Vibrational strong coupling is emerging as a promising tool to modify molecular properties, by making use of hybrid light-matter states known as polaritons. Fabry-Perot cavities filled with organic molecules are typically used, and the molecular concentration limits the maximum reachable coupling strength. Developing methods to increase the coupling strength beyond the molecular concentration limit are highly desirable. In this letter, we investigate the effect of adding a gold nanorod array into a cavity containing pure organic molecules, using FT-IR microscopy and numerical modeling. Incorporation of the plasmonic nanorod array, that acts as artificial molecules, leads to an order of magnitude increase in the total coupling strength for the cavity filled with organic molecules. Additionally, we observe a significant narrowing of the plasmon linewidth inside the cavity. We anticipate that these results will be a step forward in exploring vibropolaritonic chemistry and may be used in plasmon based bio-sensors.
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…
Dual-Gradient Plasmonic qBIC Metasurface for Time-Resolved In Situ Optimization of Molecular Vibrational Sensing in Water
Hamburg University of Technology（汉堡工业大学）；Ludwig-Maximilians-University（慕尼黑大学）；Universidade Federal de Pernambuco（伯南布哥联邦大学）；University of Trento（特伦托大学）；Monash University（蒙纳士大学）；Imperial College London（伦敦帝国学院）
Vibrational strong coupling of molecules to optical cavities based on plasmonic resonances has been explored recently, because plasmonic near-fields can provide strong coupling in sub-diffraction limited volumes. Such field localization maximizes coupling strength, which is crucial for modifying the vibrational response of molecules and, thereby, manipulating chemical reactions. Here, we demonstrate an angle-independent plasmonic nanodisk substrate that overcomes limitations of traditional Fabry-Perot optical cavities, because the design can strongly couple with all molecules on the surface of…
Coupling between tuneable broadband modes of an array of plasmonic metamolecules and a vibrational mode of carbonyl bond of poly(methyl methacrylate) is shown experimentally to produce a Fano resonance, which can be tuned in situ by varying the polarization of incident light. The interaction between the plasmon modes and the molecular resonance is investigated using both rigorous electromagnetic calculations and a quantum mechanical model describing the quantum interference between a discrete state and two continua. The predictions of the quantum mechanical model are in good agreement with the…
Infrared spectroscopy is the technique of choice for chemical identification of biomolecules through their vibrational fingerprints. However, infrared light interacts poorly with nanometric size molecules. Here, we exploit the unique electro-optical properties of graphene to demonstrate a high-sensitivity tunable plasmonic biosensor for chemically-specific label-free detection of protein monolayers. The plasmon resonance of nanostructured graphene is dynamically tuned to selectively probe the protein at different frequencies and extract its complex refractive index. Additionally, the extreme s…
Self-assembled Plasmonic Nanoparticle Networks (PNN) composed of chains of 12-nm diameter crystalline gold nanoparticles exhibit a longitudinally coupled plasmon mode cen- tered at 700 nm. We have exploited this longitudinal absorption band to efficiently confine light fields and concentrate heat sources in the close vicinity of these plasmonic chain net- works. The mapping of the two phenomena on the same superstructures was performed by combining two-photon luminescence (TPL) and fluorescence polarization anisotropy (FPA) imaging techniques. Besides the light and heat concentration, we show …
We extend the model of exciton-plasmon materials to include a ro-vibrational structure of molecules using wave-packet propagations on electronic potential energy surfaces. The new model replaces conventional two-level emitters with more complex molecules allowing to examine the influence of alignment and vibrational dynamics on strong coupling with surface plasmon-polaritons. We apply the model to a hybrid system comprising a thin layer of molecules placed on top of a periodic array of slits. Rigorous simulations are performed for two types of molecular systems described by vibrational bound-b…
Benefitting from the excellent characteristics such as low cytotoxicity, functionalization versatility, and tunable fluorescence, nanodiamonds (NDs) have shown enormous application potentials in the biomedical field. Herein, we proposed, for the first time to our best knowledge, to integrate NDs on a plasmonic interface constructed on a side-polished fiber using drop-casting method. The added NDs engineers the plasmonic interface towards improving the sensing field, thus enhancing the sensitivity, which, moreover, is significantly dependent on the number of drop-casting cycles (DCs) and the us…
Recent developments in surface-enhanced Raman scattering (SERS) enable observation of single-bond vibrations in real-time at room temperature. By contrast, mid-infrared (MIR) vibrational spectroscopy is limited to inefficient slow detection. Here we develop a new method for MIR sensing using SERS. This method utilizes nanoparticle-on-foil (NPoF) nanocavities supporting both visible and MIR plasmonic hotspots in the same nano-gap formed by a monolayer of molecules. Molecular SERS signals from individual NPoF nanocavities are modulated in the presence of MIR photons. The strength of this modulat…
Single-molecule approaches to biology offer a powerful new vision to elucidate the mechanisms that underpin the functioning of living cells. However, conventional optical single molecule spectroscopy techniques such as Förster fluorescence resonance energy transfer (FRET) or fluorescence correlation spectroscopy (FCS) are limited by diffraction to the nanomolar concentration range, far below the physiological micromolar concentration range where most biological reaction occur. To breach the diffraction limit, zero mode waveguides and plasmonic antennas exploit the surface plasmon resonances to…
Single molecule detection provides detailed information about molecular structures and functions, but it generally requires the presence of a fluorescent marker which can interfere with the activity of the target molecule or complicate the sample production. Detecting a single protein with its natural UV autofluorescence is an attractive approach to avoid all the issues related to fluorescence labelling. However, the UV autofluorescence signal from a single protein is generally extremely weak. Here, we use aluminum plasmonics to enhance the tryptophan autofluorescence emission of single protei…
Enhanced light-matter interactions are the basis of surface enhanced infrared absorption (SEIRA) spectroscopy, and conventionally rely on plasmonic materials and their capability to focus light to nanoscale spot sizes. Phonon polariton nanoresonators made of polar crystals could represent an interesting alternative, since they exhibit large quality factors, which go far beyond those of their plasmonic counterparts. The recent emergence of van der Waals crystals enables the fabrication of high-quality nanophotonic resonators based on phonon polaritons, as reported for the prototypical infrared-…
We present a computational study of terahertz optical properties of a grating-coupled plasmonic structure based on micrometer-thin InSb layers. We find two strong absorption resonances that we interpret as standing surface plasmon modes and investigate their dispersion relations, dependence on InSb thickness, and the spatial distribution of the electric field. The observed surface plasmon modes are well described by a simple theory of the air/InSb/air trilayer. The plasmonic response of the grating/InSb structure is highly sensitive to the dielectric environment and the presence of an analyte …
The plasmonic amplification of non-linear vibrational sum frequency spectroscopy (SFG) at the surfaces of gold nanoparticles is systematically investigated by tuning the incident visible wavelength. The SFG spectra of dodecanethiol-coated gold nanoparticles chemically deposited on silicon are recorded for twenty visible wavelengths. The vibrational intensities of thiol methyl stretches extracted from the experimental measurements vary with the visible color of the SFG process and show amplification by coupling to plasmonics. Since the enhancement is maximal in the orange-red region rather than…
Continuous-wave, high-resolution, ultra-broadband mid-infrared nonlinear spectroscopy with tunable plasmonic nanocavities
Institute of Physics, Ecole Polytechnique Fédérale de Lausanne (EPFL)（洛桑联邦理工学院物理研究所）；State Key Laboratory of Precision Spectroscopy, East China Normal University（华东师范大学精密光谱科学国家重点实验室）
Surface plasmon polaritons enable light concentration within subwavelength regions, opening thereby new avenues for miniaturizing the device and strengthening light-matter interactions. Here we realize effective electro-optic modulation in low-loss plasmonic waveguides with the aid of graphene, and the devices are fully integrated in the silicon-on-insulator platform. By advantageously exploiting low-loss plasmonic slot-waveguide modes, which weakly leak into a substrate while feature strong fields within the two-layer-graphene covered slots in metal, we successfully achieve a tunability of 0.…
We consider a periodically gated two-dimensional electron system, with a central gate finger biased independently creating a tunable plasmonic cavity in a planar plasmonic crystal. We demonstrate that the plasmons resonantly excited in the periodic plasmonic lattice by incident terahertz radiation can strongly pump the cavity plasmon modes leading to a deep sub-wavelength concentration of terahertz energy with giant electric field enhancement factor up to 10000.
We present a novel approach for achieving tightly concentrated optical field by a hybrid photonic-plasmonic device in an integrated platform, which is a triangle-shaped metal taper mounted on top of a dielectric waveguide. This device, which we call a plasmomic light concentrator (PLC), can achieve side-coupling of light energy from the dielectric waveguide to the plasmonic region and light focusing into the apex of the metal taper(at the scale ~10nm) at the same time. For demonstration, we numerically investigate a PLC, which is a metal (Au) taper on a dielectric (Si3N4) waveguide at working …
Purely organic materials with negative and near-zero dielectric permittivity can be easily fabricated. Here we develop a theory of nonlinear non-steady-state organic plasmonics with strong laser pulses. The bistability response of the electron-vibrational model of organic materials in the condensed phase has been demonstrated. Non-steady-state organic plasmonics enable us to obtain near-zero dielectric permittivity during a short time. We have proposed to use non-steady-state organic plasmonics for the enhancement of intersite dipolar energy-transfer interaction in the quantum dot wire that in…
Infrared spectroscopy, especially for molecular vibrations in the fingerprint region between 600 and 1500 cm-1, is a powerful characterization method for bulk materials. However, molecular fingerprinting at the nanoscale level still remains a significant challenge, due to weak light-matter interaction between micron-wavelengthed infrared light and nano-sized molecules. Here, we demonstrate molecular fingerprinting at the nanoscale level using our specially designed graphene plasmonic structure on CaF2 nanofilm. This structure not only avoids the plasmon-phonon hybridization, but also provides …
Unidirectional wave propagation in nonreciprocal structures enables exciting opportunities to control and enhance wave-matter interactions in extreme ways. Within this context, here we investigate the possibility of using terminated unidirectional plasmonic waveguides to enhance typically weak nonlinear effects by orders of magnitude. We theoretically demonstrate remarkable levels of electric field enhancement and confinement (field hot-spots) when the unidirectional waveguiding structure is terminated with a suitable boundary that fully stops the one-way mode. Such a large field enhancement, …
Seeing inside a Plasmonic Nanogap: Few-molecule Orientation and Preferential Adsorption
Ecole Polytechnique Fédérale de Lausanne (EPFL)（洛桑联邦理工学院）；Center for Quantum Science and Engineering, Ecole Polytechnique Fédérale de Lausanne (EPFL)（洛桑联邦理工学院量子科学与工程中心）
Plasmon-enhanced Raman scattering can push single-molecule vibrational spectroscopy beyond a regime addressable by classical electrodynamics. We employ a quantum electrodynamics (QED) description of the coherent interaction of plasmons and molecular vibrations that reveal the emergence of nonlinearities in the inelastic response of the system. For realistic situations, we predict the onset of \textit{phonon-stimulated Raman scattering} and an counter-intuitive dependence of the anti-Stokes emission on the frequency of excitation. We further show that this novel QED framework opens a venue to a…
We present a new method for measuring low concentrations and simultaneously small volumes of fluorescent molecules based on the use of the Ebbesen effect of the extraordinary transmission (EOT) of light through an array of nano-holes. In the method the EOT effect is realized at the fluorescence wavelength of the detected molecules with a low transmission of light at the absorption wavelength. The approach allows realizing high level of the sensor sensitivity due to suppression of the inevitable parasitic luminescence of the sensor substrate. The method was demonstrated by detecting an ultra lo…
Tip-Enhanced Vibrational Ladder Climbing in Surface Molecular System
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（综合研究大学院大学）
We propose a novel method for ultra-sensitive infrared (IR) vibrational spectroscopy of molecules with nanoscale footprints by combining the tip enhancement of the scattering-type scanning near-field optical microscope (s-SNOM) and the plasmon enhancement of the breathing-mode (BM) plasmon resonances of graphene nanodisks (GNDs). To demonstrate that, we developed a quantitative model that is capable of computing accurately the s-SNOM signals of nanoscale samples. With our modeling, we show that the s-SNOM tip can effectively excite gate-tunable BM plasmonic resonances in GNDs with strong field…
We propose a novel deterministic protocol, based on continuous light flows, that enables us to control the concentration of light in generic plasmonic nanostructures. Based on an exact inversion of the response tensor of the nanosystem, the so-called Deterministic Optical Inversion (DOPTI) protocol provides a physical solution for the incident field leading to a desired near field pattern, expressed in the form of a coherent superposition of high order beams. We demonstrate the high degree of control achieved on complex plasmonic architectures and quantify its efficiency and accuracy.
Plasmonic metamaterials can be used to enhance mid-infrared sensors and detectors for immunosensing applications. The major challenge is to integrate these technologies in low-cost, compact, and promising platforms. In this study, as an emerging approach, we utilized toroidal resonant plasmonic metasurfaces to develop an ultrasensitive label-free analytical platform for the detection of specific antibiotics in the mid-IR regime. Taking advantage of unique sensitivity of robustly squeezed electromagnetic fields in toroidal meta-atoms, we validated that our proposed technique based on toroidal m…
The absorptance of p-polarized light in superconducting-nanowire single-photon detectors (SNSPDs) was improved by integrating (1) ~quarter-wavelength nano-optical cavity closed by a gold reflector (OC-SNSPD), (2) nano-cavity-array closed by vertical and horizontal gold segments (NCAI-SNSPD), and (3) nano-cavity-deflector-array consisting of longer vertical gold segments (NCDAI-SNSPD) into short- (p-) and long- (3p-) periodic niobium-nitride (NbN) stripe-patterns. In OC-SNSPDs the highest absorptance is observable at perpendicular incidence onto NbN stripes in P-orientation due to E-field conce…
We compare the optical response of isolated nanowires, double-wire systems, and Pi-structures, and show that their radiation is well described in terms of their electric and magnetic dipole moments. We also show that both dielectric permittivity and magnetic permeability can be negative at optical and near infrared frequencies, and demonstrate the connection between the geometry of the system and its resonance characteristics. We conclude that plasmonic nanowires can be employed for developing novel negative-index materials. Finally, we demonstrate that it is possible to construct a nanowire-b…
The strong spatial confinement of a nanocavity plasmonic field has made it possible to visualize the inner structure of a single molecule and even to distinguish its vibrational modes in real space. With such ever-improved spatial resolution, it is anticipated that full vibrational imaging of a molecule could be achieved to reveal molecular structural details. Here we demonstrate full Raman images of individual vibrational modes on the Ångström level for a single Mg-porphine molecule, revealing distinct characteristics of each vibrational mode in real space. Furthermore, by exploiting the unde…
Single molecule detection has revolutionised the fields of chemistry and biology by offering powerful ways to study individual molecules under different scenarios. Nanophotonic structures, including plasmonic antennas, significantly overcome the concentration limit at which single molecule events can be observed, enabling their detection at concentrations that are relevant to biological and chemical processes. Although antennas can be fabricated in large arrays, probing dynamic events requires high temporal resolution, which is best achieved by serial antenna interrogation. Unfortunately, this…
Surface-Enhanced Raman Scattering (SERS) allows for detection and identification of molecular vibrational fingerprints in minute sample quantities. The SERS process can be also exploited for optical manipulation of molecular vibrations. We present a quantum description of Surface-Enhanced Resonant Raman scattering (SERRS), in analogy to hybrid cavity optomechanics, and compare the resonant situation with the off-resonant SERS. Our model predicts the existence of a regime of coherent interaction between electronic and vibrational degrees of freedom of a molecule, mediated by a plasmonic nanocav…
Anisotropic nanostructured porous Pd films are fabricated using oblique angle deposition in vacuum on a glass substrate. They display a dichroic response, due to localised surface plasmon resonances (LSPR) within the nanoparticles forming the film, dependent on the incident light polarisation. Ultrasensitive hydrogen sensing is reached by using these films in conjunction with a differential optical technique derived from the reflectance anisotropy spectroscopy. The evolution of the samples optical responses is monitored during the formation of Pd hydride in both the dilute alpha-phase and the …
Nanomaterials capable of confining light are desirable for enhancing spectroscopies such as Raman scattering, infrared absorption, and nonlinear optical processes. Plasmonic superlattices have shown the ability to host collective resonances in the mid-infrared, but require stringent fabrication processes to create well-ordered structures. Here, we demonstrate how short-range-ordered Au nanoparticle multilayers on a mirror, self-assembled by a sub-nm molecular spacer, support collective plasmon-polariton resonances in the visible and infrared, continuously tunable beyond 11 $μ$m by simply varyi…
An efficient parallelization approach to simulate optical properties of ensembles of quantum emitters in realistic electromagnetic environments is considered. It relies on balancing computing load of utilized processors and is built into three-dimensional domain decomposition methodology implemented for numerical integration of the Maxwell equations. The approach employed enables directly accessing dynamics of collective effects as the number of molecules in simulations can be drastically increased. Numerical experiments measuring speedup factors demonstrate the efficiency of the proposed meth…
Photonic sensors have many applications in a range of physical settings, from measuring mechanical pressure in manufacturing to detecting protein concentration in biomedical samples. A variety of sensing approaches exist, and plasmonic systems in particular have received much attention due to their ability to confine light below the diffraction limit, greatly enhancing sensitivity. Recently, quantum techniques have been identified that can outperform classical sensing methods and achieve sensitivity below the so-called shot-noise limit. Despite this significant potential, the use of definite p…
Light concentration with strong temporal and spatial confinement is crucial for tailoring light-matter interaction. Electromagnetic cavity modes in photonic and plasmonic resonators provide platforms for optical field localization. Here, we propose a concept of quasi-bound states in the continuum gap cavity and reveal that ultra spatiotemporal confinements in free-space can be realized in a dielectric nanocavity metasurface. By introducing an asymmetric air slot in a nanodisk resonator, an ultra-high quality factor $\rm Q \sim 10^6$, accompanying an ultra-small effective mode volume, $\rm V_m …
An active plasmonic switch based on single- and few-layer doped graphene ribbon array operating in the mid-infrared spectrum is investigated with theoretical and numerical calculations. It is shown that significant resonance wavelength shifts and modulation depths can be achieved with a slight variation of the doping concentration of the graphene ribbon. The few-layer graphene ribbon array device outperforms the single-layer one in terms of the achievable modulation depth. Our simulations reveal that, by modulating the Fermi-energy level between 0.2 eV and 0.25 eV, a four-layer graphene ribbon…
Plasmon-polaritons are among the most promising candidates for next generation optical sensors due to their ability to support extremely confined electromagnetic fields and empower strong coupling of light and matter. Here we propose quantum plasmonic immunoassay sensing as an innovative scheme, which embeds immunoassay sensing with recently demonstrated room temperature strong coupling in nanoplasmonic cavities. In our protocol, the antibody-antigen-antibody complex is chemically linked with a quantum emitter label. Placing the quantum-emitter enhanced antibody-antigen-antibody complexes insi…
Detection of enantiomers is a challenging problem in drug development as well as environmental and food quality monitoring where traditional optical detection methods suffer from low signals and sensitivity. Application of surface enhanced Raman scattering (SERS) for enantiomeric discrimination is a powerful approach for the analysis of optically active small organic or large biomolecules. In this work, for enantio-selective sensing we proposed the coupling of disposable chiral plasmonic shurikens supporting the chiral near-field distribution with SERS active silver nanoclusters. As a result o…
Strong coupling between light and matter is the foundation of promising quantum photonic devices such as deterministic single photon sources, single atom lasers and photonic quantum gates, which consist of an atom and a photonic cavity. Unlike atom-based systems, a strong coupling unit based on an emitter-plasmonic nanocavity system has the potential to bring these devices to the microchip scale at ambient conditions. However, efficiently and precisely positioning a single or a few emitters into a plasmonic nanocavity is challenging. In addition, placing a strong coupling unit on a designated …
