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Surface-enhanced Raman optical activity (SEROA) has been extensively investigated due to its ability to directly probe stereochemistry and molecular structure. However, most works have focused on the Raman optical activity (ROA) effect arising from the chirality of the molecules on isotropic surfaces. Here, we propose a strategy for achieving a similar effect: i.e., a surface-enhanced Raman polarization rotation effect arising from the coupling of optically inactive molecules with the chiral plasmonic response of metasurfaces. This effect is due to the optically active response of metallic nanostructures and their interaction with molecules, which could extend the ROA potential to inactive molecules and be used to enhance the sensibility performances of surface-enhanced Raman spectroscopy. More importantly, this technique does not suffer from the heating issue present in traditional plasmonic-enhanced ROA techniques, as it does not rely on the chirality of the molecules.
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Hybrid composites between nanoparticles and metal organic frameworks (MOFs) have been described as optimal materials for a wide range of applications in optical sensing, drug delivery, pollutant removal or catalysis. These materials are usually core-shell single- or multi-nanoparticles, restricting the inorganic surface available for reaction. Here, we develop a method for the preparation of yolk-shells consisting in a plasmonic gold nanostar coated with MOF. This configuration shows more colloidal stability, can sieve different molecules based on their size or charge, seems to show some interesting synergy with gold for their application in photocatalysis and present strong optical activity to be used as SERS sensors.
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Estruturas Metalorgânicas , Nanopartículas , Ouro , Sistemas de Liberação de Medicamentos , CatáliseRESUMO
Plasmonic metamaterials enable extraordinary manipulation of key constitutive properties of light at a subwavelength scale and thus have attracted significant interest. Here, we report a simple and convenient nanofabrication method for a novel meta-device by glancing deposition of gold into anodic aluminum oxide templates on glass substrates. A methodology with the assistance of ellipsometric measurements to examine the anisotropy and optical activity properties is presented. A tunable polarization conversion in both transmission and reflection is demonstrated. Specifically, giant broadband circular dichroism for reflection at visible wavelengths is experimentally realized by oblique incidence, due to the extrinsic chirality resulting from the mutual orientation of the metamaterials and the incident beam. This work paves the way for practical applications for large-area, low-cost polarization modulators, polarization imaging, displays, and bio-sensing.
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A surface-enhanced Raman scattering-based mapping technique is reported for the highly sensitive and reproducible analysis of multiple mycotoxins. Raman images of three mycotoxins, ochratoxin A (OTA), fumonisin B (FUMB), and aflatoxin B1 (AFB1) are obtained by rapidly scanning the surface-enhanced Raman scattering (SERS) nanotags-anchoring mycotoxins captured on a nanopillar plasmonic substrate. In this system, the decreased gap distance between nanopillars by their leaning effects as well as the multiple hot spots between SERS nanotags and nanopillars greatly enhances the coupling of local plasmonic fields. This strong enhancement effect makes it possible to perform a highly sensitive detection of multiple mycotoxins. In addition, the high uniformity of the densely packed nanopillar substrate minimizes the spot-to-spot fluctuations of the Raman peak intensity in the scanned area when Raman mapping is performed. Consequently, this makes it possible to gain a highly reproducible quantitative analysis of mycotoxins. The limit of detections (LODs) are determined to be 5.09, 5.11, and 6.07 pg mL-1 for OTA, FUMB, and AFB1, and these values are approximately two orders of magnitude more sensitive than those determined by the enzyme-linked immunosorbent assays. It is believed that this SERS-based mapping technique provides a facile tool for the sensitive and reproducible quantification of various biotarget molecules.
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Imunoensaio/métodos , Micotoxinas/análise , Análise Espectral Raman/métodosRESUMO
We report on the strong enhancement of mid-infrared second-harmonic generation (SHG) from SiC nanopillars due to the resonant excitation of localized surface phonon polaritons within the Reststrahlen band. A strong dependence of the SHG enhancement upon the optical mode distribution was observed. One such mode, the monopole, exhibits an enhancement that is beyond what is anticipated from field localization and dispersion of the linear and nonlinear SiC optical properties. Comparing the results for the identical nanostructures made of 4H and 6H SiC polytypes, we demonstrate the interplay of localized surface phonon polaritons with zone-folded weak phonon modes of the anisotropic crystal. Tuning the monopole mode in and out of the region where the zone-folded phonon is excited in 6H-SiC, we observe a further prominent increase of the already enhanced SHG output when the two modes are coupled. Envisioning this interplay as one of the showcase features of mid-infrared nonlinear nanophononics, we discuss its prospects for the effective engineering of nonlinear-optical materials with desired properties in the infrared spectral range.
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Recently, so-called "superlenses", made from metamaterials that are structured on a length scale much less than an optical wavelength, have shown impressive diffraction-beating image resolution, but they use materials with negative dielectric responses, and they absorb much of the light in a way that seriously degrades both the resolution and brightness of the image. Here we demonstrate an alternative "quantum metamaterials" (QM) approach that uses materials structured at the nanoscale, i.e., comparable to an electron wavelength. This allows us to use quantum mechanical design principles to generate structures with a highly elliptical isofrequency dispersion characteristic that circumvents this loss problem. The physics of the loss improvement is analyzed analytically and the QM superlens subdiffraction imaging is modeled numerically, with a finite-element method. Finally, we demonstrate a working QM superlens device, utilizing intersubband transitions between the confined electron states in a III-V semiconductor multiquantum-well. It images down to a resolution of better than â¼ λ/10 and has loss figures improved by roughly a decade over previous "classical" designs. This QM approach is an alternative paradigm for designing radiation-manipulating devices and offers the prospect of practical super-resolving devices at new wavelengths and geometries.
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Nonlinear phenomena are central to modern photonics but, being inherently weak, typically require gradual accumulation over several millimeters. For example, second harmonic generation (SHG) is typically achieved in thick transparent nonlinear crystals by phase-matching energy exchange between light at initial, ω, and final, 2ω, frequencies. Recently, metamaterials imbued with artificial nonlinearity from their constituent nanoantennas have generated excitement by opening the possibility of wavelength-scale nonlinear optics. However, the selection rules of SHG typically prevent dipole emission from simple nanoantennas, which has led to much discussion concerning the best geometries, for example, those breaking centro-symmetry or incorporating resonances at multiple harmonics. In this work, we explore the use of both nanoantenna symmetry and multiple harmonics to control the strength, polarization and radiation pattern of SHG from a variety of antenna configurations incorporating simple resonant elements tuned to light at both ω and 2ω. We use a microscopic description of the scattering strength and phases of these constituent particles, determined by their relative positions, to accurately predict the SHG radiation observed in our experiments. We find that the 2ω particles radiate dipolar SHG by near-field coupling to the ω particle, which radiates SHG as a quadrupole. Consequently, strong linearly polarized dipolar SHG is only possible for noncentro-symmetric antennas that also minimize interference between their dipolar and quadrupolar responses. Metamaterials with such intra-antenna phase and polarization control could enable compact nonlinear photonic nanotechnologies.
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Superconducting nanowire single photon detectors are rapidly emerging as a key infrared photon-counting technology. Two front-side-coupled silver dipole nanoantennas, simulated to have resonances at 1480 and 1525 nm, were fabricated in a two-step process. An enhancement of 50 to 130% in the system detection efficiency was observed when illuminating the antennas. This offers a pathway to increasing absorption into superconducting nanowires, creating larger active areas, and achieving more efficient detection at longer wavelengths.
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Hybrid plasmonic metal-graphene systems are emerging as a class of optical metamaterials that facilitate strong light-matter interactions and are of potential importance for hot carrier graphene-based light harvesting and active plasmonic applications. Here we use femtosecond pump-probe measurements to study the near-field interaction between graphene and plasmonic gold nanodisk resonators. By selectively probing the plasmon-induced hot carrier dynamics in samples with tailored graphene-gold interfaces, we show that plasmon-induced hot carrier generation in the graphene is dominated by direct photoexcitation with minimal contribution from charge transfer from the gold. The strong near-field interaction manifests as an unexpected and long-lived extrinsic optical anisotropy. The observations are explained by the action of highly localized plasmon-induced hot carriers in the graphene on the subresonant polarizability of the disk resonator. Because localized hot carrier generation in graphene can be exploited to drive electrical currents, plasmonic metal-graphene nanostructures present opportunities for novel hot carrier device concepts.
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It is demonstrated herein both theoretically and experimentally that Young's interference can be observed in plasmonic structures when two or three nanoparticles with separation on the order of the wavelength are illuminated simultaneously by a plane wave. This effect leads to the formation of intermediate-field hybridized modes with a character distinct of those mediated by near-field and/or far-field radiative effects. The physical mechanism for the enhancement of absorption and scattering of light due to plasmonic Young's interference is revealed, which we explain through a redistribution of the Poynting vector field and the formation of near-field subwavelength optical vortices.
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Partículas Elementares , Nanopartículas/química , Espalhamento de Radiação , Difração de Raios X , Absorção , Dimerização , Nanopartículas/ultraestrutura , Espectrometria de Fluorescência , TermodinâmicaRESUMO
Discrete-dipole approximation (DDA), which is used for computing scattering and absorption by particles of arbitrary geometry and material, is extended to the case of a rectangular cuboidal point lattice using an accurate, analytical expression of the polarizability of each cuboidal element at optical frequencies of up to 100 nm in size. This polarizability formulation (cuboidal lattice with depolarization or CLD) is shown to be more accurate in the computation of the extinction, scattering, and absorption cross sections when simulating dielectrics compared to other available and commonly used expressions of the polarizability. This can be used to reduce the number of dipoles N used, and therefore, the computation time while achieving the same accuracy of other formulations. The CLD formulation was applied to the Mie scattering problem and the results were compared to results from other DDA formulations, as well as to the Mie analytical solution for metal and dielectric spheres. Metal cubes were also simulated and different formulations compared.
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Plasmonics provides great promise for nanophotonic applications. However, the high optical losses inherent in metal-based plasmonic systems have limited progress. Thus, it is critical to identify alternative low-loss materials. One alternative is polar dielectrics that support surface phonon polariton (SPhP) modes, where the confinement of infrared light is aided by optical phonons. Using fabricated 6H-silicon carbide nanopillar antenna arrays, we report on the observation of subdiffraction, localized SPhP resonances. They exhibit a dipolar resonance transverse to the nanopillar axis and a monopolar resonance associated with the longitudinal axis dependent upon the SiC substrate. Both exhibit exceptionally narrow linewidths (7-24 cm(-1)), with quality factors of 40-135, which exceed the theoretical limit of plasmonic systems, with extreme subwavelength confinement of (λ(res)3/V(eff))1/3 = 50-200. Under certain conditions, the modes are Raman-active, enabling their study in the visible spectral range. These observations promise to reinvigorate research in SPhP phenomena and their use for nanophotonic applications.
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The quest for environmentally sustainable materials spans many fields and applications including optical materials. Here, we present the development of light filters using a gelatin-based nanocomposite. Owing to the plasmonic properties of metallic nanoparticles (NPs), strong light-matter interactions, these filters can be customized across the UV-Visible-NIR spectrum. The filters are designed for modular use, allowing for the addition or removal of desired spectral ranges. Moreover, the nanocomposites are composed of biodegradable and biocompatible materials which highlight the intersection of chemistry and ecological awareness for the exploration of new eco-friendly alternatives. These plasmonic gelatin-based filters block light due to the Localized Surface Plasmon Resonance (LSPR) of the NPs and can be tailored to meet various requirements, akin to a diner selecting options from a menu. This approach is inspired by culinary techniques, and we anticipate it will stimulate further exploration of biomaterials for applications in optics, materials science or electronics.
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We report herein the design of plasmonic hollow nanoreactors capable of concentrating light at the nanometer scale for the simultaneous performance and optical monitoring of thermally activated reactions. These reactors feature the encapsulation of plasmonic nanoparticles on the inner walls of a mesoporous silica capsule. A Diels-Alder cycloaddition reaction was carried out in the inner cavities of these nanoreactors to evidence their efficacy. Thus, it is demonstrated that reactions can be accomplished in a confined volume without alteration of the temperature of the bulk solvent while allowing real-time monitoring of the reaction progress.
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In this article, we use optical transmission spectroscopy to measure the changes in the resonance features of a Au plasmonic nanoresonator array consisting of concentric ring/disc cavity elements, when graphene is introduced as an encapsulating medium. We show that by using finite element modelling to best reproduce our experimental results the dielectric response of the graphene film can be determined. We discuss the potential of such structures for chemical sensing applications.
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Plasmonic resonances with a Fano lineshape observed in metallic nanoclusters often arise from the destructive interference between a dark, subradiant mode and a bright, super-radiant one. A flexible control over the Fano profile characterized by its linewidth and spectral contrast is crucial for many potential applications such as slowing light and biosensing. In this work, we show how one can easily but significantly tailor the overall spectral profile in plasmonic nanocluster systems, for example, quadrumers and pentamers, by selectively altering the particle shape without a need to change the particle size, interparticle distance, or the number of elements of the oligomers. This is achieved through decomposing the whole spectrum into two separate contributions from subgroups, which are efficiently excited at their spectral peak positions. We further show that different strengths of interference between the two subgroups must be considered for a full understanding of the resulting spectral lineshape. In some cases, each subgroup is separately active in distinct frequency windows with only small overlap, leading to a simple convolution of the subspectra. Variation in particle shape of either subgroup results in the tuning of the overall spectral lineshape, which opens a novel pathway for shaping the plasmonic response in small nanoclusters.
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An optical sensor was developed for the quantitative determination of intracellular nitric oxide. The sensor consists of plasmonic nanoprobes that have a coating of mesoporous silica and an inner gold island film functionalized with a chemoreceptor for NO.
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Técnicas Biossensoriais/métodos , Nanoestruturas/uso terapêutico , Óxidos de Nitrogênio/químicaRESUMO
In the last years there have been multiple proposals in nanophotonics to mimic topological condensed matter systems. However, nanoparticles have degrees of freedom that atoms lack of, like dimensions or shape, which can be exploited to explore topology beyond electronics. Elongated nanoparticles can act like projectors of the electric field in the direction of the major axis. Then, by orienting them in an array the coupling between them can be tuned, allowing to open a gap in an otherwise gapless system. As a proof of the potential of the use of orientation of nanoparticles for topology, we study 1D chains of prolate spheroidal silver nanoparticles. We show that in these arrays spatial modulation of the polarization allows to open gaps, engineer hidden crystalline symmetries and to switch on/off or left/right edge states depending on the polarization of the incident electric field. This opens a path toward exploiting features of nanoparticles for topology to go beyond analogues of condensed matter systems.
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Designing a broadband, wide-angle, and high-efficient polarization converter with a simple geometry remains challenging. This work proposes a simple and computationally inexpensive method for devising broadband polarization conversion metasurfaces. We focus on a cross-shape configuration consisting of two bars of different lengths connected at the center. To design the metasurface, we decompose the system into two parts with two orthogonally polarized responses and calculate the response of each part separately. By selecting the parameters with a proper phase difference in the response between the two parts, we can determine the dimensions of the system. For designing broadband polarization conversion metasurfaces, we define a fitness function to optimize the bandwidth of the linear polarization conversion. Numerical results demonstrate that the proposed method can be used to design a metasurface that achieves a relative bandwidth of [Formula: see text] for converting linearly polarized waves into cross-polarized waves. Additionally, the average polarization conversion ratio of the designed metasurface is greater than [Formula: see text] over the frequency range of 10.9-28.5 GHz. This method significantly reduces the computational expense compared to the traditional method and can be easily extended to other complex structures and configurations.
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Photoacoustics (PA) is gaining increasing credit among biomolecular imaging methodologies by virtue of its poor invasiveness, deep penetration, high spatial resolution, and excellent endogenous contrast, without the use of any ionizing radiation. Recently, we disclosed the excellent PA response of a self-structured biocompatible nanoprobe, consisting of ternary hybrid nanoparticles with a silver core and a melanin component embedded into a silica matrix. Although preliminary evidence suggested a crucial role of the Ag sonophore and the melanin-containing nanoenvironment, whether and in what manner the PA response is controlled and affected by the self-structured hybrid nanosystems remained unclear. Because of their potential as multifunctional platforms for biomedical applications, a detailed investigation of the metal-polymer-matrix interplay underlying the PA response was undertaken to understand the physical and chemical factors determining the enhanced response and to optimize the architecture, composition, and performance of the nanoparticles for efficient imaging applications. Herein, we provide the evidence for a strong synergistic interaction between eumelanin and Ag which suggests an important role in the in situ-generated metal-organic interface. In particular, we show that a strict ratio between melanin and silver precursors and an accurate choice of metal nanoparticle dimension and the kind of metal are essential for achieving strong enhancements of the PA response. Systematic variation of the metal/melanin component is thus shown to offer the means of tuning the stability and intensity of the photoacoustic response for various biomedical and theranostic applications.