a DNA circuit-aided, origami nanodevice-based plasmonic system, which performs DNA-regulated, cascade amplification of faint chemical/biological signals. In this system, two gold-nanorods (GNRs) are co-assembled onto a DNA lock-containing, tweezer-like DNA origami template. Logic circuits serve as recognition and amplification elements for specific messengers, producing DNA keys for driving conformational changes of the plasmonic nanodevices. In the presence of input signals including nucleic acids, adenosines, chiral tyrosinamides or specific receptors expressed by tumor cells, the plasmonic nanodevices can be activated to perform dynamic structural motions, reporting robust responses via plasmonic circular dichroism (CD) spectral changes. This DNA nanodevice-based system provides a different design to enrich the strategies for constructing synthetic nanomachines, enabling the customized bottom-up nanostructure construction for sensitive biological signaling.

3D aluminum/silver hierarchical nanostructure with large areas of dense hot spots for surface-enhanced raman scattering.

Plasmonic nanomaterials possessing large-volume, high-density hot spots with high field enhancement are highly desirable for ultrasensitive surface-enhanced Raman scattering (SERS) sensing. However, many as-prepared plasmonic nanomaterials are limited in available dense hot spots and in sample size, which greatly hinder their wide applications in SERS devices. Here, we develop a two-step physical deposition protocol and successfully fabricate 3D hierarchical nanostructures with highly dense hot spots across a large scale (6 × 6 cm2 ). The nanopatterned aluminum film was first prepared by thermal evaporation process, which can provide 3D quasi-periodic cloud-like nanostructure arrays suitable for noble metal deposition; then a large number of silver nanoparticles with controllable shape and size were decorated onto the alumina layer surfaces by laser molecular beam epitaxy, which can realize large-area accessible dense hot spots. The optimized 3D-structured SERS substrate exhibits high-quality detection performance with excellent reproducibility (13.1 and 17.1%), whose LOD of rhodamine 6G molecules was 10-9 M. Furthermore, the as-prepared 3D aluminum/silver SERS substrate was applied in detection of melamine with the concentration down to 10-7 M and direct detection of melamine in infant formula solution with the concentration as low 10 mg/L. Such method to realize large-area hierarchical nanostructures can greatly simplify the fabrication procedure for 3D SERS platforms, and should be of technological significance in mass production of SERS-based sensors.

Surface plasmon band tailoring of plasmonic nanostructure under the effect of water radiolysis by synchrotron radiation.

Plasmonic metal nanostructures have a significant impact on a diverse domain of fields, including photocatalysis, antibacterial, drug vector, biosensors, photovoltaic cell, optical and electronic devices. Metal nanoparticles (MNps) are the simplest nanostructure promising ultrahigh stability, ease of manufacturing and tunable optical response. Silver nanoparticles (AgNp) dominate in the class of MNps because of their relatively high abundance, chemical activity and unique physical properties. Although MNps offer the desired physical properties, most of the synthesis and fabrication methods lag at the electronic grade due to an unbidden secondary product as a result of the direct chemical reduction process. In this paper, a facile protocol is presented for fabricating high-yield in situ plasmonic AgNps under monochromatic X-rays irradiation, without the use of any chemical reducing agent which prevents the formation of secondary products. The ascendancy of this protocol is to produce high quantitative yield with control over the reaction rate, particle size and localized surface plasmon resonance response, and also to provide the feasibility for in situ characterization. The role of X-ray energy, beam flux and integrated dose towards the fabrication of plasmonic nanostructures has been studied. This experiment extends plasmonic research and provides avenues for upgrading production technologies of MNps.

Plasmonic nanosnowmen with a conductive junction as highly tunable nanoantenna structures and sensitive, quantitative and multiplexable surface-enhanced Raman scattering probes.

The precise design and synthesis of plasmonic nanostructures allow us to manipulate, enhance, and utilize the optical characteristics of metallic materials. Although many multimeric structures (e.g., dimers) with interparticle nanogap have been heavily studied, the plasmonic nanostructures with a conductive junction have not been well studied mostly because of the lack of the reliable synthetic methods that can reproducibly and precisely generate a large number of the plasmonic nanostructures with a controllable conductive nanojunction. Here, we formed various asymmetric Au-Ag head-body nanosnowman structures with a highly controllable conductive nanojunction and studied their plasmon modes that cover from visible to near-infrared range, electromagnetic field enhancement, and surface-enhanced Raman scattering (SERS) properties. It was shown that change in the plasmonic neck region between Au head and Ag body nanoparticles and symmetry breaking using different sizes and compositions within a structure can readily and controllably introduce various plasmon modes and change the electromagnetic field inside and around a nanosnowman structure. The charge-transfer and capacitive coupling plasmon modes at low frequencies are tunable in the snowman structure, and subtle change in the conductive junction area of the nanosnowman dramatically affects the resulting electromagnetic field and optical signal. The relationships between the electromagnetic field distribution and enhancement in the snowman structure, excitation laser wavelength, and Raman dye were also studied, and it was found that the strongest electromagnetic field was observed in the crevice area on the junction and synthesizing a thinner and sharper neck junction is critical to generate the stronger electromagnetic field in the crevice area and to obtain the charge-transfer mode-based near-infrared signal. We have further shown that highly reproducible SERS signals can be generated from these nanosnowman structures with a linear dependence on particle concentration (5 fM to 1 pM) and the SERS-enhancement factor values of >10(8) can be obtained with the aid of the resonance effect in SERS. Finally, a wide range of LSPR bands with high tunability along with high structural reproducibility and high synthetic yield make the nanosnowman structures as very good candidates for practically useful multiple-wavelength-compatible, quantitative and sensitive SERS probes, and highly tunable nanoantenna structures.

3D Plasmonic Nanostructure-Based Polarized ECL Sensor for Exosome Detection in Tumor Microenvironment.

Exosomes of cancer cells play an important role in the proliferation, adhesion, and migration of tumors. Especially, exosomes in the tumor microenvironment can reflect the proliferation of tumors directly, thus serving as ideal referenced markers of the possibility and grade of malignancy in neoplasms. However, the sensitive and accurate detection of exosomes remains challenging. In this work, a novel three-dimensional (3D) plasmonic nanostructure was constructed for exosomal miRNA detection. It combined the advantages of Au nanostar monolayer and Ag nanowire monolayer to provide multiple hot spots. Moreover, Au nanostar monolayer changed the isotropic electrochemiluminescence (ECL) into polarized emission. The Ag nanowire monolayer worked as waveguides for the light direction. As a result, the polarized resolution and intensity of ECL signal were improved. The polarized ECL emission was significantly increased by 47.1 times. This high-resolution polarized ECL sensor was used for detecting exosomal miRNA-146b-5p in the thyroid tumor microenvironment. This sensor showed the linear range from 1 fM to 1 nM with a detection limit of 0.3 fM. The satisfactory results indicated the developed 3D plasmonic nanostructure-based ECL sensor had great potential in biosensing and clinical diagnosis.

Active Site Engineering on Plasmonic Nanostructures for Efficient Photocatalysis.

Plasmonic nanostructures have shown immense potential in photocatalysis because of their distinct photochemical properties associated with tunable photoresponses and strong light-matter interactions. The introduction of highly active sites is essential to fully exploit the potential of plasmonic nanostructures in photocatalysis, considering the inferior intrinsic activities of typical plasmonic metals. This review focuses on active site-engineered plasmonic nanostructures with enhanced photocatalytic performance, wherein the active sites are classified into four types (i.e., metallic sites, defect sites, ligand-grafted sites, and interface sites). The synergy between active sites and plasmonic nanostructures in photocatalysis is discussed in detail after briefly introducing the material synthesis and characterization methods. Active sites can promote the coupling of solar energy harvested by plasmonic metal to catalytic reactions in the form of local electromagnetic fields, hot carriers, and photothermal heating. Moreover, efficient energy coupling potentially regulates the reaction pathway by facilitating the excited state formation of reactants, changing the status of active sites, and creating additional active sites using photoexcited plasmonic metals. Afterward, the application of active site-engineered plasmonic nanostructures in emerging photocatalytic reactions is summarized. Finally, a summary and perspective of the existing challenges and future opportunities are presented. This review aims to deliver some insights into plasmonic photocatalysis from the perspective of active sites, expediting the discovery of high-performance plasmonic photocatalysts.

Towards Digital Twins of Plasmonic Sensors: Constructing the Complex Numerical Model of a Plasmonic Sensor Based on Hexagonally Arranged Gold Nanoparticles.

In this work, we aim to design the digital twin of a plasmonic sensor based on hexagonally arranged ellipsoidal gold nanoparticles fixed to a glass substrate. Based on electron microscopy images of three experimentally realized nanoparticle arrangement types, we constructed numerical models in environments based on finite element method (FEM) and boundary element method (BEM), namely COMSOL Multiphysics for FEM and the MNPBEM Matlab Toolbox for BEM. Models with nonperiodic and periodic boundary conditions with different unit cells were constructed to study the plasmonic behavior of both the single ellipsoidal particles and the hexagonal nanoparticle arrangements. The effect of the geometrical parameters, namely the interparticle distance, the nanoparticle diameter and thickness, on the resulting LSPR peak positions and bulk refractive index sensitivities were studied in detail, also taking into account the effect of the SiO2 substrate (pillars) under the ellipsoidal particles. We have demonstrated that by optimizing the models, the LSPR peak positions (and sensitivities) can match the experimentally measured values within 1 nm (nm/RIU) precision. The comparison of simulation conditions and the detailed discussion of the effect of the geometrical parameters and used gold dielectric functions on the obtained sensitivities can be very beneficial for the optimization of plasmonic sensor constructions through numerical simulations.

Plasmonic genosensor for detecting hazelnut Cor a 14-encoding gene for food allergen monitoring.

A plasmonic nanostructure was constructed as a biorecognition element coupled to an optical sensing platform in sandwich format, targeting the hazelnut Cor a 14 allergen-encoding gene. The analytical performance of the genosensor presented a linear dynamic range between 100 amol L-1 and 1 nmol L-1, a limit of detection (LOD) < 19.9 amol L-1, and a sensitivity of 13.4 ± 0.6 m°. The genosensor was successfully hybridized with hazelnut PCR products, tested with model foods, and further validated by real-time PCR. It reached a LOD <0.001% (10 mg kg-1) of hazelnut in wheat material (corresponding to 1.6 mg kg-1 of protein) and a sensitivity of -17.2 ± 0.5 m° for a linear range of 0.001%-1%. Herein, a new genosensing approach is proposed as a highly sensitive and specific alternative tool with potential application in monitoring hazelnut as an allergenic food, protecting the health of sensitized/allergic individuals.

Plasmonic Superstructure Arrays Fabricated by Laser Near-Field Reduction for Wide-Range SERS Analysis of Fluorescent Materials.

Surface-enhanced Raman scattering (SERS) enables trace-detection for biosensing and environmental monitoring. Optimized enhancement of SERS can be achieved when the energy of the localized surface plasmon resonance (LSPR) is close to the energy of the Raman excitation wavelength. The LSPR can be tuned using a plasmonic superstructure array with controlled periods. In this paper, we develop a new technique based on laser near-field reduction to fabricate a superstructure array, which provides distinct features in the formation of periodic structures with hollow nanoclusters and flexible control of the LSPR in fewer steps than current techniques. Fabrication involves irradiation of a continuous wave laser or femtosecond laser onto a monolayer of self-assembled silica microspheres to grow silver nanoparticles along the silica microsphere surfaces by laser near-field reduction. The LSPR of superstructure array can be flexibly tuned to match the Raman excitation wavelengths from the visible to the infrared regions using different diameters of silica microspheres. The unique nanostructure formed can contribute to an increase in the sensitivity of SERS sensing. The fabricated superstructure array thus offers superior characteristics for the quantitative analysis of fluorescent perfluorooctanoic acid with a wide detection range from 11 ppb to 400 ppm.

Highly sensitive SERS substrates with multi-hot spots for on-site detection of pesticide residues.

Pesticide residues will be a huge threat to food security and ecological environment; therefore, there is an urgent need to achieve rapid and on-site detection of pesticide residues. Herein, a plasmonic substrate with multiple "hot spots" was fabricated by transferring three-dimensional (3D) Au nanoparticles (NPs) onto the polydimethylsiloxane (PDMS) membrane for highly sensitive surface-enhanced Raman scattering (SERS) detection of pesticide residues. In combination with 3D-FDTD simulations, high SERS enhancement (EF = 1.2 × 108) and high detection sensitivity (LOD = 6.3 × 10-10 M) were achieved, mainly due to the enhanced electromagnetic fields around the "hot spots". Additionally, the PDMS-based SERS substrate held good transparency and flexibility, enabling conformal contact with non-planar surfaces and allowing the laser to penetrate the back of the analytes. Combined with a portable Raman spectrometer, the substrates holds great potential for rapid, high-sensitive, and on-site detection of contaminants in food, especially for the analyte on the nonplanar surfaces.

Instantaneous Property Prediction and Inverse Design of Plasmonic Nanostructures Using Machine Learning: Current Applications and Future Directions.

Advances in plasmonic materials and devices have given rise to a variety of applications in photocatalysis, microscopy, nanophotonics, and metastructures. With the advent of computing power and artificial neural networks, the characterization and design process of plasmonic nanostructures can be significantly accelerated using machine learning as opposed to conventional FDTD simulations. The machine learning (ML) based methods can not only perform with high accuracy and return optical spectra and optimal design parameters, but also maintain a stable high computing efficiency without being affected by the structural complexity. This work reviews the prominent ML methods involved in forward simulation and inverse design of plasmonic nanomaterials, such as Convolutional Neural Networks, Generative Adversarial Networks, Genetic Algorithms and Encoder-Decoder Networks. Moreover, we acknowledge the current limitations of ML methods in the context of plasmonics and provide perspectives on future research directions.