Spectroscopic analysis of large biomolecules is critical in a number of applications, including medical diagnostics and label-free biosensing. Recently, it has been shown that Raman spectroscopy of proteins can be used to diagnose some diseases, including a few types of cancer. These experiments have however been performed using traditional Raman spectroscopy and the development of the Surface enhanced Raman spectroscopy (SERS) assays suitable for large biomolecules could lead to a substantial decrease in the amount of specimen necessary for these experiments. We present a new method to achieve high local field enhancement in surface enhanced Raman spectroscopy through the simultaneous adjustment of the lattice plasmons and localized surface plasmon polaritons, in a periodic bilayer nanoantenna array resulting in a high enhancement factor over the sensing area, with relatively high uniformity. The proposed plasmonic nanostructure is comprised of two interacting nanoantenna layers, providing a sharp band-edge lattice plasmon mode and a wide-band localized surface plasmon for the separate enhancement of the pump and emitted Raman signals. We demonstrate the application of the proposed nanostructure for the spectral analysis of large biomolecules by binding a protein (streptavidin) selectively on the hot-spots between the two stacked layers, using a low concentration solution (100 nM) and we successfully acquire its SERS spectrum.
Interaction between plasmonic nanostructures and molecules is modeled based on the concept of quantized optical cavity for surface enhanced Raman scattering process. We have found that the background emission from plasmonic nanostructures is not constant as speculated ordinarily, it is enhanced accompanying with the molecules Raman scattering. The plasmonic nanostructures not only scatter elastically the energy coupling from the molecules excited states, but also radiate it inelastically as surface plasmon emission partly resulting an enhanced background. According to single nanoparticle exper…
Using a hydrodynamic model of the free electron gas of metal, we theoretically investigate optically-induced DC current loops in a plasmonic nanostructure. Such current loops originate from an optical rectification process relying on three electromotive forces, one of which arises from an optical spin-orbit interaction. The resulting static magnetic field is found to be maximum and dramatically confined at the corners of the plasmonic nanostructure, which reveals the ability of metallic discontinuities to concentrate and tailor static magnetic fields on the nanoscale.
Graphene is a unique material to study fundamental limits of plasmonics. Apart from the ultimate single-layer thickness, its carrier concentration can be tuned by chemical doping or applying an electric field. In this manner the electrodynamic properties of graphene can be varied from highly conductive to dielectric. Graphene supports strongly confined, propagating surface plasmon-polaritons (SPPs) in a broad spectral range from terahertz to mid-infrared frequencies. It also possesses a strong magneto-optical response and thus provides complimentary architectures to conventional magneto-plasmo…
We show that second harmonic generation can be enhanced by Fano resonant coupling of asymmetric plasmonic metal nanostructures. We develop a theoretical model examining the effects of electromagnetic interaction between two metal nanostructures on the second harmonic generation. We compare the second harmonic generation efficiency of a single plasmonic metal nanostructure with that of two coupled ones. We show that second harmonic generation from a single metal nanostructure can be enhanced about 30 times by attaching a second metal nanostructure with a 10 times higher quality factor than that…
We demonstrate that the fluorescent emitters can increase light emission from the plasmonic nanostructures in turn. With the help of atomic force microscopy, a hybrid system consisting of a fluorescent nanodiamond and a gold nanoparticle was assembled step-by-step for in situ optical measurements. We found that the emission from the nanoparticle increased compared with that before coupling. The interaction between plasmonic nanostructures and fluorescent emitter was understood as an entity based on the concept of a quantized optical cavity by considering the nanodiamond and the nanoparticle as…
Simple high-performance two-stage hybrid technique was developed for fabrication of different plasmonic nanostructures, including nanorods, nanorings, as well as more complex structures on glass substrates. In this technique a thin noble metal film on a dielectric substrate is irradiated by a tightly focused single nanosecond laser pulse and then the modified region is slowly polished by an accelerated argon ion (Ar+) beam. As a result, each nanosecond laser pulse locally modifies the initial metal film through initiation of fast melting and subsequent hydrodynamic processes, while the followi…
We introduce a numerical framework for calculating decay rate contributions when excited two-level quantum emitters are located near layered plasmonic nanostructures, particularly emphasizing the case of plasmonic nanostructures atop metal substrates where three decay channels exist: free space radiation, Ohmic losses, and excitation of surface plasmon polaritons (SPPs). The calculation of decay rate contributions is based on Huygen's equivalence principle together with a near-field to far-field transformation of the local electric field, thereby allowing us to discern the part of the electrom…
Plasmonic- and Electronic-Enhancement-Free Coherent Raman Detection of Ångström-Scale Molecular Layers at Metal Interfaces
Institute for Molecular Science, National Institutes of Natural Sciences（国立自然科学研究所分子科学研究所）；Graduate Institute for Advanced Studies, SOKENDAI（SOKENDAI高等研究院）；RIKEN Spring-8 Center（理化学研究所Spring-8中心）
This paper presents high-order (HO) electromagnetic modeling of plasmonic nanostructures based on the Locally Corrected Nystrom (LCN) method. Advanced nanophotonic and nanoplasmonic structures involve electrically large electromagnetic structures that are very complex in both geometry and material composition. Hence, advanced analysis and design tools are required in order to predict the performance of such structures and optimize the geometrical parameters prior to costly prototype development. In this perspective, the LCN is exploited to solve the electromagnetic scattering of plasmonic nano…
We present a comprehensive review of recent developments in the field of chiral plasmonics. Significant advances have been made recently in understanding the working principles of chiral plasmonic structures. With advances in micro- and nanofabrication techniques, a variety of chiral plasmonic nanostructures have been experimentally realized; these tailored chiroptical properties vastly outperform those of their molecular counterparts. We focus on chiral plasmonic nanostructures created using bottom-up approaches, which not only allow for rational design and fabrication but most intriguingly i…
The search for miniaturized components for nonlinear optical processes needs a way to overcome the efficiency loss due to the effective size reduction of the active medium. We investigate here a combination of a nanosized nonlinear dielectric crystal and metallic nanoantennas that benefits from both the intrinsic nonlinear conversion efficiency of the nonlinear medium and the local-field enhancement of plasmonic resonances in metallic nanostructures. Careful comparison between experiments and numerical simulations reveals that the observed 10 to 1000 fold enhancement in Second Harmonic Generat…
The theory of energy transfer dynamics of a pair of donor and acceptor molecules located in the plasmonic hot spots is developed by means of the master equation approach and the electromagnetic Green's tensor technique. A nonlocal effect has been considered by using a hydrodynamic model. The coherent interaction between the two molecules in plasmonic nanostructures is investigated under some strong coupling conditions. It is shown that the energy transfer efficiency of a pair of molecules can be improved largely and the transfer time decreases to dozens of femtoseconds when the contribution of…
Hotspots of surface-enhanced resonance Raman scattering (SERRS) are localized within 1 nm at gaps or crevices of plasmonic nanoparticle (NP) dimers. We demonstrate SERRS hotspots with volumes that are extended in one dimension tens of thousand times compared to standard zero-dimensional hotspots using gaps or crevices of plasmonic nanowire (NW) dimers.
Plasmonic hot carrier devices extract excited carriers from metal nanostructures before equilibration, and have the potential to surpass semiconductor light absorbers. However their efficiencies have so far remained well below theoretical limits, which necessitates quantitative prediction of carrier transport and energy loss in plasmonic structures to identify and overcome bottlenecks in carrier harvesting. Here, we present a theoretical and computational framework, Non-Equilibrium Scattering in Space and Energy (NESSE), to predict the spatial evolution of carrier energy distributions that com…
The ability of metallic nanostructures to confine light at the sub-wavelength scale enables new perspectives and opportunities in the field of nanotechnology. Making use of this unique advantage, nano-optical trapping techniques have been developed to tackle new challenges in a wide range of areas from biology to quantum optics. In this work, starting from basic theories, we present a review of research progress in near-field optical manipulation techniques based on metallic nanostructures, with an emphasis on some of the most promising advances in molecular technology, such as the precise con…
We present a theoretical study of the characteristics of the nonlinear spin-orbital angular momentum coupling induced by second-harmonic generation in plasmonic and dielectric nanostructures made of centrosymmetric materials. In particular, the connection between the phase singularities and polarization helicities in the longitudinal components of the fundamental and second-harmonic optical fields and the scatterer symmetry properties are discussed. By in-depth comparison between the interaction of structured optical beams with plasmonic and dielectric nanostructures, we have found that all-di…
A significant interest in combining plasmonics and magnetism at the nanoscale gains momentum in both photonics and magnetism sectors that are concerned with the resonant enhancement of light-magnetic-matter interaction in nanostructures. These efforts result in a considerable amount of literature, which is difficult to collect and digest in limited time. Furthermore, there is insufficient exchange of results between the two research sectors. Consequently, the goal of this review paper is to bridge this gap by presenting an overview of recent progress in the field of magneto-plasmonics from two…
Recently, a new device to measure the Orbital Angular Momentum (OAM) electronic spectrum after elastic/inelastic scattering in a transmission electron microscope has been introduced. We modified the theoretical framework needed to describe conventional low loss electron energy loss spectroscopy (EELS) experiments in transmission electron microscopes (TEM) to study surface plasmons in metallic nanostructures, to allow for an OAM post selection and devise new experiments for the analysis of these excitations in nanostructures. We found that unprecedented information on the symmetries and on the …
In this thesis various plasmonic materials, such as hyperbolic metamaterial nanohole arrays and Au-coated free standing nanoassembly supporting nanopores, are investigated with the aim to perform optical sensing of DNA molecules with Surface-Enhanced Raman Spectroscopy in flow-through configuration.
In this work, we demonstrated on-chip label-free imaging microscopy using real and Fourier Plane (FP) microscopic dark field images of Surface Plasmons (SP), excited on engineered 1D and 2D low aspect ratio periodic plasmonic nanostructures. The periodic plasmonic nanostructures with period almost equal to resonance wavelength, were engineered to exhibit transmission resonances as transmission peaks in visible spectrum at normal incidence, without using extraordinary optical transmission phenomena. The plasmonic nanostructures exhibited a polarization rotation of 90 degree mediated by differen…
We study how the collective effects of nanoparticles arranged in rectangular arrays influence their temporal plasmon response and field enhancement property. By systematically changing the lattice constant for arrays containing identical metal nanorods, we experimentally demonstrate how grating induced effects affect the position and, more importantly, the broadening of extinction spectra. We correlate these effects with the achievable field enhancement and the temporal duration of plasmon transients and formulate criteria for the generation of enhanced few-cycle localized plasmon oscillations…
The use of magneto-optical techniques to tune the plasmonic response of nanostructures is a hot topic in active plasmonics, with fascinating implications for several plasmon-based applications and devices. For this emerging field, called magnetoplasmonics, plasmonic nanomaterials with strong optical response to magnetic field are desired, which is generally challenging to achieve with pure noble metals. To overcome this issue, several efforts have been carried out to design and tailor the magneto-optical response of metal nanostructures, mainly by combining plasmonic and magnetic materials in …
We present a quantum-mechanical model for surface-assisted carrier excitation by optical fields in plasmonic nanostructures of arbitrary shape. We derive an explicit expression, in terms of local fields inside the metal structure, for surface absorbed power and surface scattering rate that determine the enhancement of carrier excitation efficiency near the metal-dielectric interface. We show that surface scattering is highly sensitive to the local field polarization, and can be incorporated into metal dielectric function along with phonon and impurity scattering. We also show that the obtained…
In this work, we report numerical simulations and experiments of the optical response of a gold nanostrip embedded in a silicon strip waveguide gap at telecom wavelengths. We show that the spectral features observed in transmission and reflection when the metallic nanostructure is inserted in the gap are extremely different to those observed in free-space excitation. First, we find that interference between the guided field and the electric dipolar resonance of the metallic nanostructure results in high-contrast (> 10) spectral features showing an asymmetric Fano spectral profile. Secondly, we…
We theoretically investigate several types of plasmonic slot waveguides for enhancing the measured signal in Raman spectroscopy, which is a consequence of electric field and Purcell factor enhancements, as well as an increase in light-matter interaction volume and the Raman signal collection efficiency. An intuitive methodology is presented for calculating the accumulated Raman enhancement factor of an ensemble of molecules in waveguide sensing, which exploits an analytical photon Green function expansion in terms of the waveguide normal modes, and we combine this with a quantum optics formali…
Plasmonic and Mie resonances in subwavelength nanostructures provide an efficient way to manipulate light below the diffraction limit that has fostered the growth of plasmonics and nanophotonics. Plasmonic resonances have been mainly related with the excitation of free charge carriers, initially in metals, and Mie resonances have been identified in Si nanostructures. Remarkably, although much less studied, semi-metals, semiconductors and topological insulators of the p-block enable plasmonic resonances without free charge carriers and Mie resonances with enhanced properties compared with Si. I…
A tri-layer metamaterial perfect absorber of light, consisting of (Al/ZnS/Al) films with the top aluminium layer patterned as an array of circular disk nanoantennas, is investigated for resonantly enhancing Raman scattering from C-60 fullerene molecules deposited on the metamaterial. The metamaterial is designed to have resonant bands due to plasmonic and electromagnetic resonances at the Raman pump frequency (725 nm) as well as Stokes emission bands. The Raman scattering from C60 on the metamaterial with resonantly matched bands is measured to be enhanced by an order of magnitude more than fr…
Under the local plasmonic excitation, the Raman images of a single molecule can now reach sub-nanometer resolution. We report here a theoretical description of the interaction between a molecule and a highly confined plasmonic field. It is shown that when the spatial distribution of the plasmonic field is comparable with the size of the molecule, the optical transition matrix of the molecule becomes to be dependent on the position and the spatial distribution of the plasmonic field, resulting in spatially resolved Raman image of a molecule. It is found that the resonant Raman image reflects th…
Metal nanowires and nanoparticles that facilitate surface plasmons are of contemporary interest in nanophotonics, thermoplasmonics and optoelectronics. They facilitate not only subwavelength light propagation and localization capabilities, but also provide an excellent platform for opto-thermal effects confined to volumes down to the nanoscale. This brief review article aims to provide an overview of a specific nanophotonic geometry: a plasmonic nanowire coupled to a zero-dimensional nanostructure. We discuss the methods to prepare such nano-architectures and review some interesting nanophoton…
We derive and present systematic relationships between the analytical formulas for calculation of the localized surface plasmon resonances (LSPR) of some plasmonic nano-structures which we have categorized as simple. These relationships, including some new formulas, are summarized in a tree diagram which highlights the core-shell plasmons as the generators of solid and cavity plasmons. In addition, we show that the LSPR of complex structures can be reduced to that of simpler ones, using the LSPR of a nanorice as a case study, in the dipole limit. All the formulas were derived using a combinati…
Topology optimization techniques have been applied in integrated optics and nanophotonics for the inverse design of devices with shapes that cannot be conceived by human intuition. At optical frequencies, these techniques have only been utilized to optimize nondispersive materials using frequency-domain methods. However, a time-domain formulation is more efficient to optimize materials with dispersion. We introduce such a formulation for the Drude model, which is widely used to simulate the dispersive properties of metals, conductive oxides, and conductive polymers. Our topology optimization a…
Molecular motor proteins form the basis of cellular dynamics. Recently, notable efforts have led to the creation of their DNA-based mimics, which can carry out complex nanoscale motion. However, such functional analogues have not yet been integrated or operated inside synthetic cells toward the goal of realizing artificial biological systems entirely from the bottom-up. In this Letter, we encapsulate and actuate DNA-assembled dynamic nanostructures inside cell-sized microfluidic compartments. These encapsulated DNA nanostructures not only exhibit structural reconfigurability owing to their pH-…
Molecular vibrations and their dynamics are of outstanding importance for electronic and thermal transport in nanoscale devices as well as for molecular catalysis. The vibrational dynamics of <100 molecules are studied through three-colour time-resolved coherent anti-Stokes Raman spectroscopy (trCARS) using plasmonic nanoantennas. This isolates molecular signals from four-wave mixing (FWM), while using exceptionally low nanowatt powers to avoid molecular damage via single-photon lock-in detection. FWM is found to be strongly suppressed in nm-wide plasmonic gaps compared to plasmonic nanopartic…
Dewetting of thin metal films is one of the most widespread method for functional plasmonic nanostructures fabrication. However, simple thermal-induced dewetting does not allow to control degree of nanostructures order without additional lithographic process steps. Here we propose a novel method for lithography-free and large-scale fabrication of plasmonic nanostructures via controllable femtosecond laser-induced dewetting. The method is based on femtosecond laser surface pattering of a thin film followed by a nanoscale hydrodynamical instability, which is found to be very controllable under s…
We propose a novel method to enhance the transverse magneto-optical Kerr effect (TMOKE) in the magneto-plasmonic (MP) nanostructures by means of the active dielectric layer. We report the theoretical analysis of the magnetoplasmonic structure with a ferromagnetic dielectric doped with rear-earth ions (Nd3+) as the example of a gain layer. The enhancement takes place near the surface plasmon polariton (SPP) resonances of the nanostructures. The stimulated emission of the dopants in the field of SPP wave partially compensates its losses. It is shown that due to a decrease of SPP damping a Q-fact…
We present a rigorous finite element method to calculate circular dichroism (CD) in various systems consisting of nanostructures and oriented chiral molecules with electric quadrupole transitions. The interaction between oriented molecule materials, which are regarded as anisotropic chiral media, and metallic nanostructures has been investigated. Our results show that the plasmon-induced CD is sensitive to the orientations of the molecules. In many cases, the contribution of molecular electric quadrupole transitions to the total CD signal can play a key role. More interesting, we have demonstr…
The Fano and Rabi models represent remarkably common effects in optics. Here we study the coherent time dynamics of plasmonic systems exhibiting Fano and Rabi resonances. We demonstrate that these systems show fundamentally different dynamics. A system with a Fano resonance displays at most one temporal beat under pulsed excitation, whereas a system in the Rabi regime may have any number of beats. Remarkably, the Fano-like systems show time dynamics with very characteristic coherent tails despite the strong decoherence that is intrinsic for such systems. The coherent Fano and Rabi dynamics tha…
The spectral response of a plasmonic nanostructure may heavily depend on the refractive index of its surroundings. The key idea of this paper is to control this response by coherent optical means, i.e. with an optically controlled electromagnetically-induced-transparency medium. In such environment, an external laser provides a knob to shift the position of plasmonic resonances without the need to change the geometry of the nanostructure. Additionally, the setup can be exploited to excite narrow-band surface plasmon polaritons.
Trapping light in open cavities is a long sought "holy grail" of nanophotonics. Plasmonic materials may offer a unique opportunity in this context, as they may fully suppress the radiation loss and enable the observation of spatially localized light states with infinite lifetime in an open system. Here, we investigate how the spatial dispersion effects, e.g., caused by the electron-electron interactions in a metal, affect the trapped eigenstates. Heuristically, one may expect that the repulsive-type electron-electron interactions should act against light localization, and thereby that they sho…
Characteristic Mode Analysis of Plasmonic Nanostructures Using Hydrodynamic Volume Integral Equation
King Abdullah University of Science and Technology (KAUST)（阿卜杜拉国王科技大学）；University of Electronic Science and Technology of China (UESTC)（电子科技大学）；Light Academy College of Engineering（轻工业学院工程学院）
