Highly Responsive Plasmon Modulation in Dopant-Segregated Nanocrystals.

Electron transfer to and from metal oxide nanocrystals (NCs) modulates their infrared localized surface plasmon resonance (LSPR), revealing fundamental aspects of their photophysics and enabling dynamic optical applications. We synthesized and chemically reduced dopant-segregated Sn-doped In2O3 NCs, investigating the influence of radial dopant segregation on LSPR modulation and near-field enhancement (NFE). We found that core-doped NCs show large LSPR shifts and NFE change during chemical titration, enabling broadband modulation in LSPR energy of over 1000 cm-1 and of peak extinction over 300%. Simulations reveal that the evolution of the LSPR spectra during chemical reduction results from raising the surface Fermi level and increasing the donor defect density in the shell region. These results establish dopant segregation as a useful strategy to engineer the dynamic optical modulation in plasmonic semiconductor NC heterostructures going beyond what is possible with conventional plasmonic metals.

Enhanced Near-Infrared Ultra-Narrow Absorber Based on a Dielectric Nano-Resonant Ring for Refractive Index Sensing.

In this paper, a plasmon resonance-enhanced narrow-band absorber based on the nano-resonant ring array of transparent conductive oxides (TCOs) is proposed and verified numerically. Due to the unique properties of TCOs, the structure achieves an ultra-narrowband perfect absorption by exhibiting a near-field enhancement effect. Consequently, we achieve a peak absorption rate of 99.94% at 792.2 nm. The simulation results indicate that the Full Width Half Maximum (FWHM) can be limited to within 8.8 nm. As a refractive index sensor, the device reaches a sensitivity S of 300 nm/RIU and a Figure of Merit (FOM) value of 34.1 1/RIU. By analyzing the distribution characteristics of the electromagnetic field at the 792.2 nm, we find high absorption with a narrow FWHM of the ITO nano-resonant ring (INRR) owing to plasmon resonance excited by the free carriers at the interface between the metal and the interior of the ITO. Additionally, the device exhibits polarization independence and maintains absorption rates above 90% even when the incident formed by the axis perpendicular to the film is greater than 13°. This study opens a new prospective channel for research into TCOs, which will increase the potential of compact photoelectric devices, such as optical sensing, narrowband filtering, non-radiative data transmission and biomolecular manipulation.

Defect Detection of Aluminium Plates Based on Near-Field Enhancement of Lamb Waves Generated Using an Electromagnetic Acoustic Tranducer.

Ultrasonic testing is an important means to detect defacing defects, such as scratches and cracks, but when the size of these defects is smaller than the wavelength of ultrasonic waves, it is difficult to detect them using traditional methods like the pulse-echo method and broadband ultrasound attenuation method for the diffraction of ultrasonic waves at the defects. Based on the non-contact characteristic of electromagnetic acoustic transducers (EMATs), a transducer for scanning inspection was developed in this paper. The transducer was utilized to detect and measure the depth of the defacing defects on an aluminium plate based on the near-field enhancement of ultrasonic Lamb waves. The results show that the amplitude of the S0 Lamb wave experiences a large enhancement when the transducer is passed over the scratch defects and the enhancement has a clearly positive correlation with the depth of the scratch defects. When the depth increases from 0.1 mm to 0.9 mm, the amplitude of S0 Lamb waves increases from 1.13 times to 2.27 times the S0 Lamb waves received on the aluminium plate without defects. The new method can be utilized to detect the defacing defects on the aluminium plate and get better detection effects than the traditional methods without analyzing the relatively small reflection waves.

Efficient Emission Enhancement of Single CdSe/CdS/PMMA Quantum Dots through Controlled Near-Field Coupling to Plasmonic Bullseye Resonators.

A strong increase of spontaneous radiative emission from colloidally synthesized CdSe/CdS/PMMA hybrid particles is achieved when manipulated into plasmonic bullseye resonators with the tip of an atomic force microscope (AFM). This type of antenna provides a broadband resonance, which may be precisely matched to the exciton ground state energy in the inorganic cores. Statistically analyzing the spectral photoluminescence (PL) of a large number of individual coupled and uncoupled CdSe/CdS/PMMA quantum dots, we find an order of magnitude of intensity enhancement due to the Purcell effect. Time-resolved PL shows a commensurate increase of the spontaneous emission rate with radiative lifetimes below 230 ps for the bright exciton transition. The combination of AFM and PL imaging allows for sub-200 nm localization of the particle position inside the plasmonic antenna. This capability unveils a different coupling behavior of dark excitonic states: even stronger PL enhancement occurs at positions with maximum spatial gradient of the nearfield, effectively adding a dipolar component to original quadrupole transitions. The broadband maximization of light-matter interaction provided by our nanoengineered compound systems enables an attractive class of future experiments in ultrafast quantum optics.

Defect Engineering in Plasmonic Metal Oxide Nanocrystals.

Defects may tend to make crystals interesting but they do not always improve performance. In doped metal oxide nanocrystals with localized surface plasmon resonance (LSPR), aliovalent dopants and oxygen vacancies act as centers for ionized impurity scattering of electrons. Such electronic damping leads to lossy, broadband LSPR with low quality factors, limiting applications that require near-field concentration of light. However, the appropriate dopant can mitigate ionized impurity scattering. Herein, we report the synthesis and characterization of a novel doped metal oxide nanocrystal material, cerium-doped indium oxide (Ce:In2O3). Ce:In2O3 nanocrystals display tunable mid-infrared LSPR with exceptionally narrow line widths and the highest quality factors observed for nanocrystals in this spectral region. Drude model fits to the spectra indicate that a drastic reduction in ionized impurity scattering is responsible for the enhanced quality factors, and high electronic mobilities reaching 33 cm(2)V(-1) s(-1) are measured optically, well above the optical mobility for tin-doped indium oxide (ITO) nanocrystals. We investigate the microscopic mechanisms underlying this enhanced mobility with density functional theory calculations, which suggest that scattering is reduced because cerium orbitals do not hybridize with the In orbitals that dominate the bottom of the conduction band. Ce doping may also reduce the equilibrium oxygen vacancy concentration, further enhancing mobility. From the absorption spectra of single Ce:In2O3 nanocrystals, we determine the dielectric function and by simulation predict strong near-field enhancement of mid-IR light, especially around the vertices of our synthesized nanocubes.

Excitonic Lasing in Solution-Processed Subwavelength Nanosphere Assemblies.

Lasing in solution-processed nanomaterials has gained significant interest because of the potential for low-cost integrated photonic devices. Still, a key challenge is to utilize a comprehensive knowledge of the system's spectral and temporal dynamics to design low-threshold lasing devices. Here, we demonstrate intrinsic lasing (without external cavity) at low-threshold in an ultrathin film of coupled, highly crystalline nanospheres with overall thickness on the order of ∼λ/4. The cavity-free geometry consists of ∼35 nm zinc oxide nanospheres that collectively localize the in-plane emissive light fields while minimizing scattering losses, resulting in excitonic lasing with fluence thresholds at least an order of magnitude lower than previous UV-blue random and quantum-dot lasers (<75 µJ/cm(2)). Fluence-dependent effects, as quantified by subpicosecond transient spectroscopy, highlight the role of phonon-mediated processes in excitonic lasing. Subpicosecond evolution of distinct lasing modes, together with three-dimensional electromagnetic simulations, indicate a random lasing process, which is in violation of the commonly cited criteria of strong scattering from individual nanostructures and an optically thick sample. Subsequently, an electron-hole plasma mechanism is observed with increased fluence. These results suggest that coupled nanostructures with high crystallinity, fabricated by low-cost solution-processing methods, can function as viable building blocks for high-performance optoelectronics devices.

M-shaped grating by nanoimprinting: a replicable, large-area, highly active plasmonic surface-enhanced Raman scattering substrate with nanogaps.

Plasmonic nanostructures separated by nanogaps enable strong electromagnetic-field confinement on the nanoscale for enhancing light-matter interactions, which are in great demand in many applications such as surface-enhanced Raman scattering (SERS). A simple M-shaped nanograting with narrow V-shaped grooves is proposed. Both theoretical and experimental studies reveal that the electromagnetic field on the surface of the M grating can be pronouncedly enhanced over that of a grating without such grooves, due to field localization in the nanogaps formed by the narrow V grooves. A technique based on room-temperature nanoimprinting lithography and anisotropic reactive-ion etching is developed to fabricate this device, which is cost-effective, reliable, and suitable for fabricating large-area nanostructures. As a demonstration of the potential application of this device, the M grating is used as a SERS substrate for probing Rhodamine 6G molecules. Experimentally, an average SERS enhancement factor as high as 5×108 has been achieved, which verifies the greatly enhanced light-matter interaction on the surface of the M grating over that of traditional SERS surfaces.

Plasmon-Free Surface-Enhanced Raman Spectroscopy Using α-Type MoO3 Semiconductor Nanorods with Strong Light Scattering in the Visible Regime.

Recent developments in semiconductor-based surface-enhanced Raman scattering (SERS) have achieved numerous advancements, primarily centered on the chemical mechanism. However, the role of the electromagnetic (electromagnetic mechanism) contribution in advancing semiconductor SERS substrates is still underexplored. In this study, we developed a SERS substrate based on densely aligned α-type MoO3 (α-MoO3) semiconductor nanorods (NRs) with rectangular parallelepiped ribbon shapes with width measuring several hundred nanometers. These structural attributes strongly affect light transport in the visible range by multiple light scattering generated in narrow gaps between NRs, contributing to the improvement of SERS performance. Engineering the nanostructure and chemical composition of NRs realized high SERS sensitivity with an enhancement factor of 2 × 108 and a low detection limit of 5 × 10-9 M for rhodamine 6G (R6G) molecules, which was achieved by the stoichiometric NR sample with strong light scattering. Furthermore, it was observed that the scattering length becomes significantly shorter compared with the excitation wavelength in the visible regime, which indicates that light transport is strongly modified by mesoscopic interference related to Anderson localization. Additionally, high electric fields were found to be localized on the NR surfaces, depending on the excitation wavelength, similar to the SERS response. These optical phenomena indicate that electromagnetic excitation processes play an important role in plasmon-free SERS platforms based on α-MoO3 NRs. We postulate that our study provides important guidance for designing effective EM-based SERS-active semiconductor substrates.

Up-to-Five-Photon Upconversion from Near-Infrared to Ultraviolet Luminescence Coupled to Aluminum Plasmonic Lattices.

The incorporation of upconversion luminescence (UCL) materials into various plasmonic structures promotes light-matter interactions in nanophotonic systems. It has been experimentally demonstrated that UCL enhancement entailing two photons exhibits a quadratic dependence on the excitation intensity. However, in the field of plasmonics, there have not been sufficient studies on high-order multi-photon upconversion processes. We report up-to-five-photon UCL, wherein λ = 1550 nm near-infrared light is converted to 382 nm ultraviolet light, from core-inert shell nanoparticles coupled to aluminum plasmonic lattices. The five-photon UCL intensity of nanoparticles on the plasmonic lattice is over 800 times stronger than that on the flat glass. We demonstrate that the enhancement of UCL scales with the nth power of the local field enhancement for n-photon process. These findings give a strategy to obtain high-order multi-photon UPL with aluminum plasmonic nanostructures and can contribute to anti-counterfeiting application.

Optimally Configured Optical Fiber Near-Field Enhanced Plasmonic Resonance Immunoprobe for the Detection of Alpha-Fetoprotein.

The detection of trace biomarkers is an important supplementary approach for early screening and diagnoses of tumors. An optical fiber near-field enhanced plasmonic resonance immunoprobe is developed for the detection of the hepatocellular carcinoma biomarker, i.e., the alpha-fetoprotein. Generic principles based on dispersion models and finite element analysis (FEA) models are developed to realize the optimized configuration of spectral characteristics of the immunoprobe. Dispersion models provide theoretical guidance for the design of the multilayer sensing structure from the perspective of the ray optics theory. FEA models provide theoretical guidance for the selection of coating materials from the perspective of the self-defined dielectric constant ratio, i.e., the ratio of the real part to the imaginary part. The optimized configuration of the antibody coupling further improves the biosensing performance of the immunoprobe. The limit of detection (LOD) can reach down to 0.01 ng mL-1 , which is one order of magnitude lower than those relevant reported works. Such a low LOD can more effectively avoid the accuracy degradation of detection results due to measurement errors. Human serum samples have also been detected, with the good precision achieved. This work shows promising prospects in applications of label-free, low-cost, rapid, and convenient early screening of tumors.

Broad-Band-Enhanced Plasmonic Perovskite Solar Cells with Irregular Silver Nanomaterials.

The localized surface plasmon resonance (LSPR) from noble metal nanomaterials (NMs) is a promising solution to approach the theoretical efficiency for photovoltaic devices. However, the plasmon resonance of metal NMs with particular shapes and sizes can only be excited within narrow spectral ranges, which can hardly cover the broad-band solar spectrum. To address this issue, in this article, Ag NMs with irregular shapes and sizes are synthesized and embedded in the electron transport layer of perovskite solar cells. With the outstanding conductivity of Ag NMs, the series resistance and charge transfer resistance of the devices are dramatically decreased. The Ag NMs with larger size could enhance the light-trapping of the devices owing to the far-field light scattering effect. The near-field enhancement by LSPR of Ag NMs with a small size mainly contributes to the promotion of carrier transport and extraction. As a result, broad-band improvements in photovoltaic performance are achieved due to the significant enhancement of light absorption and electrical features. The highest power conversion efficiency of the perovskite solar cells increases from 19.52 to 22.42% after the incorporation of Ag NMs.

Optical Properties of Ag Nanoparticle Arrays: Near-Field Enhancement and Photo-Thermal Temperature Distribution.

The near-field and photo-thermal properties of nanostructures have always been the focus of attention due to their wide applications in nanomaterials. In this work, we numerically investigate the near-field and photo-thermal temperature distribution in a nanoparticle array when the scattering light field among particles is considered. 'Hot spots', which represent strong electric field enhancement, were analyzed at the difference of the particle size, particle spacing and the polarization direction of the incident light. Interestingly, it is found that the position of the 'hot spots' does not rotate with the polarization direction of the incident light and always remains in the particle gaps along the line between particle centers. Moreover, the near-field is independent of the polarization in some special areas, and the factor of near-field enhancement keeps constant in these spots when the illumination polarization varies. As for photo-induced heating, our results show that both the temperature of the structure center and maximum temperature increase linearly with the particle number of the array while decreasing with the increase in particle spacing. This work provides some theoretical considerations for the near-field manipulation and photo-thermal applications of nanoarrays.

Toroidal dipole-modulated dipole-dipole double-resonance in colloidal gold rod-cup nanocrystals for improved SERS and second-harmonic generation.

Colloidal metal nanocrystals (NCs) show great potential in plasmon-enhanced spectroscopy owing to their attractive and structure-depended plasmonic properties. Herein, unique Au rod-cup NCs, where Au nanocups are embedded on the one or two ends of Au nanorods (NRs), are successfully prepared for the first time via a controllable wet-chemistry strategy. The Au rod-cup NCs possess multiple plasmon modes including transverse and longitudinal electric dipole (TED and LED), magnetic dipole (MD), and toroidal dipole (TD) modulated LED resonances, producing large extinction cross-section and huge near-field enhancements for plasmon-enhanced spectroscopy. Particularly, Au rod-cup NCs with two embedded cups show excellent surface-enhanced Raman spectroscopy (SERS) performance than Au NRs (75.6-fold enhancement excited at 633 nm) on detecting crystal violet owing to the strong electromagnetic hotspots synergistically induced by MD, LED, and TED-based plasmon coupling between Au cup and rod. Moreover, the strong TD-modulated dipole-dipole double-resonance and MD modes in Au rod-cup NCs bring a 37.3-fold enhancement of second-harmonic generation intensity compared with bare Au NRs, because they can efficiently harvest photoenergy at fundamental frequency and generate large near-field enhancements at second-harmonic wavelength. These findings provide a strategy for designing optical nanoantennas for plasmon-enhanced applications based on multiple plasmon modes. Electronic Supplementary Material: Supplementary material (SEM image of Au rod-one-cup NCs; TEM image of Au/PbS hybrids; SEM image of Au rod-two-cup NCs; low-amplification SEM image of Au rod-two-cup NCs; experimental extinction and calculated electric field distributions of Au NR excited at different wavelengths; calculated absorption and scattering spectra of Au rod-one-cup NCs; schematic illustration of the cut plane and the corresponding magnetic field distribution under L3 excitation; Raman spectra of CV (10-6 M) adsorbed on Au rod-cup NCs with different cup sizes; calculated magnetic field distribution of Au rodcup NCs excited at 532 and 633 nm; calculated electric field distributions of Au rod-one-cup NC excited at 600 nm along TE and LE; the models of Au rod-cup NCs used in the simulations) is available in the online version of this article at 10.1007/s12274-022-4562-5.

Exploring near-field sensing efficiency of complementary plasmonic metasurfaces for immunodetection of tumor markers.

Plasmonic metasurface biosensors have great potential on label-free high-throughput clinical detection of human tumor markers. In the past decades, nanopillar and nanohole metasurfaces have become the common choices for plasmonic biosensing, because they typically enable universal simple large-area nanopatterns via a low-cost reproducible fabrication manner. The two kinds of metasurfaces have the complementary shapes and are used to be assumed as the same type of two-dimensional plasmonic nanograting for biosensing. Up to date, there is still a lack of comparison study on their biosensing performance, which is critical to guide their better applications on tumor marker detection. In this study, we compare the bulk/surface refractive index and sensitivity of plasmonic nanopillar (PNP) and plasmonic nanohole (PNH) metasurfaces in order to evaluate their biosensing capabilities. The sensing physics about their space near-field utilization is systematically revealed. The PNH metasurface demonstrates a higher biomolecule sensitivity versus the complementary PNP metasurface, and its limit of detection for bovine serum albumin reaches ∼0.078 ng/mL, which implies a greater potential of detecting cancer biomarkers. We further adopt the PNH metasurfaces for immunoassay of three typical tumor markers by testing clinical human serum samples. The results imply that the immunodetection of alpha-fetoprotein has the most optimal sensing efficiency with the lowest detection concentration (<5 IU/mL), which is much lower than its clinical diagnosis threshold of ∼16.5 IU/mL for medical examination. Our work has not only illuminated the distinct biosensing properties of complementary metasurfaces, but also provided a promising way to boost plasmonic biosensing for point-of-care testing.

Terminal Groups-Dependent Near-Field Enhancement Effect of Ti3C2Tx Nanosheets.

Both multilayered (ML) and few-layered (FL) Ti3C2Tx nanosheets have been prepared through a typical etching and delaminating procedure. Various characterizations confirm that the dominant terminal groups on ML-Ti3C2Tx and FL-Ti3C2Tx are different, which have been assigned to O-related and hydroxyl groups, respectively. Such deviation of the dominant terminals results in the different physical and chemical performance and eventually makes the nanosheets have different potential applications. In particular, before coupling to Ag nanoparticles, ML-Ti3C2Tx can present stronger near-field enhancement effect; however, Ag/FL-Ti3C2Tx hybrid structure can confine stronger near-field due to the electron injection, which can be offered by the terminated hydroxyl groups.

Active Individual Nanoresonators Optimized for Lasing and Spasing Operation.

Plasmonic nanoresonators consisting of a gold nanorod and a spherical silica core and gold shell, both coated with a gain layer, were optimized to maximize the stimulated emission in the near-field (NF-c-type) and the outcoupling into the far-field (FF-c-type) and to enter into the spasing operation region (NF-c*-type). It was shown that in the case of a moderate dye concentration, the nanorod has more advantages: smaller lasing threshold and larger slope efficiency and larger achieved intensities in the near-field in addition to FF-c-type systems' smaller gain and outflow threshold, earlier dip-to-peak switching in the spectrum and slightly larger far-field outcoupling efficiency. However, the near-field (far-field) bandwidth is smaller for NF-c-type (FF-c-type) core-shell nanoresonators. In the case of a larger dye concentration (NF-c*-type), although the slope efficiency and near-field intensity remain larger for the nanorod, the core-shell nanoresonator is more advantageous, considering the smaller lasing, outflow, absorption and extinction cross-section thresholds and near-field bandwidth as well as the significantly larger internal and external quantum efficiencies. It was also shown that the strong-coupling of time-competing plasmonic modes accompanies the transition from lasing to spasing occurring, when the extinction cross-section crosses zero. As a result of the most efficient enhancement in the forward direction, the most uniform far-field distribution was achieved.

Optically Induced Molecular Logic Operations.

Molecular electronics is a promising route for down-sizing electronic devices. Tip-enhanced Raman spectroscopy provides us a setup to probe current-driven molecular junctions that are considered as prototypes of molecular electronic devices. In this setup, the plasmonic tip concentrates optical fields to a degree that allows observing optical response of single molecules. Simultaneously, the tip can also induce a localized optical angular momentum, which has been seldomly considered in previous studies. Here, we propose that the induced optical angular momentum can interact with the probed molecule and strongly modify the response signal. Specifically, we demonstrate the ability to control the vibrational resonance of current-driven molecular junctions with the optical angular momentum. This precise control of light-matter interactions at the nanoscale allows us to demonstrate multiple logic operations. These results provide a fundamental understanding of future molecular electronics applications.

Nano-Architecture Driven Plasmonic Field Enhancement in 3D Graphene Structures.

The limited spatial coverage of the plasmon enhanced near-field in 2D graphene ribbons presents a major hurdle in practical applications. In this study, diverse self-assembled 3D graphene architectures are explored that induce hybridized plasmon modes by simultaneous in-plane and out-of-plane coupling to overcome the limited coverage in 2D ribbons. While 2D graphene can only demonstrate in-plane, bidirectional coupling through the edges, 3D architectures benefit from fully symmetric 360° coupling at the apex of pyramidal graphene, orthogonal four-directional coupling in cubic graphene, and uniform cross-sectional radial coupling in tubular graphene. The 3D coupled vertices, edges, surfaces, and volume induce corresponding enhancement modes that are highly dependent on the shape and dimensions comprising the 3D geometries. The hybridized modes introduced through the 3D coupling amplify the limited plasmon response in 2D ribbons to deliver nondiffusion limited sensors, high efficiency fuel cells, and extreme propagation length optical interconnects.

Analysis of the Limits of the Near-Field Produced by Nanoparticle Arrays.

Periodic arrays are an exceptionally interesting arrangement for metallic nanostructures because of their ability to support collective lattice resonances. These modes, which arise from the coherent multiple scattering enabled by the lattice periodicity, give rise to very strong and spectrally narrow optical responses. Here, we investigate the enhancement of the near-field produced by the lattice resonances of arrays of metallic nanoparticles when illuminated with a plane wave. We find that, for infinite arrays, this enhancement can be made arbitrarily large by appropriately designing the geometrical characteristics of the array. On the other hand, in the case of finite arrays, the near-field enhancement is limited by the number of elements of the array that interact coherently. Furthermore, we show that, as the near-field enhancement increases, the length scale over which it extends above and below the array becomes larger and its spectral linewidth narrows. We also analyze the impact that material losses have on these behaviors. As a direct application of our results, we investigate the interaction between a nanoparticle array and a dielectric slab placed a certain distance above it and show that the extraordinary near-field enhancement produced by the lattice resonance can lead to very strong interactions, even at significantly large separations. This work provides a detailed characterization of the limits of the near-field produced by lattice resonances and, therefore, advances our knowledge of the optical response of periodic arrays of nanostructures, which can be used to design and develop applications exploiting the extraordinary properties of these systems.

Distinguishable Plasmonic Nanoparticle and Gap Mode Properties in a Silver Nanoparticle on a Gold Film System Using Three-Dimensional FDTD Simulations.

We present a computational study of the near-field enhancement properties from a plasmonic nanomaterial based on a silver nanoparticle on a gold film. Our simulation studies show a clear distinguishability between nanoparticle mode and gap mode as a function of dielectric layer thickness. The observed nanoparticle mode is independent of dielectric layer thickness, and hence its related plasmonic properties can be investigated clearly by having a minimum of ~10-nm-thick dielectric layer on a metallic film. In case of the gap mode, the presence of minimal dielectric layer thickness is crucial (~≤4 nm), as deterioration starts rapidly thereafter. The proposed simple tunable gap-based particle on film design might open interesting studies in the field of plasmonics, extreme light confinement, sensing, and source enhancement of an emitter.