We extend the Purcell's original idea [Phys. Rev. \textbf{69}, 682 (1946)] on modification of photon spontaneous \textit{emission} rate to modification of photon spontaneous \textit{scattering} rate. We find the interplay of local incident field enhancement and local density of photon states enhancement in close proximity to a silver nanoparticle may result in up to $10^{14}$-fold rise of Raman scattering cross-section. Thus single molecule Raman detection is found to be explained by consistent quantum electrodynamic description without any chemical mechanism involved. A model of the so-called "hot points" in surface enhanced spectroscopy has been elaborated as local areas with high Q-factor at incident and scattered (emitted) light frequencies. For verification of the model we consider further experiments including transient Raman experiments to clarify incident field enhancement and scanning near-field optical mapping of local density of photon states.
The expression for the SEHR cross-section of symmetrical molecules within the framework of the dipole-quadrupole theory is obtained. It is formed by contributions, which depend on various dipole and quadrupole moments. Estimation of the enhancement coefficients for the quadrupole enhancement mechanism in some limited case can achieve the value . It is demonstrated that the contributions follow some selection rules. Qualitative classification of the contributions after the enhancement degree is given.
Surface-enhanced coherent anti-Stokes Raman scattering (SE-CARS) takes advantage of surface plasmon resonances supported on metallic nanostructures to amplify the coherent Raman response of target molecules. While these metallic antennas have found significant success in SE-CARS studies, photo-induced morphological changes to the nanoantenna under ultrafast excitation introduce significant hurdles in terms of stability and reproducilibty. These hurdles need to be overcome in order to establish SE-CARS as a reliable tool for rapid biomolecular sensing. Here we address this challenge by performi…
Conjugated metallic nanoparticles are a promising means to achieve ultrasensitive and multiplexed sensing in intact three-dimensional samples, especially for biological applications, via surface enhanced Raman scattering (SERS). We show that enhancement and extinction are linked and compete in a collection of metallic nanoparticles. Counterintuitively, the Raman signal vanishes when nanoparticles are excited at their plasmon resonance, while increasing nanoparticle concentrations at off-resonance excitation sometimes leads to decreased signal. We develop an effective medium theory that explain…
Microscopic pyramidal pits in a reflective surface, a geometry similar to a retroreflector, are frequently used to enhance signal strength. The enhancement effect is generally attributed to surface plasmons, however, the sub-wavelength to near-wavelength dimensions of the pyramidal 3D geometry suggest contributions from diffraction and near-field effects. Our theoretical analysis of the light intensity distribution in the similar (but simpler) 2D geometry assuming a perfect conductor screen, that is, in the absence of any plasmon effects, shows that interference patterns forming within the cav…
We demonstrate efficient generation of a Raman-type optical frequency comb by employing adiabatic Raman excitation in an enhancement cavity. A broad frequency comb spanning over 130 THz is realized with an excitation power reduction exceeding three orders of magnitude compared with a single-pass configuration.
Resonantly enhanced Raman scattering in dielectric nanostructures has been recently proven to be an effcient tool for developing nanothermometry and experimental determination of their mode- composition. In this paper, we develop a rigorous analytical theory based on the Green's function approach to calculate the Raman emission from crystalline high-index dielectric nanoparticles. As an example, we consider silicon nanoparticles which have a strong Raman response due to active optical phonon modes. We relate enhancement of Raman signal emission to Purcell effect due to the excitation of Mie mo…
This article reviews the new developments in Tip-enhanced Raman scattering (TERS). The fundamental mechanisms underlying the Raman enhancement are discussed, including the role of the plasmonic character of the metallic tips, the nature of the optical tip-sample coupling and the resulting local-field confinement responsible for ultrahigh spatial resolution down to just several nanometers. Criteria for the distinction of near-field signature from far-field imaging artifacts are addressed and TERS results of molecules and nanostructures are presented. With enhancement factors as high as 10$^9$, …
We used broad-band diamond-shape antennas, whose bandwidth could cover the frequency range between the pump laser and the scattered modes, in conjunction with uniformly deposited graphene test films.
We study transmission stabilization against radiation emission in soliton-based nonlinear optical waveguides with weak linear gain-loss, cubic loss, and delayed Raman response. We show by numerical simulations with perturbed nonlinear Schrödinger propagation models that transmission quality in waveguides with frequency independent linear gain and cubic loss is not improved by the presence of delayed Raman response due to the lack of an efficient mechanism for suppression of radiation emission. In contrast, we find that the presence of delayed Raman response leads to significant enhancement of …
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…
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…
Raman scattering signal can be enhanced through localization of incident field into sub-wavelength hot-spots through plasmonic nano-structures (Surface-enhanced Raman scattering-SERS). Recently, further enhancement of SERS signal via quantum objects are proposed by [1] without increasing the hot-spot intensity (\textit{silent-enhancement}) where this suggestion prevents the modification of vibrational modes or the breakdown of molecules. The method utilizes path interference in the non-linear response of Stokes-shifted Raman modes. In this work, we extend this phenomenon to tune the spectral p…
We propose a method for increasing the Raman scattering from an ensemble of molecules by up to four orders of magnitude. Our method requires an additional coherent source of IR radiation with the half-frequency of the Stokes shift. This radiation excites the molecule electronic subsystem that in turn, via Fröhlich coupling, parametrically excites nuclear oscillations at a resonant frequency. This motion is coherent and leads to a boost of the Raman signal in comparison to the spontaneous signal because its intensity is proportional to the squared number of molecules in the illuminated volume.
In this work, we introduce the platform of plasmonic Doppler grating (PDG) to experimentally investigate the enhancement effect of plasmonic gratings in the input and output beams of nonlinear surface-enhanced coherent anti-Stokes Raman scattering (SECARS). PDGs are designable azimuthally chirped gratings that provide broadband and spatially dispersed plasmonic enhancement. Therefore, they offer the opportunity to observe and compare the overall enhancement from different combinations of enhancement in individual input and output beams. We first confirm PDG's capability of spatially separating…
Surface enhanced Raman scattering (SERS) process results in a tremendous increase of Raman scattering cross section of molecules adsorbed to plasmonic metals and influenced by numerous physico-chemical factors such as geometry and optical properties of the metal surface, orientation of chemisorbed molecules and chemical environment. While SERS holds promise for single molecule sensitivity and optical sensing of DNA sequences, more detailed understanding of the rich physico-chemical interplay between various factors is needed to enhance predictive power of existing and future SERS-based DNA sen…
Surface-enhanced Raman spectroscopy (SERS) allows single-molecule detection due to the strong field localization occurring at sharp bends or kinks of the metal-vacuum interface. An important question concerns the limits of the signal enhancement that can be achieved via a judicious design of the surface. By using a specific example of a technologically realizable nanopatterned surface, we demonstrate that while very high enhancement factors (~10^12) can be found for an ideal surface, these are unlikely to be achieved in laboratory samples, because even a minute, inevitable rounding-off strongl…
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）
The Dipole-Quadrupole theory of Surface Enhanced Hyper Raman Scattering (SEHRS), created by the authors is expounded in details. Peculiarities of the behavior of electromagnetic field on rough metal surfaces are considered. It is demonstrated that there is an enhancement of the dipole and quadrupole light-molecule interaction near the places with a large curvature. The expression for the SEHRS cross-section of symmetrical molecules, which consists of several contributions is obtained. Selection rules for the scattering contributions are obtained and a qualitative classification of the contribu…
We report the observations of spontaneous Raman scattering in silicon photonic crystal waveguides. Continuous-wave measurements of Stokes emission for both wavelength and power dependence is reported in single line-defect waveguides in hexagonal lattice photonic crystal silicon membranes. By utilizing the Bragg gap edge dispersion of the TM-like mode for pump enhancement and the TE-like fundamental mode-onset for Stokes enhancement, the Stokes emission was observed to increase by up to five times in the region of slow group velocity. The results show explicit nonlinear enhancement in a silicon…
Photo-Induced Enhanced Raman Spectroscopy (PIERS) is a new surface enhanced Raman spectroscopy (SERS) modality with an order-of-magnitude Raman signal enhancement of adsorbed analytes over that of typical SERS substrates. Despite the impressive PIERS enhancement factors and explosion in recent demonstrations of its utility, the detailed enhancement mechanism remains undetermined. Using a range of optical and X-ray spectroscopies, supported by density functional theory calculations, we elucidate the chemical and atomic-scale mechanism behind the PIERS enhancement. Stable PIERS substrates with e…
We have fabricated layered nanocomposite consisting of a nanoporous anodic alumina sublayer (AOA), an ultrathin metal-containing polymer Langmuir-Blodgett (LB) film coating AOA, and multi-walled carbon nanotube (MCNT) - bundles which are arranged on the LB-film. MCNTs were preliminarily chemically modified by carboxyl groups and functionalized by stearic acid. We have experimentally observed an enhancement of Raman light scattering on surface plasmons in the LB-monolayers. This enhancement is due to charge and energy transfer. We demonstrate that propidium iodide (PI) fluorescence is quenched …
The interaction between two metallic spheres with radius R with external electromagnetic (EM) field polarized in the symmetric z direction is described. Solutions of Laplace equation with bi-spherical coordinates are developed. Hot spots are obtained under the condition that the shortest distance between the two spheres surfaces is very small relative to their radius. Boundary conditions are applied which assume very large real negative value for the dielectric constant of the metallic spheres which is valid for atoms like that of AG or Au at certain frequencies. Under these conditions the EM …
Hyperspectral stimulated Raman scattering (SRS) microscopy is a label-free technique for biomedical and mineralogical imaging which can suffer from low signal to noise ratios. Here we demonstrate the use of an unsupervised deep learning neural network for rapid and automatic denoising of SRS images: UHRED (Unsupervised Hyperspectral Resolution Enhancement and Denoising). UHRED is capable of one-shot learning; only one hyperspectral image is needed, with no requirements for training on previously labelled datasets or images. Furthermore, by applying a k-means clustering algorithm to the process…
We theoretically investigate the enhancement of surface enhanced Raman spectroscopy (SERS) using hyperbolic stratified nanostructures and compare to metal nanoresonators. The photon Green function of each nanostructure within its environment is first obtained from a semi-analytical modal theory, which is used in a quantum optics formalism of the molecule-nanostructure interaction to model the SERS spectrum. An intuitive methodology is presented for calculating the single molecule enhancement factor (SMEF), which is also able to predict known experimental SERS enhancement factors of an example …
Raman spectroscopy reveals chemically specific information and provides label-free insight into the molecular world. However, the signals are intrinsically weak and call for enhancement techniques. Here, we demonstrate Purcell enhancement of Raman scattering in a tunable high-finesse microcavity, and utilize it for molecular diagnostics by combined Raman and absorption imaging. Studying individual single-wall carbon nanotubes, we identify crucial structural parameters such as nanotube radius, electronic structure and extinction cross-section. We observe a 320-times enhanced Raman scattering sp…
To develop highly sensitive, stable and repeatable surface-enhanced Raman scattering (SERS) substrates is crucial for analytical detection, which is a challenge for traditional metallic structures. Herein, by taking advantage of the high surface activity of 1T' transition metal telluride, we have fabricated high-density gold nanoparticles (AuNPs) that are spontaneously in-situ prepared on the 1T' MoTe2 atomic layers via a facile method, forming a plasmonic-2D material hybrid SERS substrate. This AuNP formation is unique to the 1T' phase, which is repressed in 2H MoTe2 with less surface activit…
Surface-enhanced Raman spectroscopy (SERS) demands reliable, high enhancement substrates in order to be used in different fields of application. Here, we introduce freestanding porous gold membranes (PAuM) as easy to produce, scalable, mechanically stable, and effective SERS substrates. We fabricate large-scale sub-30 thick PAuM, that form freestanding membranes with varying morphologies depending on the nominal gold thickness. These PAuM are mechanically stable for pressures up to $>3$ bar, and exhibit surface-enhanced Raman scattering with local enhancement factors of $10^4$ to $10^5$, which…
Enhancement of optical response with high-index dielectric nanoparticles is attributed to the excitation of their Mie-type magnetic and electric resonances. Here we study Raman scattering from crystalline silicon nanoparticles and reveal that magnetic dipole modes have much stronger effect on the scattering than electric modes of the same order. We demonstrate experimentally a 140-fold enhancement of Raman signal from individual silicon spherical nanoparticles at the magnetic dipole resonance. Our results confirm the importance of the optically-induced magnetic response of subwavelength dielec…
Molecular optomechanics stems from the description of Raman scattering in the presence of an optical resonator using a cavity optomechanics formalism. We extend the molecular optomechanics formalism to the case of hybrid dielectric-plasmonic resonators, with multiple optical resonances and with both free-space and waveguide addressing. We demonstrate how the Raman enhancement is the product of a pump enhancement and a modified LDOS, that simply depend on the complex response functions of the hybrid system. The Fano lineshapes that result from hybridization of a broadband and narrowband modes a…
We study coherent anti-Stokes Raman spectroscopy in air-filled anti-resonance hollow-core photonic crystal fiber, otherwise known as 'revolver' fiber. We compare the vibrational coherent anti-Stokes Raman signal of N$_2$, at 2331 cm$^{-1}$, generated in ambient air (no fiber present), with the one generated in a 2.96 cm of a revolver fiber. We show a 170 times enhancement for the signal produced in the fiber, due to an increased interaction path. Remarkably, the N$_2$ signal obtained in the revolver fiber shows near-zero non-resonant background, due to near-zero overlap between the laser field…
Giant field enhancement and field singularities are a natural consequence of the commonly employed local-response framework. We show that a more general nonlocal treatment of the plasmonic response leads to new and possibly fundamental limitations on field enhancement with important consequences for our understanding of SERS. The intrinsic length scale of the electron gas serves to smear out assumed field singularities, leaving the SERS enhancement factor finite even for geometries with infinitely sharp features. For silver nano-groove structures, mimicked by periodic arrays of half-cylinders …
We couple photoluminescent semiconducting 7-atom wide armchair edge graphene nanoribbons to plasmonic nanoantenna arrays and demonstrate an enhancement of the photoluminescence and Raman scattering intensity of the nanoribbons by more than one order of magnitude. The increase in signal allows us to study Raman spectra with high signal-to-noise ratio. Using plasmonic enhancement we are able to detect the off-resonant Raman signals from the modified radial breathing-like mode (RBLM) due to physisorbed molecules, the 3rd order RBLM, and C-H vibrations. We find excellent agreement between data and…
We investigate for the first time the enhancement of the stimulated Raman scattering in slow-light Silicon-on-Insulator (SOI) photonic crystal line defect waveguides. By applying the Bloch-Floquet formalism to the guided modes in a planar photonic crystal, we develop a formalism that relates the intensity of the down-shifted Stokes signal to the pump intensity and the modal group velocities. The formalism is then applied to two prospective schemes for enhanced stimulated Raman generation in slow-light photonic crystal waveguides. The results demonstrate a maximum factor of 10^4 (66,000) enhanc…
We report plasmon-enhanced Raman scattering in graphene coupled to a single plasmonic hotspot measured as a function of laser energy. The enhancement profiles of the G peak show strong enhancement (up to $10^5$) and narrow resonances (30 meV) that are induced by the localized surface plasmon of a gold nanodimer. We observe the evolution of defect-mode scattering in a defect-free graphene lattice in resonance with the plasmon. We propose a quantum theory of plasmon-enhanced Raman scattering, where the plasmon forms an integral part of the excitation process. Quantum interferences between scatte…
Stimulated Raman spectroscopy has become a powerful tool to study the spatiodynamics of molecular bonds with high sensitivity, resolution and speed. However, sensitivity and speed of state-of-the-art stimulated Raman spectroscopy are currently limited by the shot-noise of the light beam probing the Raman process. Here, we demonstrate an enhancement of the sensitivity of continuous-wave stimulated Raman spectroscopy by reducing the quantum noise of the probing light below the shot-noise limit by means of amplitude squeezed states of light. Probing polymer samples with Raman shifts around 2950 $…
We demonstrate a novel technique of coherent Raman spectroscopy with a femtosecond laser. We apply to a molecular sample a sequence of pairs of ultrashort excitation and probe pulses, with a linearly increasing time delay between the two pulses from one pair to the next. We measure, as a function of the delay, the intensity modulation in the signal resulting from the differential detection of the Stokes and anti-Stokes radiations generated at the sample. The Fourier transform of such time-domain signal reveals the spectrum of the excited vibrational Raman transitions. The experimental proof-of…
We investigate theoretically the optical properties associated to plasmon resonances of metal nanowires with cross section given by low-order Chebyshev nanoparticles (like rounded-tip nanostars or nanoflowers). The impact of the nanoflower shape is analyzed for varying symmetry and deformation parameter through the spectral dependence of resonances, and their corresponding near field distributions. Large field intensity enhancements are obtained at the gaps between petals, apart from the tips themselves, which make these nanostars/nanoflowers specially suitable to host molecules for SERS sensi…
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 achiev…
The conventional explanation of plasmon-enhanced Raman scattering attributes the enhancement to the antenna effect focusing the electromagnetic field into sub-wavelength volumes. Here we introduce a new model that additionally accounts for the dynamical and coherent nature of the plasmon-molecule interaction and thereby reveals an enhancement mechanism not contemplated before: dynamical backaction amplification of molecular vibrations. We first map the problem onto the canonical model of cavity optomechanics, in which the molecular vibration and the plasmon are \textit{parametrically coupled}.…
The sensitivity of classical Raman spectroscopy methods, such as Coherent Anti-Stokes Raman spectroscopy (CARS) or Stimulated Raman spectroscopy (SRS), is ultimately limited by shot-noise from the stimulating fields. We present the complete theoretical analysis of a squeezing-enhanced version of Raman spectroscopy that overcomes the shot-noise limit of sensitivity with enhancement of the Raman signal and inherent background suppression, while remaining fully compatible with standard Raman spectroscopy methods. By incorporating the Raman sample between two phase-sensitive parametric amplifiers …
Surface Enhanced Raman Spectroscopy (SERS) is a well-established technique for enhancing Raman signals. Recently photonic integrated circuits have been used, as an alternative to microscopy based excitation and collection, to probe SERS signals from external metallic nanoparticles. However, in order to develop quantitative on-chip SERS sensors, integration of dedicated nanoplasmonic antennas and waveguides is desirable. Here we bridge this gap by demonstrating for the first time the generation of SERS signals from integrated bowtie nanoantennas, excited and collected by a single mode waveguide…
We demonstrate the stimulated Raman near-field microscopy of few molecules, measured only using near-field optical forces thereby eliminating the need for far-field optical detection. The molecules were excited in the near-field without resonant electronic enhancement. We imaged gold nanoparticles of 30 nm diameter functionalized with a self-assembled monolayer (SAM) of 4-nitrobenzenethiol (4-NBT) molecules. The maximum number of molecules detected by the gold-coated nano-probe at the position of maximum field enhancement could be fewer than 20 molecules. The molecules were imaged by vibrating…
A theoretical framework is presented that permits investigations of the relation between inelastic backscattering from microparticles and bulk samples of Raman-active materials. It is based on the Lorentz reciprocity theorem and no fundamental restrictions concerning the microparticle shape apply. The approach provides a simple and intuitive explanation for the enhancement of the differential backscattering cross-section in particles in comparison to bulk. The enhancement factor for scattering of water droplets in the diameter range from 0 to 60\,\textmu m (vitally important for the \emph{a pr…
Surface enhanced Raman spectroscopy, is a technique of fundamental importance to analytical science and technology where the amplified Raman spectrum of analytes is used for chemical fingerprinting. Here, we showcase an engineered hierarchical substrate in which the plasmonically active regions are restricted to a micron scale, 2D hexagonal pattern. The Raman signal enhancement of any analyte uniformly coating the substrate is consequently bears a high registry with the 2D pattern. This spatially segregated enhancement allows optical imaging of the 2D pattern solely using the Raman scattered p…
Raman intensity of Rhodamine B (RhB) is enhanced by inserting a thin high \k{appa} dielectric layer which reduces the surface plasmon damping at the gold-graphene interface. The results indicate that the Raman intensity increases sharply by plasmonic resonance enhancement while maintaining efficient fluorescence quenching with optimized dielectric layer thickness.
We present a self-consistent quantum optics approach to calculating the surface enhanced Raman spectrum of molecules coupled to arbitrarily shaped plasmonic systems. Our treatment is intuitive to use and provides fresh analytical insight into the physics of the Raman scattering near metallic surfaces and can be applied to a wide range of geometries including resonators, waveguides, as well as hybrid photonic-plasmonic systems. Our general theory demonstrates that the detected Raman spectrum originates from an interplay between nonlinear light generation and propagation. Counter intuitively, at…
We demonstrate gold coated polymer surface enhanced Raman scattering (SERS) substrates with a pair of complementary structures--positive and inverted pyramids array structures fabricated by multiple-step molding and replication process. The uniform SERS enhancement factors over the entire device surfaces were measured as 7.2 X 10^4 for positive pyramids substrate while 1.6 X 10^6 for inverted pyramids substrate with Rhodamine 6G as the target analyte. Based on the optical reflection measurement and FDTD simulation result, the enhancement factor difference is attributed to plasmon resonance mat…
We propose an integrated surface enhanced Raman scattering (SERS) chip based on liquid-core waveguide with total reflection, through which the depression of leaky mode enable a long propagating distance. An Raman enhancement factor for rhodamine 6G of 2.5*105 is obtained, and a excellent repeatability is shown. The peaks in the SERS spectrum of DNA of silkworm clearly illustrate the information of the molecule structure. The integration of the SERS substrate, micro-fluid, and liquid-core waveguide make such a SERS chip attractive for biochemical detection with high performance.
Plasmonic nanostructures enhance nonlinear response, such as surface enhanced Raman scattering (SERS), by localizing the incident field into hot spots. The localized hot spot field can be enhanced even further when linear Fano resonances (FR) take place in a double resonance scheme. However, hot spot enhancement is limited with the modification of the vibrational modes, the break-down of the molecule and the tunnelling regime. Here, we present a method which can circumvent these limitations. Our analytical model and solutions of 3D Maxwell equations show that: enhancement due to the localized …
The low efficiency of Raman spectroscopy can be overcome by placing the active molecules in the vicinity of scatterers, typically rough surfaces or nanostructures with various shapes. This surface-enhanced Raman scattering (SERS) leads to substantial enhancement that depends on the scatterer that is used. In this work, we find fundamental upper bounds on the Raman enhancement for arbitrary-shaped scatterers, depending only on its material constants and the separation distance from the molecule. According to our metric, silver is optimal in visible wavelengths while aluminum is better in the ne…
Coherent Raman scattering spectroscopy is studied purposely, with the Gaussian ultrashort pulses as a hands-on elucidatory extraction tool of the clean coherent Raman resonant spectra from the overall measured data contaminated with the non-resonant four wave mixing background. The integral formulae for both the coherent anti-Stokes and Stokes Raman scattering are given in the semiclassical picture, and the closed-form solutions in terms of a complex error function are obtained. An analytic form of maximum enhancement of pure coherent Raman spectra at threshold time delay depending on bandwidt…
