Single Plasmonic Nanoparticles Research Articles

Radially polarized light in single particle optical extinction microscopy identifies silver nanoplates

Quantifying the optical extinction cross section of a single plasmonic nanoparticle (NP) has recently emerged as a powerful method to characterize the NP morphometry, i.e., size and shape, with a precision comparable to electron microscopy while using a simple optical microscope. Here, we enhance the capabilities of extinction microscopy by introducing a high numerical aperture annular illumination coupled with a radial polarizer to generate a strong axial polarization component. This enables us to probe the NP response to axial polarized light, and, in turn, to distinguish flat-lying nanoplates from other geometries. Polarization-resolved optical extinction cross sections were acquired on 219 individual colloidal silver NPs of a nominally triangular nanoplate shape but, in practice, exhibiting heterogeneous morphometries, including decahedrons and non-plate spheroids. An unsupervised machine learning cluster analysis algorithm was developed, which allowed us to separate NPs into different groups, owing to the measured differences in cross sections. Comparison of the measurements with a computational model of the absorption and scattering cross section accounting for nanoplates of varying geometries beyond simple triangles provided insight into the NP shape of each group. The results provide a significant improvement of polarization-resolved optical extinction microscopy to reconstruct NP shapes, further boosting the utility of the method as an alternative to electron microscopy analysis.

Single AgNF@ZIF-8 nanoparticle for deep learning assisted SERS detection of gaseous molecule

Random nanogaps between plasmonic nanoparticles formed by the surface tension of solution bring a great challenge in the application of Surface Enhanced Raman Spectroscopy (SERS) technique. Meanwhile, due to its natural nanogaps on the surface, single plasmonic nanoflower exhibits a unique charm for avoiding random gaps in the quantitative analysis of SERS. Herein, a single core-shell plasmonic nanoparticle consisting of an Ag nanoflower (AgNF) core and zeolite imidazolate frame-8 (ZIF-8) shell is synthesized for SERS detection of the gaseous molecule. Benefiting the porous shell of ZIF-8 to capture gaseous molecules and natural nanogaps on the surface of AgNF to enhance Raman intensity, SERS spectra of the gaseous molecule are successfully collected with high sensitivity at 10−6 M, which also exhibit high SERS stability with RSD at 2.29 % for single nanoparticle and 9.86 % for multiple single nanoparticles. In addition, two levels of automatic identification based on deep learning (DL) are also implemented in this work, whose data demonstrate artificial neural network (ANN) algorithm could identify gaseous glutaraldehyde (GA) as typical volatile organic compounds (VOCs) with high accuracy at 97.5 %. This single core-shell plasmonic MOF nanoparticle overcomes the limitations of traditional SERS detection in nanoparticle aggregating and realizes the detection of gaseous molecules, which enlarges the application of SERS technique.

Unraveling the Chirality Transfer from Circularly Polarized Light to Single Plasmonic Nanoparticles.

Due to their broken symmetry, chiral plasmonic nanostructures have unique optical properties and numerous applications. However, there is still a lack of comprehension regarding how chirality transfer occurs between circularly polarized light (CPL) and these structures. Here, we thoroughly investigate the plasmon-assisted growth of chiral nanoparticles from achiral Au nanocubes (AuNCs) via CPL without the involvement of any chiral molecule stimulators. We identify the structural chirality of our synthesized chiral plasmonic nanostructures using circular differential scattering (CDS) spectroscopy, which is correlated with scanning electron microscopy imaging at both the single-particle and ensemble levels. Theoretical simulations, including hot-electron surface maps, reveal that the plasmon-induced chirality transfer is mediated by the asymmetric distribution of hot electrons on achiral AuNCs under CPL excitation. Furthermore, we shed light on how this plasmon-induced chirality transfer can also be utilized for chiral growth in bimetallic systems, such as Ag or Pd on AuNCs. The results presented here uncover fundamental aspects of chiral light-matter interaction and have implications for the future design and optimization of chiral sensors and chiral catalysis, among others.

Unraveling the Chirality Transfer from Circularly Polarized Light to Single Plasmonic Nanoparticles

AbstractDue to their broken symmetry, chiral plasmonic nanostructures have unique optical properties and numerous applications. However, there is still a lack of comprehension regarding how chirality transfer occurs between circularly polarized light (CPL) and these structures. Here, we thoroughly investigate the plasmon‐assisted growth of chiral nanoparticles from achiral Au nanocubes (AuNCs) via CPL without the involvement of any chiral molecule stimulators. We identify the structural chirality of our synthesized chiral plasmonic nanostructures using circular differential scattering (CDS) spectroscopy, which is correlated with scanning electron microscopy imaging at both the single‐particle and ensemble levels. Theoretical simulations, including hot‐electron surface maps, reveal that the plasmon‐induced chirality transfer is mediated by the asymmetric distribution of hot electrons on achiral AuNCs under CPL excitation. Furthermore, we shed light on how this plasmon‐induced chirality transfer can also be utilized for chiral growth in bimetallic systems, such as Ag or Pd on AuNCs. The results presented here uncover fundamental aspects of chiral light‐matter interaction and have implications for the future design and optimization of chiral sensors and chiral catalysis, among others.

One-Shot Dual-Detection-Based Single-Molecule Super-Resolution Imaging Method for Real-Time Observation of Spatiotemporal Catalytic Activity Variations on the Plasmonic Gold Nanoparticle Surface.

Understanding the relationship between the surface properties of a single plasmonic nanoparticle and its catalytic performance is critical for developing highly efficient nanocatalysts. In this study, a one-shot dual-detection-based single-molecule super-resolution imaging method in the evanescent field was developed to observe real-time spatiotemporal catalytic activity on a single plasmonic gold nanoparticle (AuNP) surface. The scattering intensity of AuNPs and the fluorescence of resorufin molecules produced on the AuNP surface were obtained simultaneously to investigate the relationship between nanoparticles and catalytic reactions at a single-molecule level. Chemisorbed adsorbates (i.e., catalytic product and resorufin) changed the electron density of individual AuNPs throughout the catalytic cycle, resulting in the fluctuation of the scattering intensity of individual AuNPs, which was attributed to the electron transfer between reactant resazurin molecules and AuNPs. The increase in the electron density of individual AuNPs affected the catalytic reaction rate. Furthermore, sequential mapping of individual catalytic events at the subdiffraction limit resolution was completed for real-time surface dynamics and spatiotemporal activity variations on the single AuNP surface. The developed method can aid in understanding surface-property-dependent catalytic kinetics and facilitate the development of nanoparticle-based heterogeneous catalysts at subdiffraction limit resolution.

Energy-Resolved Femtosecond Hot Electron Dynamics in Single Plasmonic Nanoparticles.

Efficient excitation and harvesting of hot carriers from nanoscale metals is central to many emerging photochemical, photovoltaic, and ultrafast optoelectronic applications. Nevertheless, direct experimental evidence of the energy-dependent femtosecond dynamics in ubiquitous tens-of-nanometer gold structures remains elusive, despite the potentially rich interplay between interfacial and internal plasmonic fields, excitation distributions, and scattering processes. To explore the effects of nanoscale structure on these dynamics, we employ simultaneous time-, angle-, and energy-resolved photoemission spectroscopy of single plasmonic nanoparticles. Photoelectron velocity and electric field distributions reveal bulk-like ballistic hot electron transport in different geometries, lacking any signatures of surface effects. Energy-resolved dynamics are measured in the 1-2 eV range and extrapolated to lower energies via Boltzmann theory, providing a detailed view of hot electron lifetimes within nanoscale gold. We find that particles with relevant dimensions as small as 10 nm serve as exemplary platforms for studying intrinsic metal dynamics.

Scattering spectroscopy on single plasmonic nanoparticles using a confocal darkfield setup

We demonstrate how to measure scattering spectra of single plasmonic nanoparticles using a confocal darkfield setup. We give an overview of considerations and problems we encountered when employing a darkfield technique based on filtering illumination under low angles instead of the conventional high-angle filtering by darkfield objectives.

Single-Particle Measurements of Nanocatalysis with Dark-Field Microscopy

Due to the complexity of heterogeneous reactions and heterogeneities of individual catalyst particles in size, morphology, and the surrounding medium, it is very important to characterize the structure of nanocatalysts and measure the reaction process of nanocatalysis at the single-particle level. Traditional ensemble measurements, however, only provide averaged results of billions of nanoparticles (NPs), which do not help reveal structure–activity relationships and may overlook a few NPs with high activity. The advent of dark-field microscopy (DFM) combined with plasmonic resonance Rayleigh scattering (PRRS) spectroscopy provides a powerful means for directly recording the localized surface plasmon resonance (LSPR) spectrum of single plasmonic nanoparticles (PNPs), which also enables quantitative measurements. In recent years, DFM has developed rapidly for a series of single-particle catalytic reactions such as redox reactions, electrocatalytic reactions, and DNAzyme catalysis, with the ability to monitor the catalytic reaction process in real time and reveal the catalytic mechanism. This review provides a comprehensive overview of the fundamental principles and practical applications of DFM in measuring various kinds of catalysis (including chemocatalysis, electrocatalysis, photocatalysis, and biocatalysis) at the single-particle level. Perspectives on the remaining challenges and future trends in this field are also proposed.

Strong mode coupling-enabled hybrid photon-plasmon laser with a microfiber-coupled nanorod.

Laser based on single plasmonic nanoparticle can provide optical frequency radiation far beyond the diffraction limit and is one of the ultimate goals of nanolasers, yet it remains a challenge to be realized because of the inherently high Ohmic loss. Here, we report the direct observation of lasing in microfiber-coupled single plasmonic nanoparticles enabled by strong mode coupling. We show that, by strongly coupling a gold nanorod (GNR) with the whispering gallery cavity of a dye-doped polymer microfiber (with diameter down to 2.0 μm), the substantially enhanced optical coherence of the hybrid photon-plasmon mode and effective gain accumulated from the active microfiber cavity enable single-mode laser emission from the GNR at room temperature with a threshold as low as 2.71 MW/cm2 and a linewidth narrower than 2 nm.

Strong coupling of single plasmonic nanoparticles and nanogaps with quantum emitters

In cavity quantum electrodynamics, when the interaction between quantum emitter and cavity mode is strong enough to overcome the mean decay rate of the system, it will enter into a strong coupling regime, thereby forming part-light part-matter polariton states. Strong coupling can serve as a promising platform for room temperature Bose-Einstein condensation, polariton lasing, single photon nonlinearity, quantum information, etc. Localized surface plasmons supported by single metal nanostructures possess extremely small mode volume, which is favorable for realizing strong coupling. Moreover, the nanoscale dimensions of plasmonic structures can facilitate the miniaturization of strong coupling systems. Here, the research progress of strong plasmon-exciton coupling between single metal nanoparticles/nanogaps and quantum emitters is reviewed. The theory background of strong coupling is first introduced, including quantum treatment, classical coupled oscillator model, as well as the analytical expressions for scattering and photoluminescence spectra. Then, strong coupling between different kinds of plasmonic nanostructures and quantum emitters is reviewed. Single metal nanoparticles, nanoparticle dimers, and nanoparticle-on-mirror structures constitute the most typical plasmonic nanostructures. The nanogaps in the latter two systems can highly concentrate electromagnetic field, providing optical nanocavities with smaller mode volume than single nanoparticles. Therefore, the larger coupling strength can be achieved in the nanogap systems, which is conducive to strong coupling at the single-exciton level. In addition, the active tuning of strong coupling based separately on thermal, electrical and optical means are reviewed. The energy and oscillator strength of the excitons in transition metal dichalcogenide (TMDC) monolayers are dependent on temperature. Therefore, the strong coupling can be tuned by heating or cooling the system. The excitons in TMDC monolayers can also be tuned by electrical gating, enabling electrical control of strong coupling. Optically tuning the quantum emitters provides another way to actively control the strong coupling. Overall, the research on active tuning of strong plasmon-exciton coupling is still very limited, and more investigations are needed. Finally, this review is concluded with a short summary and the prospect of this field.

Plasmonic Au@Ag@mSiO2 Nanorattles for In Situ Imaging of Bacterial Metabolism by Surface-Enhanced Raman Scattering Spectroscopy.

It is well known that microbial populations and their interactions are largely influenced by their secreted metabolites. Noninvasive and spatiotemporal monitoring and imaging of such extracellular metabolic byproducts can be correlated with biological phenotypes of interest and provide new insights into the structure and development of microbial communities. Herein, we report a surface-enhanced Raman scattering (SERS) hybrid substrate consisting of plasmonic Au@Ag@mSiO2 nanorattles for optophysiological monitoring of extracellular metabolism in microbial populations. A key element of the SERS substrate is the mesoporous silica shell encapsulating single plasmonic nanoparticles, which furnishes colloidal stability and molecular sieving capabilities to the engineered nanostructures, thereby realizing robust, sensitive, and reliable measurements. The reported SERS-based approach may be used as a powerful tool for deciphering the role of extracellular metabolites and physicochemical factors in microbial community dynamics and interactions.

Plasmonic Nanoarchitectures for Single‐Molecule Explorations: An Overview

Plasmonic nanostructures have immense potentials for extreme concentration of light into deep‐subwavelength spaces with giant local field intensity, which can be exploited for novel applications including nanoscale optical trapping, biosensing, and enhanced spectroscopy. Herein, a succinct overview of the potentials of engineered plasmonic nanoarchitectures of various geometries including nanoparticles, nanodimers, nanoapertures, nanoporous surfaces, and picometer‐scale gap systems for single‐molecule analysis is provided. In particular, the potentials of single plasmonic nanoparticles for single‐molecule sensing, coupled plasmonic nanodimers for few‐molecule strong coupling, metallic nanocavities for optical manipulation of single molecules, nanoporous metasurfaces for enhanced single‐molecule spectroscopy, and plasmonic picocavities for single‐molecule optomechanics are extensively discussed. Finally, as an outlook, exploiting such novel nanoarchitectures for developing innovative biosensing platforms that will be able to trap and detect objects at the single‐molecule level is forwarded.

Toward Quantitative Nanothermometry Using Single-Molecule Counting.

Photothermal heating of nanoparticles has applications in nanomedicine, photocatalysis, photoelectrochemistry, and data storage, but accurate measurements of temperature at the nanoparticle surface are lacking. Here we demonstrate progress toward a super-resolution DNA nanothermometry technique capable of reporting the surface temperature on single plasmonic nanoparticles. Gold nanoparticles are functionalized with double-stranded DNA, and the extent of DNA denaturation under heating conditions serves as a reporter of temperature. Fluorescently labeled DNA oligomers are used to probe the denatured DNA through transient binding interactions. By counting the number of fluorescent binding events as a function of temperature, we reconstruct DNA melting curves that reproduce trends seen for solution-phase DNA. In addition, we demonstrate our ability to control the temperature of denaturation by changing the Na+ concentration and the base pair length of the double-stranded DNA on the nanoparticle surface. This degree of control allows us to select narrow temperature windows to probe, providing quantitative measurements of temperature at nanoscale surfaces.

Bowtie-based plasmonic metal nanoparticle complexes to enhance the opto-electronic performance of thin-film solar cells.

This computational study investigates the possibility of using different multi-particle plasmonic nanoparticle complexes to enhance the opto-electronic performance of thin-film solar cells (TFSCs). The nanoparticle complexes are in a bowtie nanocomplex (BNC) configuration whereby each of the BNCs comprises a set of bowtie nanoantenna and a spherical nanoparticle. The results show that such plasmonic BNCs significantly enhance the opto-electronic performance of thin-film solar cells when compared to a bare TFSC or a TFSC modified with a single plasmonic nanoparticle. These results indicate a potential new, to the best of our knowledge, avenue of designing high-performance TFSCs of the future.

Interferometric scattering of a single plasmonic nanoparticle cluster assembled in a nanostructured template.

In this work, we investigate the light scattering of a single Au nanoparticle cluster assembled in a nanostructured substrate and study how the substrate geometry influences the scattering spectrum. An explicit model was built with the help of the Green's tensor theory, showing that there are two distinct types of substrate effects, namely, the interferometric scattering caused by the local corrugation and the spectral modulation caused by the global features (i.e., the layered substrate in this work). The result predicted by the model agrees with the experimental results well, providing a simple yet quantitative tool for the spectral interpretation of plasmonic nanostructures with complex substrates.

Single-particle scattering spectroscopy: fundamentals and applications

Abstract Metallic nanoparticles supporting a localized surface plasmon resonance have emerged as promising platforms for nanoscopic labels, sensors, and (photo-) catalysts. To use nanoparticles in these capacities, and to gain mechanistic insight into the reactivity of inherently heterogeneous nanoparticles, single-particle characterization approaches are needed. Single-particle scattering spectroscopy has become an important, highly sensitive tool for localizing single plasmonic nanoparticles and studying their optical properties, local environment, and reactivity. In this review, we discuss approaches taken for collecting the scattered light from single particles, their advantages and disadvantages, and present some recent applications. We introduce techniques for the excitation and detection of single-particle scattering such as high-angle dark-field excitation, total internal reflection dark-field excitation, scanning near-field microscopy, and interferometric scattering. We also describe methods to achieve polarization-resolved excitation and detection. We then discuss different approaches for scanning, ratiometric, snapshot, and interferometric hyperspectral imaging techniques used to extract spectral information. Finally, we provide a brief overview of specialized setups for in situ measurements of nanoparticles in liquid systems and setups coupled to scanning tip microscopes.

A caging strategy for tuning the magneto-optical properties of cobalt ferrite using a single plasmonic nanoparticle

Investigations of the Faraday effect in silica capsules with numerous CoFe2O4 nanoparticles and one single gold nanoparticle demonstrate the plasmon-induced changes in the MOA of the ferrite and highlights the caging strategy designed.

Real-Time Study of Protein Phase Separation with Spatiotemporal Analysis of Single-Nanoparticle Trajectories.

Liquid-liquid phase separation (LLPS) underlies the formation mechanism of membraneless biomolecular condensates locally to perform important physiological functions such as selective autophagy, but little is known about the relationship between their dynamic structural organization and biophysical properties. Here, a dark-field microscopy based single plasmonic nanoparticle tracking (DFSPT) technique was introduced to simultaneously monitor the diffusion dynamics of multiple gold nanorod (AuNR) probes in a protein LLPS system and to quantitatively characterize the spatiotemporal heterogeneity of the LLPS condensates during their phase transformation. Based on spatially and temporally resolved analysis of the diffusional behavior of the AuNRs, structure and material properties of p62 condensates, such as the viscoelasticity, the compartmentalization, and the recruitment of protein-covered nanoparticles into the large droplet, have been observed. Moreover, the nonsmooth droplet interface, its solidification after further phase transition or maturation, and the size effect of the inner vacuoles have also been revealed. Our method can be potentially applied to in vitro investigation of different reconstituted membrane-free biomolecular condensates and in vivo study of their dynamic evolution.

Investigation of electron transfer between single plasmon and graphene by dark field spectroscopy

We investigated the electron transfer time between single plasmonic gold nanoparticles and graphene with our home-build spectral imaging dark-field microscope. The process of electron transfer is supposed to be shuttling of hot electrons on the nanoparticle-graphene interface, resulting in a slight broadening of the scattering spectrum. For detecting the minor spectrum broadening, we firstly characterized our setup systematically and then calibrated its intrinsic error. We found the mechanism of a common but normally neglected setup error, scattering spectrum broadening, which is caused by the bandwidth of the incident light and could exist in most fast dark-field microscopy setups. We corrected the linewidth of plasmon scattering spectra theoretically by both numerical and analytical solution, and then realized it experimentally by tuning the bandwidth of the incident light. After calibration, we revisited scattering spectra of 700 small aspect ratio nanorods on glass and monolayer graphene revealing a typical 14.3 meV linewidth broadening. Furthermore, we measured four other kinds of gold nanoparticles on glass, mono- and bilayer graphene for deeper understanding of the electron transfer. A common linewidth broadening is found for each kind of particle agreeing well with previous theory. However, an unconventional linewidth narrowing is also discovered for big particles whose resonance wavelength is close to the near infrared region. It implies a competitive mechanism in the electron transfer process which could not only increase the damping of small particles, causing a linewidth broadening, but also simplify the electric field pattern for big particles, leading to a linewidth narrowing, according to our Mie theory simulation.

Single Particle Approaches to Plasmon-Driven Catalysis.

Plasmonic nanoparticles have recently emerged as a promising platform for photocatalysis thanks to their ability to efficiently harvest and convert light into highly energetic charge carriers and heat. The catalytic properties of metallic nanoparticles, however, are typically measured in ensemble experiments. These measurements, while providing statistically significant information, often mask the intrinsic heterogeneity of the catalyst particles and their individual dynamic behavior. For this reason, single particle approaches are now emerging as a powerful tool to unveil the structure-function relationship of plasmonic nanocatalysts. In this Perspective, we highlight two such techniques based on far-field optical microscopy: surface-enhanced Raman spectroscopy and super-resolution fluorescence microscopy. We first discuss their working principles and then show how they are applied to the in-situ study of catalysis and photocatalysis on single plasmonic nanoparticles. To conclude, we provide our vision on how these techniques can be further applied to tackle current open questions in the field of plasmonic chemistry.