Plasmonic Particles Research Articles

Nonclassical Optical Response of Particle Plasmons With Quantum‐Informed Local Optics

AbstractAs the dimensions of plasmonic structures or the field confinement length approach the mean free path of electrons, mesoscopic optical response effects, including nonlocality, electron spill‐in or spill‐out, and Landau damping, are expected to become observable. In this work, a quantum‐informed local analogue model (QILAM) that maps these nonclassical optical responses onto a local dielectric film is presented. The primary advantage of this model lies in its compatibility with the highly efficient boundary element method (BEM), which includes retardation effects with relatively large particle sizes. Furthermore, the approach offers a unified framework that connects two important semiclassical theories: the generalized nonlocal optical response (GNOR) theory and the Feibelman d‐parameters formalism. It is envisioned that QILAM can evolve into a multiscale electrodynamic tool for exploring nonclassical optical responses in diverse plasmonic structures in the future. This can be achieved by directly translating mesoscopic effects into observable phenomena, such as plasmon resonance energy shifts and linewidth broadening in the scattering spectrum.

Half-wave nanolasers and intracellular plasmonic lasing particles

Half-wave nanolasers and intracellular plasmonic lasing particles

Theoretical insights into charge transfer plasmon lifetime

In this Letter, we present a theoretical study based on the Lorentz function and harmonic oscillator model to explore temporal dynamics of charge transfer plasmon (CTP) resonances. By fitting scattering curves and near-field oscillations, we determine the dephasing time of CTP modes in conductively connected gold nanodisk dimers. We show that, compared with the well-known particle plasmon and dimer plasmon modes, the CTP mode has a narrow spectral width and longer lifetime. Moreover, quantitative analysis of optical near-fields reveals that CTP modes oscillate completely out-of-phase with the particle plasmon and dimer plasmon modes. The dephasing time, near-field decay rate and charge transfer time of the CTP mode are found to be on a few femtosecond timescales, implying that conductively connected plasmonic nanoparticles hold great promise as channels for ultrafast transfer of information in all-optical computing and optoelectronic devices.

Multifunctional Janus particles composed of inorganic nanoparticles through emulsion confined assembly.

Janus particles, consisting of two or more chemically distinct composites within a single structural system, have attracted significant attention for their solid surfactant functionality, as well as their potential applications in micro/nanomotors and functional materials. Here, we present a simple and robust method to prepare plasmonic Janus particles consisting of a polystyrene-tethered gold nanorod (AuNRs@PS) head and a poly(4-vinylpyridine) (P4VP) head through emulsion confined assembly. The balance of the Janus particles can be finely tuned by adjusting the volume ratio of the AuNRs@PS solution and P4VP solution. The result shows that the diameter ratio (r) of AuNRs@PS5k/P4VP is proportional to the volume ratio (R) of the AuNRs@PS and P4VP solutions. Furthermore, the obtained Janus particles with AuNR head have a peak absorbance of around 800 nm, which can be applied in photothermal therapy. Additionally, multifunctionality can be achieved by reducing nanoparticle (NP) precursors on a prefabricated scaffold of P4VP or co-assembling P4VP-tethered NPs with AuNRs@PS building blocks. These multifunctional Janus particles hold great potential for applications in micro/nanomotors, catalysts, and biological materials.

Chiroptical response of an array of isotropic plasmonic particles having a chiral arrangement under coherent interaction.

The chirality and chiroptical response of materials have attracted significant attention for their potential to introduce the new science of light-matter interactions. We demonstrate that collective mode formation under modal coupling between localized surface plasmon resonances (LSPRs) with a chiral arrangement and Fabry-Pérot (FP) nanocavity modes can induce chiroptical responses. We fabricated a cluster of isotropic gold nanodisks with a chiral arrangement (gold nano-windmills, Au-NWs) on the FP nanocavities of TiO2 and Au film. The differential absorption of the Au-NWs coupled with the FP nanocavities under left- and right-handed circularly polarized light irradiations in the far field was significantly enhanced compared with the differential absorption without the FP nanocavities. Far- and near-field analyses by numerical simulation revealed that the Au-NWs coupled with the FP nanocavities formed a collective mode in the near field, and the collective mode represented the chiroptical response in the far field. The light field with the large helicity, can be used in chiral light-matter interactions. The concept of collective mode formation using isotropic metal nanodisks coupled with FP nanocavities provides a platform for controlling complex light fields.

Engineering plasmonic charge kinetics and broadband photoelectrochemical spectral responses using a multi-resonant Au-TiO2 plasmonic particle grating-based optical resonator.

The plasmonic integrated semiconductor has widened the operational spectral region of semiconductors for light-matter interaction-driven solar energy harvesting applications. However, a specific plasmonic resonance has moderate light absorption and is only active in a specific width of the visible spectrum. We present a tailored plasmonic particle grating-based Au-TiO2 Schottky photoelectrode-based broadband absorber that operates in the extended spectral region of 400-800 nm due to the synergistic interaction of multi-resonant photonic and plasmonic modes of the plasmonic particle grating structure. In the visible spectrum, the proposed photoelectrode increased the incoming photon to electron conversion efficiency (IPCE%) by seven and five times more than TiO2 for TM (along the grating vector) and TE (perpendicular to the grating vector) incidence, respectively. The plasmonic response of the gold nanoparticle and the grating-coupled surface plasmon polariton (SPP)-guided mode resonance (GMR) are responsible for such increments. Ultrafast pump-probe spectroscopy verifies that the plasmon-GMR interaction causes extended plasmonic charge generation and lifetime. The kinetics of plasmonic-generated charges in grating-coupled SPP and LSPR was investigated through TM and TE polarized pump and probe excitation. Such findings are consistent with the observed PEC spectral responses under their respective polarization illumination. Therefore, our research provides a simple method for integrating photonic and plasmonic materials for innovative broadband spectrum responses in photovoltaic and energy harvesting applications.

Analysis of the radiative corrections and dynamic extensions to the local field in the effective refractive index of particle suspensions

We analyze the predictions of two recently developed effective-medium approximations for the effective refractive index of a system of either transparent or plasmonic spherical particles, dispersed randomly in a transparent liquid matrix, as a function of their geometrical and physical parameters. The importance and significance of these approximations is that besides the radiative corrections to the optical response of the particles, they include full dynamic corrections to the field exciting any given particle. We perform this analysis by comparing the values obtained using them with the ones obtained from three well-known and widely used effective-medium approximations: Maxwell Garnett, Maxwell Garnett-Mie and van de Hulst. We provide plots of the real and imaginary parts of the effective index of refraction, for the five approximations considered, for polystyrene and gold nanoparticles of different sizes, as a function of the filling fraction and wavelength, pointing out the relevance of the new predictions, as well as the actual physical processes behind the so-called dependent scattering and what we now call dependent absorption.

Surface-enhanced Raman spectroscopy substrates for monitoring antibiotics in dairy products: Mechanisms, advances, and prospects.

Antibiotic residues in dairy products have become an undeniable threat to human health. Surface-enhanced Raman spectroscopy (SERS) has been widely used in efficiently detecting antibiotics because of its characteristics including fast response, high resolution, and strong resistance to moisture interference. However, as a core part of SERS technology, the design principle and detection performance of enhanced substrates used in monitoring antibiotics in dairy products have not yet received enough attention. Thus, it is necessary to give a critical review of the recent developments of SERS substrates for monitoring antibiotics in dairy products, which can be expected to provide inspiration for the efficient utilization of SERS technology. In this work, advances in various SERS substrates applied in sensing antibiotics in dairy products were comprehensively reviewed. First, the enhancement mechanisms were introduced in detail. Significantly, the types of enhanced materials (plasmonic metal particles [PMPs], PMPs/semiconductor composite materials) and biometric design strategies including immunoassay, aptamer, and molecularly imprinted polymers-based SERS biosensors applied in dairy products were systematically summarized for the first time. Meanwhile, the performance of SERS substrates used for the detection of antibiotics in dairy products was addressed from the aspects of dynamic linear range and detection restriction strategy. Finally, the conclusions, challenges, and future prospects of SERS substrates for antibiotic monitoring in dairy products were deeply discussed, which also provide new opinions and key points for constructing SERS substrates applied in complex food matrix in the future.

Enhancement of visible light adsorption and photocatalytic degradation activity of organic dye by coating semiconducting TiO2 shell on plasmonic Au particles

The plasmonic effect enhances light absorption in semiconductor photocatalysts, while the noble metal-semiconductor interface promotes charge carrier transfer and separation, boosting photocatalytic activity. However, current methods for synthesizing metal-core TiO2-shell nanoparticles face challenges, such as keeping stable and preventing aggregation. This study presents a simple and moderate synthesis method for Au@TiO2 core-shell nanoparticles, enabling precise control over the TiO2 shell thickness and stable photocatalytic performance. Various characterization techniques were employed to assess the optical and structural properties of the synthesized Au@TiO2 core-shell nanostructures. The results demonstrated that increasing the Au core concentration led to a gradual decrease in TiO2 shell thickness. The adsorption properties and photocatalytic degradation efficiency of the synthesized Au@TiO2 core-shell nanostructured catalysts were thoroughly examined, particularly focusing on their performance with methyl orange (MO) and methylene blue (MB). Au@TiO2 achieved excellent adsorption performance for MO, with a maximum capacity of 231±6 mg/g. Furthermore, Au@TiO2 exhibited higher photocatalytic degradation activity of both MO and MB than pure TiO2. The mechanism study indicated that it attributed to enhanced visible light absorption, reduced bandgap, and higher valence band energy. Additionally, the Au@TiO2 catalysts showed good cyclic stability, making them promising for future applications. This research offers insights into designing efficient photocatalysts, addressing existing synthesis challenges, and contributing valuable references for future advancements.

Investigation of dependent scattering criterion for dispersed particulate medium: Effects of metal particle plasmon resonances and host medium absorption

Spectral radiative transfer between particles within dispersed particulate medium is prevalent across various fields, which may be influenced by the microscopic dependent scattering effect (DSE). However, independent scattering assumption (ISA) is only employed in the radiative transfer of most studies, which can lead to significant errors. Consequently, there is an urgent need to establish the more accurate and widely applicable dependent scattering criterion for determining whether the radiative transfer is independent or dependent scattering. However, the most existing criteria are only applicable under the assumption of optically soft particles with weak absorption. This limitation results in the criteria being valid only for certain types of particles, excluding nonmetal particles with highly complex refractive indices and metal particles with strongly absorption. Furthermore, the existing criteria also fail to consider the impact of host medium absorption (HMA) on the localized surface plasmon resonance (LSPR) of metal particles and the DSE between particles. It would represent another significant limitation. To address these above limitations, this paper develops a comprehensive and systematic dependent scattering criterion with considering the plasmon resonances for metal particle and host medium absorption. The multiple sphere T-matrix (MSTM) method, generalized Mie scattering, and Monte Carlo ray tracing (MCRT) method are further employed to calculate and compare the radiative properties across different scales. The extinction cross section is the most suitable contrast parameter in the dependent scattering criterion with the consideration of host medium absorption. Clearance-to-wavelength ratio c/λ is used to characterize dependent scattering criterion. Consequently, the dependent scattering criterion c/λ for nonmetal particles is 6. While the dependent scattering criterion c/λ for metal particles is 5.5.

Plasmonic Particle Integration into Near-Infrared Photodetectors and Photoactivated Gas Sensors: Toward Sustainable Next-Generation Ubiquitous Sensing.

Current challenges in environmental science, medicine, food chemistry as well as the emerging use of artificial intelligence for solving problems in these fields require distributed, local sensing. Such ubiquitous sensing requires components with 1) high sensitivity, 2) power efficiency, 3) miniaturizability, and 4) the ability to directly interface with electronic circuitry, i.e., electronic readout of sensing signals. Over the recent years, several nanoparticle-based approaches have found their way into this field and have demonstrated high performance. However, challenges remain, such as the toxicity of many of today's narrow bandgap semiconductors for NIR detection and the high energy consumption as well as low selectivity of state-of-the-art commercialized gas sensors. With their unique light-matter interaction and ink-based fabrication schemes, plasmonic nanostructures provide potential technological solutions to these challenges, leading also to better environmental performance. In this perspective recent approaches of using plasmonic nanoparticles are discussed for the fabrication of NIR photodetectors and light-activated, energy-efficient gas sensing devices. In addition, new strategies implying computational approaches are pointed out for miniaturizable spectrometers, exploiting the wide spectral tunability of plasmonic nanocomposites, and for selective gas sensors, utilizing dynamic light activation. The benefits of colloidal approaches for device fabrication are discussed with regard to technological advantages and environmental aspects, which are barely considered so far.

Optical trapping-induced crystallization promoted by gold and silicon nanoparticles.

This study investigates the promotion of sodium chlorate (NaClO3) crystallization through optical trapping, enhanced by the addition of gold nanoparticles (AuNPs) and silicon nanoparticles (SiNPs). Using a focused laser beam at the air-solution interface of a saturated NaClO3 solution with AuNPs or SiNPs, the aggregates of these particles were formed at the laser focus, the nucleation and growth of metastable NaClO3 (m-NaClO3) crystals were induced. Continued laser irradiation caused these m-NaClO3 crystals to undergo repeated cycles of growth and dissolution, eventually transitioning to a stable crystal form. Our comparative analysis showed that AuNPs, due to their significant heating due to higher photon absorption efficiency, caused more pronounced size fluctuations in m-NaClO3 crystals compared to the stable behavior observed with SiNPs. Interestingly, the maximum diameter of the m-NaClO3 crystals that appeared during the size fluctuation step was consistent, regardless of nanoparticle type, concentration, or size. The crystallization process was also promoted by using polystyrene nanoparticles, which have minimal heating and electric field enhancement, suggesting that the reduction in activation energy for nucleation at the particle surface is a key factor. These findings provide critical insights into the mechanisms of laser-induced crystallization, emphasizing the roles of plasmonic heating, particle surfaces, and optical forces.

Analytical Modeling of Coated Plasmonic Particles

Analytical Modeling of Coated Plasmonic Particles

Label-Free Biosensor Based on Particle Plasmon Resonance Coupled with Diffraction Grating Waveguide.

Particle plasmon resonance (PPR), or localized surface plasmon resonance (LSPR), utilizes intrinsic resonance in metal nanoparticles for sensor fabrication. While diffraction grating waveguides monitor bioaffinity adsorption with out-of-plane illumination, integrating them with PPR for biomolecular detection schemes remains underexplored. This study introduces a label-free biosensing platform integrating PPR with a diffraction grating waveguide. Gold nanoparticles are immobilized on a glass slide in contact with a sample, while a UV-assisted embossed diffraction grating is positioned opposite. The setup utilizes diffraction in reflection to detect changes in the environment's refractive index, indicating biomolecular binding at the gold nanoparticle surface. The positional shift of the diffracted beam, measured with varying refractive indices of sucrose solutions, shows a sensitivity of 0.97 mm/RIU at 8 cm from a position-sensitive detector, highlighting enhanced sensitivity due to PPR-diffraction coupling near the gold nanoparticle surface. Furthermore, the sensor achieved a resolution of 3.1 × 10-4 refractive index unit and a detection limit of 4.4 pM for detection of anti-DNP. The sensitivity of the diffracted spot was confirmed using finite element method (FEM) simulations in COMSOL Multiphysics. This study presents a significant advancement in biosensing technology, offering practical solutions for sensitive, rapid, and label-free biomolecule detection.

Noninvasive Prenatal Genetic Screening of Cell-Free Fetal DNA for Early Prediction of β-Thalassemia Using Fiber Optic Nanogold-Linked Sorbent Assay.

β-Thalassemia is a prevalent type of severe inherited chronic anemia, primarily identified in developing countries. The identification of single nucleotide polymorphisms (SNPs) plays a vital role in the early diagnosis of genetic diseases. Here, we reported the development of an amplification-free fiber optic nanogold-linked sorbent assay method using a fiber optic particle plasmon resonance (FOPPR) biosensor for rapid and ultrasensitive detection of SNPs. Herein, MutS protein was selected as the biorecognition capture probe and immobilized on the sensing region to capture the target mutant DNA, which was hybridized with a single-base mismatched single-stranded DNA labeled by a gold nanoparticle (AuNP). The AuNP acts as a signaling agent to be detected by the FOPPR biosensor when it is bound on the fiber core surface. The method effectively differentiates mismatched double-stranded DNA by MutS protein from perfectly matched/complementary dsDNA. It exhibits an impressively low detection limit for the detection of SNPs at approximately 10-16 M using low-cost sensor chips and devices. By determination of the ratio of mutant DNA to normal DNA in cell-free genomic DNA from blood samples, this method is promising for diagnosing β-thalassemia in fetuses without invasive testing techniques.

Surface Plasmon Resonance Modulation by Complexation of Platinum on the Surface of Silver Nanocubes.

The use of plasmonic particles, specifically, localized surface plasmonic resonance (LSPR), may lead to a significant improvement in the electrical, electrochemical, and optical properties of materials. Chemical modification of the dielectric constant near the plasmonic surface should lead to a shift of the optical resonance and, therefore, the basis for color tuning and sensing. In this research, we investigated the variation of the LSPR by modifying the chemical environment of Ag nanoparticles (NPs) through the complexation of Pt(IV) metal cations near the plasmonic surface. This study is carried out by measuring the shift of the plasmon dipole resonance of Ag nanocubes (NCs) and nanowires (NWs) of differing sizes upon coating the Ag surface with a layer of polydopamine (PDA) as a coordinating matrix for Pt(IV) complexes. The red shift of up to 45 nm depends linearly on the thickness of the PDA/Pt(IV) layer and the Pt(IV) content. Additionally, we calculated the dielectric constant of the surrounding medium using a numerical method.

Plasmon Mediated Single Photon Emission from a Nanocrystal Ensemble.

Quantum photonic devices require robust sources of single photons to perform basic computational and communication protocols. Thus, developing scalable, integrable, and efficient quantum light sources has become crucial for the realization of quantum photonic devices. Single quantum dots are promising sources of quantum light due to their tunable emission wavelength. Here, we show the emergence of quantum-emitter-like antibunched emission behavior when multiple quantum dots are located in the vicinity of plasmonic particles. To evaluate the robustness of this phenomenon, we consider both monometallic and bimetallic particles. We find that the photoluminescence intensity of the plasmon coupled quantum dots fits well to a single sublinear power law exponent that is distinct from the behavior of CQD aggregates. Significantly, we find that plasmon coupling results in reduced flickering, thus enabling the realization of a more stable and reliable single photon source. Possible roles of emergent excitonic interactions in the coupled system are discussed.

Oxidizing Role of Cu Cocatalysts in Unassisted Photocatalytic CO2 Reduction Using p-GaN/Al2O3/Au/Cu Heterostructures.

Photocatalytic CO2 reduction to CO under unassisted (unbiased) conditions was recently demonstrated using heterostructure catalysts that combine p-type GaN with plasmonic Au nanoparticles and Cu nanoparticles as cocatalysts (p-GaN/Al2O3/Au/Cu). Here, we investigate the mechanistic role of Cu in p-GaN/Al2O3/Au/Cu under unassisted photocatalytic operating conditions using Cu K-edge X-ray absorption spectroscopy and first-principles calculations. Upon exposure to gas-phase CO2 and H2O vapor reaction conditions, the composition of the Cu nanoparticles is identified as a mixture of CuI and CuII oxide, hydroxide, and carbonate compounds without metallic Cu. These composition changes, indicating oxidative conditions, are rationalized by bulk Pourbaix thermodynamics. Under photocatalytic operating conditions with visible light excitation of the plasmonic Au nanoparticles, further oxidation of CuI to CuII is observed, indicating light-driven hole transfer from Au-to-Cu. This observation is supported by the calculated band alignments of the oxidized Cu compositions with plasmonic Au particles, where light-driven hole transfer from Au-to-Cu is found to be thermodynamically favored. These findings demonstrate that under unassisted (unbiased) gas-phase reaction conditions, Cu is found in carbonate-rich oxidized compositions rather than metallic Cu. These species then act as the active cocatalyst and play an oxidative rather than a reductive role in catalysis when coupled with plasmonic Au particles for light absorption, possibly opening an additional channel for water oxidation in this system.

Structural Color Materials with Color Mixing Effect Using Noble Metal‐Free Plasmonic Particles in SiO2–ZrN System (Advanced Optical Materials 19/2024)

Structural Color Materials with Color Mixing Effect Using Noble Metal‐Free Plasmonic Particles in SiO₂–ZrN System (Advanced Optical Materials 19/2024)

Optically printed plasmonic fiber tip-assisted SERS-based chemical sensing and single biological cell studies

BackgroundPrecise localized printing of plasmonic nanoparticles at desired locations can find a plethora of applications in diverse areas, including nanophotonics, nanomedicine, and microelectronics. The focused laser beam-assisted optical printing technique has illustrated its potential for the localized printing of differently shaped plasmonic particles. However, the technique is either time-consuming or often requires focused optical radiation, limiting its practical applications. While the optothermal printing technique has recently emerged as a promising technique for the direct and rapid printing of plasmonic nanoparticles onto transparent substrates at lower laser intensities, its potential to print the plasmonic nanoparticles to the core of the optical fiber platforms and utilize it for biological cell trapping as well as an analytical platform remains unexplored. ResultsHerein, we demonstrate the thermal-convection-assisted printing of the Ag plasmonic nanoparticles from the plasmonic colloidal solution onto the core of single-mode optical fiber and its multi-functional applications. The direct printing of plasmonic structure on the fiber core via the thermal-convection mechanism is devoid of the requirement of any additional chemical ligand to the fiber core. Further, we demonstrated the potential of the developed plasmonic fiber probe as a multifunctional surface-enhanced Raman spectroscopic (SERS) platform for sensing, chemical reaction monitoring, and single-cell studies. The developed SERS fiber probe is found to detect crystal violet in an aqueous solution as low as 100 pM, with a plasmonic enhancement of 107. Additionally, the capability of the fiber-tip platform to monitor the surface plasmon-driven chemical reaction of 4-nitrothiophenol (4NTP) dimerizing into p, p’-dimercaptoazobenzene (DMAB) is demonstrated. Further, the versatility of the fiber probe as an effective platform for opto-thermophoretic trapping of single biological cells such as yeast, along with its Raman spectroscopic studies, is also shown here. SignificanceIn this study, we illustrate for the first time the optothermal direct printing of plasmonic nanoparticles onto the core of a single-mode fiber. Further, the study demonstrates that such plasmonic nanoparticle printed fiber tip can act as a multi-functional analytical platform for optothermally trap biological particles as well as monitoring plasmon-driven chemical reactions. In addition, the plasmonic fiber tip can be used as a cost-effective SERS analytical platform and is thus expected to find applications in diverse areas.