Surface-enhanced Spectroscopies Research Articles

Transmission electron microscopy reveals clusters of Au–Ag nanoparticles formed in TiO2 thin film, with enhanced plasmonic response

This work reports on the influence of nanoparticle (NP) size distribution and the chemical nature of gold (Au) and/or silver (Ag) NPs in the localized surface plasmon resonance (LSPR) responses. The NPs were produced embedded in a titanium dioxide (TiO2) thin film, deposited by reactive magnetron sputtering technique followed by in-vacuum thermal treatment at 400 °C. High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) gave quantitative key information in terms of both the size and distribution of the noble metal NPs. The average Feret diameter was 17 nm (σ = 8) and 55 nm (σ = 28) for Au/TiO2 and Ag/TiO2 films, respectively, while the Au–Ag/TiO2 film showed intermediate values, with an average size of 22 nm (σ = 9). HAAD-STEM, complemented by EDX chemical mapping, revealed an unusual formation of cluster structures containing local distributions of bimetallic (alloyed) Au–Ag NPs. The synergetic characteristics and properties of such bimetallic Au–Ag NPs resulted in an outstanding LSPR sensitivity compared to the monometallic counterparts. Furthermore, the analysis of the average nearest neighbor distances (about one order of magnitude lower than counterparts) suggests the existence of plasmonic hotspots relevant to be explored in sensing and surface-enhanced spectroscopies.

Plasmon-induced magnetic anapole mode assisted strong field enhancement.

Optical metamaterials, sensing, nonlinear optics, and surface-enhanced spectroscopies have witnessed the remarkable potential of the anapole mode. While dielectric particles with a high refractive index have garnered significant attention in recent years, the exploration of plasmonic anapole modes with intense localized electric field enhancements in the visible frequency range remains limited. In this study, we present a theoretical investigation on the relationship between the strongest near-field response and magnetic anapole modes, along with their substantial enhancement of Raman signals from probing molecules. These captivating findings arise from the design of a practical metallic oblate spheroid-film plasmonic system that generates magnetic anapole resonances at frequencies within the visible-near-infrared range. This research not only sheds light on the underlying mechanisms in a wide range of plasmon-enhanced spectroscopies but also paves the way for innovative nano-device designs.

Nanoparticle Size Influences the Self-Assembly of Gold Nanorods Using Flexible Streptavidin-Biotin Linkages.

The self-assembly of colloidal nanocrystals remains of robust interest due to its potential in creating hierarchical nanomaterials that have advanced function. For gold nanocrystals, junctions between nanoparticles yield large enhancements in local electric fields under resonant illumination, which is suitable for surface-enhanced spectroscopies for molecular sensors. Gold nanorods can provide such plasmonic fields at near-infrared wavelengths of light for longitudinal excitation. Through the use of careful concentration and stoichiometric control, a method is reported herein for selective biotinylation of the ends of gold nanorods for simple, consistent, and high-yielding self-assembly upon addition of the biotin-binding protein streptavidin. This method was applied to four different sized nanorods of similar aspect ratio and analyzed through UV-vis spectroscopy for qualitative confirmation of self-assembly and transmission electron microscopy to determine the degree of self-assembly in end-linked nanorods. The yield of end-linked assemblies approaches 90% for the largest nanorods and approaches 0% for the smallest nanorods. The number of nanorods linked in one chain also increases with an increased nanoparticle size. The results support the notion that the lower ligand density at the ends of the larger nanorods yields preferential substitution reactions at those ends and hence preferential end-to-end assembly, while the smallest nanorods have a relatively uniform ligand density across their surfaces, leading to spatially random substitution reactions.

Atomistic polarization model for Raman scattering simulations of large metal tips with atomic-scale protrusions at the tip apex

Abstract Tip-enhanced Raman spectroscopy (TERS) has recently been developed to push the spatial resolution down to single-chemical-bond scale. The morphology of the scanning tip, especially the atomistic protrusion at the tip apex, plays an essential role in obtaining both high spatial resolution and large field enhancement at the Ångström level. Although it is very difficult to directly characterize the atomistic structures of the tip, the Raman scattering from the apex’s own vibrations of the metal tip can provide valuable information about the stacking of atoms at the tip apex. However, conventional quantum chemistry packages can only simulate the Raman scattering of small metal clusters with few atoms due to huge computational cost, which is not enough since the shaft of the tip behind the apex also makes significant contributions to the polarizabilities of the whole tip. Here we propose an atomistic polarization model to simulate the Raman spectra of large metal tips at subwavelength scales based on the combination of the atomistic discrete dipole approximation model and the density functional theory. The atomistic tip with different sizes and stacking structures is considered in its entirety during the calculation of polarizabilities, and only the vibrational contributions from the tip apex are taken into account to simulate the Raman spectra of the tip. The Raman spectral features are found to be very sensitive to the local constituent element at the tip apex, atomic stacking modes, and shape of the tip apex, which can thus be used as a fingerprint to identify different atomistic structures of the tip apex. Moreover, our approaches can be extended to the metal tips with sub-wavelength sizes, making it possible to consider both the large scale and the atomistic detail of the tip simultaneously. The method presented here can be used as a basic tool to simulate the Raman scattering process of the metal tips and other nanostructures in an economic way, which is beneficial for understanding the roles of atomistic structures in tip- and surface-enhanced spectroscopies.

Chemical Sensing and Analysis with Optical Nanostructures

Nanostructures and nanomaterials, especially plasmonic nanostructures, often show optical properties that conventional materials lack and can manipulate light, as well as various light–matter interactions, in both their near-field and far-field regions with a high efficiency. Thanks to these unique properties, not only can they be used to enhance the sensitivity of chemical sensing and analysis techniques, but they also provide a solution for designing new sensing devices and simplifying the design of analytical instruments. The earliest applications of optical nanostructures are surface-enhanced spectroscopies. With the help of the resonance field enhancement of plasmonic nanostructures, molecular signals, such as Raman, infrared absorption, and fluorescence can be significantly enhanced, and even single-molecule analysis can be realized. Moreover, the resonant field enhancements of plasmonic nanostructures are often associated with other effects, such as optical forces, resonance shifts, and photothermal effects. Using these properties, label-free plasmonic sensors, nano-optical tweezers, and plasmonic matrix-assisted laser desorption/ionization have also been demonstrated in the past two decades. In the last few years, the research on optical nanostructures has gradually expanded to non-periodic 2D array structures, namely metasurfaces. With the help of metasurfaces, light can be arbitrarily manipulated, leading to many new possibilities for developing miniaturized integrated intelligent sensing and analysis systems. In this review, we discuss the applications of optical nanostructures in chemical sensing and analysis from both theoretical and practical aspects, aiming at a concise and unified framework for this field.

In Situ/Operando Characterization Techniques of Electrochemical CO2 Reduction.

Electrocatalytic conversion of carbon dioxide to valuable chemicals and fuels driven by renewable energy plays a crucial role in achieving net-zero carbon emissions. Understanding the structure-activity relationship and the reaction mechanism is significant for tuning electrocatalyst selectivity. Therefore, characterizing catalyst dynamic evolution and reaction intermediates under reaction conditions is necessary but still challenging. We first summarize the most recent progress in mechanistic understanding of heterogeneous CO2/CO reduction using in situ/operando techniques, including surface-enhanced vibrational spectroscopies, X-ray- and electron-based techniques, and mass spectroscopy, along with discussing remaining limitations. We then offer insights and perspectives to accelerate the future development of in situ/operando techniques.

Self-assembled PVP-gold nanostar films as plasmonic substrates for surface-enhanced spectroscopies: influence of the polymeric coating on the enhancement efficiency.

Colloidal nanoparticles exhibiting anisotropic morphologies are preferred in the structural design of spectroscopically active substrates due to the remarkable optical properties of this type of nano-object. In the particular case of star-like nanoparticles, their sharp tips can act as antennae for capturing and amplifying the incident light, as well as for enhancing the light emitted by nearby fluorophores or the scattering efficiency of Raman active molecules. In the current work, we aimed to implement such star-shaped nanoparticles in the fabrication of nanoparticle films and explore their use as solid plasmonic substrates for surface-enhanced optical spectroscopies. High-density, compact and robust self-assembled gold nanostar films were prepared by directly depositing them from aqueous colloidal suspension on polystyrene plates through convective self-assembly. We investigated the role of the polymeric coating, herein polyvinylpyrrolidone (PVP), in the particle assembly process, the resulting morphology and consequently, the plasmonic response of the obtained films. The efficacy of the plasmonic films as dual-mode surface-enhanced fluorescence (SEF) and surface-enhanced Raman scattering (SERS) substrates was evidenced by testing Nile Blue A (NB) and Rhodamine 800 (Rh800) molecular chromophores under visible (633 nm) versus NIR (785 nm) laser excitation. Steady-state and time-resolved fluorescence investigations highlight the fluorescence intensity and fluorescence lifetime modification effects. The experimental results were corroborated with theoretical modelling by finite-difference time-domain (FDTD) simulations. Furthermore, to prove the extended applicability of the proposed substrates in the detection of biologically relevant molecules, we tested their SERS efficiency for sensing metanephrine, a metabolite currently used for the biochemical diagnosis of neuroendocrine tumors, at concentration levels similar to other catecholamine metabolites.

Electrochemical Approaches to CO2 Conversion on Copper-Based Catalysts

ConspectusAs one of the essential pathways to carbon neutrality or carbon negativity, the electrochemical reduction of CO2 offers tremendous prospects for platform chemicals and fuel production. Copper (Cu) is currently the only metal material that is able to reduce CO2 to multicarbon (C2+) products. Despite the fact that copper-based materials have been investigated for decades, we still confront numerous challenges on the path to the fundamental understanding and large-scale deployment of copper-based electrocatalysts for CO2 reduction. For fundamental investigations, it remains a variety of open questions about the CO2 reduction mechanisms. The convoluted C–C coupling pathways and product bifurcation processes confuse the design of efficient catalysts. The active sites of copper-based catalysts remain ambiguous due to surface reconstruction. As for theoretical calculations, the construction of electrolyte–electrode models and the investigation of solvation effects are premature for obtaining confident conclusions. In addition, simple and easily scalable techniques for catalyst synthesis still need to be continuously developed.For practical applications, the CO2 electrolyzer with copper-based materials must be operated with high current densities, high Faradaic efficiencies, high energetic efficiencies, high single-pass conversion rates (high product concentration), and long stability. Nevertheless, due to the intricate nature of electrochemical systems, a high-performance copper-based electrocatalyst alone is not sufficient to meet all of the above commercialization requirements. Therefore, reactor design involving mass transfer enhancement calls for more research input. Based on the above background and the urgency of the net-zero goal, we initiated our research on CO2 electrolysis using copper-based materials with an emphasis on active site identification and mass transfer enhancement.This Account describes our contribution to the field of C2+ products formation. We first discuss the synthesis of copper-based materials with a controlled atomic arrangement and valence states based on neural network-accelerated computational simulations. Using the synthesized catalyst, the selectivity of the target product is improved and the energy consumption of CO2 electrolysis is reduced. Then, we describe the efforts to investigate the reaction mechanisms, such as using first-principles calculations at the atomic level, in situ surface-enhanced vibrational spectroscopies at the micrometer level, and electrochemical kinetics studies at the apparent performance level. We also overview our efforts in the field of reaction system engineering, consisting of a vapor-fed CO2 three-compartment flow cell and a large-scale CO2 membrane electrode assembly, which can increase the reaction rates and single-pass yield. Furthermore, we put forward the main technical obstacles that currently need to be surmounted and provide insights into the commercial application of CO2 electrolysis technology.

Temperature-sensitive hybridization of propagating and localized surface phonon polaritons in polar 4H-SiC nano-resonators

Polar 4H-SiC nano-resonators can host localized surface phonon polaritons (SPhPs) with low optical loss and fully exploit light–matter interactions for promising nanophotonic applications such as surface-enhanced spectroscopies and thermal imaging. To expand the mid-infrared and infrared application spaces, a sound knowledge of temperature effect on infrared dielectric functions and SPhPs of 4H-SiC is required, yet it remains largely unexplored. Herein, we focus on exploiting the temperature influence on dielectric functions, hybridization of propagating and localized SPhPs, and tailed spectral radiation properties of 4H-SiC nanopillar arrays through spectroscopic ellipsometry (SE) measurements as well as multiscale simulations. The 4H-SiC crystal is grown using the physical vapor transport method, and SE experiments measure infrared dielectric functions at temperatures between 300 and 800 K. Finite-element electromagnetic simulations confirm the emerged Monopole and transverse dipoles (TD1 and TD2) resonance modes in 4H-SiC nano-resonators, which agrees with the literature experiment. At high temperatures with strong lattice vibration, the amplitudes of resonant optical absorption peaks gradually decrease and the linewidths broaden, accompanied by the weakened electric resonances. First-principles calculations show that the anharmonic phonon scattering strengthens and less optical phonons are coupled to incident photons as temperature increases. Moreover, the propagating and localized SPhPs’ hybridization and spectral radiation properties of 4H-SiC nanopillar arrays can be largely tailed by modifying the morphology and incident angle of light. This work provides physical insights into the temperature-induced spectral tuning of 4H-SiC nano-resonators and helps exploit their applications in the high-temperature working conditions.

Surface enhanced fluorescence immuno-biosensor based on gold nanorods

Gold nanoparticles (AuNPs) are attractive structures for biosensing, most due to different properties at nanoscale and biocompatibility. Localized surface plasmon resonance (LSPR) is one of these properties; LSPR enable the electromagnetic field enhancement closer to metallic surface, which allows surface-enhanced spectroscopies, like surface enhanced fluorescence (SEF). In this study, an immuno-biosensor based on gold nanorods (AuNRs) and SEF was constructed for simple and fast analysis to detect albumin antibody (anti-BSA) using antigen–antibody (anti-BSA/BSA) interaction as the biorecognition model. AuNRs were presented in two distinct configurations, in suspension (S-AuNRs) and adsorbed on glass slides (AuNRs-chip), and the detection was performed through an extrinsic method, wherein the SEF signal of a reporter molecule (IR-820 cyanine-type dye) was monitored. The analyte detection was evidenced by SEF mapping, where the average signal in the presence of anti-BSA was three times more intense than for the assay in the absence of analyte. A digital protocol was proposed to simplify the spectroscopic data analysis and reduce the intensity variability; in this protocol the number of positive events in the presence of anti-BSA is much larger (around two times) compared to the absence of analyte. The AuNRs based SEF immuno-biosensor allowed an efficient and simple analysis with specific biorecognition and may contribute as an efficient spectroscopy platform for immuno-biosensing.

Plasmonic crystals fabricated by nanosphere lithography for advanced biosensing.

Plasmonic nanostructures have attracted wide attention in the past few years for their promising applications such as surface-enhanced spectroscopies, chemical or biosensing, and so on. However, the fabrication of plasmonic nanostructures relies on traditional photolithography methods such as electron beam lithography and focused ion beam lithography, which have inherent shortcomings, such as high fabrication cost and being time-consuming. Here, using the nanosphere lithography approach, we fabricate large-area long-range ordered periodic Au nanohole arrays on an opaque Au substrate. The structure supports spectral-isolation and well-defined plasmonic resonances favorable to spectral monitoring at normal incidence of light. The bulk sensitivity of up to 403 nm/RIU is measured for the plasmon modes. Furthermore, we assess the surface-sensing performance of the system and obtain a near-field decay length of about 240 nm, meaning that it is desirable to detect the biological protein molecules. The suggested plasmonic-sensing platform has broad application prospects in the development of low-cost and high-throughput biosensor chips.

Opportunities and Challenges for Alternative Nanoplasmonic Metals: Magnesium and Beyond.

Materials that sustain localized surface plasmon resonances have a broad technology potential as attractive platforms for surface-enhanced spectroscopies, chemical and biological sensing, light-driven catalysis, hyperthermal cancer therapy, waveguides, and so on. Most plasmonic nanoparticles studied to date are composed of either Ag or Au, for which a vast array of synthetic approaches are available, leading to controllable size and shape. However, recently, alternative materials capable of generating plasmonically enhanced light–matter interactions have gained prominence, notably Cu, Al, In, and Mg. In this Perspective, we give an overview of the attributes of plasmonic nanostructures that lead to their potential use and how their performance is dictated by the choice of plasmonic material, emphasizing the similarities and differences between traditional and emerging plasmonic compositions. First, we discuss the materials limitation encapsulated by the dielectric function. Then, we evaluate how size and shape maneuver localized surface plasmon resonance (LSPR) energy and field distribution and address how this impacts applications. Next, biocompatibility, reactivity, and cost, all key differences underlying the potential of non-noble metals, are highlighted. We find that metals beyond Ag and Au are of competitive plasmonic quality. We argue that by thinking outside of the box, i.e., by looking at nonconventional materials such as Mg, one can broaden the frequency range and, more importantly, combine the plasmonic response with other properties essential for the implementation of plasmonic technologies.

Carbon Nanotubes for the Optical Far-Field Readout of Processes That Are Mediated by Plasmonic Near-Fields

As science progresses at the nanoscopic level, it becomes more and more important to comprehend the interactions taking place at the nanoscale, where optical near-fields play a key role. Their phenomenology differs significantly from the propagative light we experience at the macroscopic level. This is particularly important in applications such as surface-enhanced spectroscopies for single-molecule detection, where often the optimization of the plasmonic structures and surfaces relies on far-field characterizations. The processes dominating in the far-field picture, though, are not the same dominating in the near-field. To highlight this, we resort to very simple metallic systems: Isolated gold nanorods in solution. We show how single-walled nanotubes can be exploited to read out processes occurring at the near-field level around metallic nanoparticles and make the information accessible in the far-field region. This is implemented by monitoring the spectral profile of the enhancement of the photoluminescence and Raman signal of the nanotubes for several excitation wavelengths. Through this excitation-resolved study, we show that the far-field optical read-out detects the transversal and longitudinal dipolar plasmonic oscillations of gold nanorods, whereas the near-field read-out through the nanotubes reveals other mechanisms to dominate. The spectral position of the maximum enhancement of the optical near-field mediated signals are located elsewhere than the far-field bands. This dichotomy between near-field and far-field response should be taken into account when optimizing plasmonic nanostructures for applications such as surface-enhanced spectroscopies.

Electrochemical Approaches for CO2 Conversion to Chemicals: A Journey toward Practical Applications.

Carbon capture, utilization, and sequestration play an essential role to address CO2 emissions. Among all carbon utilization technologies, CO2 electroreduction has gained immense interest due to its potential for directly converting CO2 to a variety of valuable commodity chemicals using clean, renewable electricity as the sole energy source. The research community has witnessed rapid advances in CO2 electrolysis technology in recent years, including highly selective catalysts, larger-scale reactors, specific process modeling, as well as a mechanistic understanding of the CO2 reduction reaction. The rapid advances in the field brings promise to the commercial application of the technology and the rapid rollout of the CO2 electroreduction for chemical manufacturing.This Account focuses on our contributions in both fundamental and applied research in the field of electrocatalytic CO2 and CO reduction reactions. We first discuss (1) the development of novel electrocatalysts for CO2/CO electroreduction to enhance the product selectivity and lower the energy consumption. Specifically, we synthesized nanoporous Ag and homogeneously mixed Cu-based bimetallic catalysts for the enhanced production of CO from CO2 and multicarbon products from CO, respectively. Then, we review our efforts in (2) the field of reactor engineering, including a dissolved CO2 H-type cell, vapor-fed CO2 three-compartment flow cell, and vapor-fed CO2 membrane electrode assembly, for enhancing reaction rates and scalability. Next, we describe (3) the investigation of reaction mechanisms using in situ and operando techniques, such as surface-enhanced vibrational spectroscopies and electrochemical mass spectroscopy. We revealed the participation of bicarbonate in CO2 electroreduction on Au using attenuated total-reflectance surface-enhanced infrared absorption spectroscopy, the presence of an "oxygenated" surface of Cu under CO electroreduction conditions using surface-enhanced Raman spectroscopy, and the origin of oxygen in acetaldehyde and other CO electroreduction products on Cu using flow electrolyzer mass spectrometry. Lastly, we examine (4) the commercial potential of the CO2 electrolysis technology, such as understanding pollutant effects in CO2 electroreduction and developing techno-economic analysis. Specifically, we discuss the effects of SO2 and NOx in CO2 electroreduction using Cu, Ag, and Sn catalysts. We also identify technical barriers that need to be overcome and offer our perspective on accelerating the commercial deployment of the CO2 electrolysis technology.

Collective Phonon-Polaritonic Modes in Silicon Carbide Subarrays.

Localized surface phonon polaritons (LSPhPs) can be implemented to engineer light-matter interactions through nanoscale patterning for a range of midinfrared application spaces. However, the polar material systems studied to date have mainly focused on simple designs featuring a single element in the periodic unit cell. Increasing the complexity of the unit cell can serve to modify the resonant near-fields and intra- and inter-unit-cell coupling as well as to dictate spectral tuning in the far-field. In this work, we exploit more complicated unit-cell structures to realize LSPhP modes with additional degrees of design freedom, which are largely unexplored. Collectively excited LSPhP modes with distinctly symmetric and antisymmetric near-fields are supported in these subarray designs, which are based on nanopillars that are scaled by the number of subarray elements to ensure a constant unit-cell size. Moreover, we observe an anomalous mode-matching of the collective symmetric mode in our fabricated subarrays that is robust to changing numbers of pillars within the subarrays as well as to defects intentionally introduced in the form of missing pillars. This work therefore illustrates the hierarchical design of tailored LSPhP resonances and modal near-field profiles simultaneously for a variety of IR applications such as surface-enhanced spectroscopies and biochemical sensing.

Metallic Plasmonic Array Structures: Principles, Fabrications, Properties, and Applications (Adv. Mater. 50/2021)

Metallic Plasmonic Arrays Metallic plasmonic array structures provide a powerful platform to control light–matter interactions and show fascinating, rich, and tunable optical properties through morphology and parameter engineering enabled by nanofabrication. In article number 2007988, Bowen Liu, Bin Ren, and co-workers review light-management mechanisms, fabrication techniques, and applications, such as plasmonic sensing, surface-enhanced spectroscopies, nanolasing, and perfect light absorption, for metallic plasmonic array structures.

DNA Origami Nanoantennas for Fluorescence Enhancement.

The possibility to increase fluorescence by plasmonic effects in the near-field of metal nanostructures was recognized more than half a century ago. A major challenge, however, was to use this effect because placing single quantum emitters in the nanoscale plasmonic hotspot remained unsolved for a long time. This not only presents a chemical problem but also requires the nanostructure itself to be coaligned with the polarization of the excitation light. Additional difficulties arise from the complex distance dependence of fluorescence emission: in contrast to other surface-enhanced spectroscopies (such as Raman spectroscopy), the emitter should not be placed as close as possible to the metallic nanostructure but rather needs to be at an optimal distance on the order of a few nanometers to avoid undesired quenching effects.Our group addressed these challenges almost a decade ago by exploiting the unique positioning ability of DNA nanotechnology and reported the first self-assembled DNA origami nanoantennas. This Account summarizes our work spanning from this first proof-of-principle study to recent advances in utilizing DNA origami nanoantennas for single DNA molecule detection on a portable smartphone microscope.We summarize different aspects of DNA origami nanoantennas that are essential for achieving strong fluorescence enhancement and discuss how single-molecule fluorescence studies helped us to gain a better understanding of the interplay between fluorophores and plasmonic hotspots. Practical aspects of preparing the DNA origami nanoantennas and extending their utility are also discussed.Fluorescence enhancement in DNA origami nanoantennas is especially exciting for signal amplification in molecular diagnostic assays or in single-molecule biophysics, which could strongly benefit from higher time resolution. Additionally, biophysics can greatly profit from the ultrasmall effective detection volumes provided by DNA nanoantennas that allow single-molecule detection at drastically elevated concentrations as is required, e.g., in single-molecule DNA sequencing approaches.Finally, we describe our most recent progress in developing DNA NanoAntennas with Cleared HOtSpots (NACHOS) that are fully compatible with biomolecular assays. The developed DNA origami nanoantennas have proven robustness and remain functional after months of storage. As an example, we demonstrated for the first time the single-molecule detection of DNA specific to antibiotic-resistant bacteria on a portable and battery-driven smartphone microscope enabled by DNA origami nanoantennas. These recent developments mark a perfect moment to summarize the principles and the synthesis of DNA origami nanoantennas and give an outlook of new exciting directions toward using different nanomaterials for the construction of nanoantennas as well as for their emerging applications.

Rod–sphere cluster irradiation with femtosecond laser pulses: cut and paste at the nanoscale

Abstract We report on the irradiation of gold rod–sphere assemblies with ultrashort laser pulses, producing structures that are very difficult to obtain by other methods. The optical response of these assemblies displays several peaks arising from the interaction of the plasmon modes of the individual particles, offering thus great flexibility to control the energy deposited on the individual particles. Judicious selection of the wavelength and fluence of the laser pulses allow fine control over the changes produced: the particles can be melted, welded and/or the organic links cleaved. In this way, it is possible to generate structures “à la carte” with a degree of control unmatched by other synthetic protocols. The method is exemplified with gold nanoparticles, but it can be easily implemented on particles composed of different metals, widening considerably the range of possibilities. The final structures are excellent candidates for surface-enhanced spectroscopies or plasmonic photothermal therapy as they have a very intense electric field located outside the structure, not in the gaps.

Engineering Electromagnetic Hot-Spots in Nanoparticle Cluster Arrays on Reflective Substrates for Highly Sensitive Detection of (Bio)molecular Analytes.

Intense electromagnetic (EM) hot-spots arising at the junctions or gaps in plasmonic nanoparticle assemblies can drive ultrahigh sensitivity in molecular detection by surface-enhanced spectroscopies. Harnessing this potential however requires access to the confined physical space at the EM hot-spots, which is a challenge for larger analytes such as biomolecules. Here, we demonstrate self-assembly derived gold nanoparticle cluster arrays (NCAs) on gold substrates exhibiting controlled interparticle (<1 nm wide) and intercluster (<10 nm wide) hot-spots as highly promising in this direction. Sensitivity of the NCAs toward detection of small (<1 nm) or large (protein-receptor interactions) analytes in surface-enhanced Raman and metal-enhanced fluorescence assays is found to be strongly impacted by the size of the cluster and the presence of reflective substrates. Experiments supported by numerical simulations attribute the higher sensitivity to higher EM field enhancements at the hot-spots, as well as greater analyte leverage over EM hot-spots. The best-performing arrays could push the sensitivity down to picomolar detection limits for sub-nanometric organic analytes as well as large protein analytes. The investigation paves the way for rational design of plasmonic biosensors and highlights the unique capabilities of a molecular self-assembly approach toward catering to this objective.

Metallic Plasmonic Array Structures: Principles, Fabrications, Properties, and Applications.

The vast development of nanofabrication has spurred recent progress for the manipulation of light down to a region much smaller than the wavelength. Metallic plasmonic array structures are demonstrated to be the most powerful platform to realize controllable light-matter interactions and have found wide applications due to their rich and tunable optical performance through the morphology and parameter engineering. Here, various light-management mechanisms that may exist on metallic plasmonic array structures are described. Then, the typical techniques for fabrication of metallic plasmonic arrays are summarized. Next, some recent applications of plasmonic arrays are reviewed, including plasmonic sensing, surface-enhanced spectroscopies, plasmonic nanolasing, and perfect light absorption. Lastly, the existing challenges and perspectives for metallic plasmonic arrays are discussed. The aim is to provide guidance for future development of metallic plasmonic array structures.