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 the substrate regardless of molecular orientation. We demonstrate that the plasmonic substrate provides strong coupling with the C=O vibrational stretch of deposited films of PMMA. We also show that the large linewidths of the plasmon resonance allows for simultaneous strong coupling to two, orthogonal water symmetric and asymmetric vibrational modes in a thin film of copper sulfate monohydrate deposited on the substrate surface. A three-coupled-oscillator model is developed to analyze the coupling strength of the plasmon resonance with these two water modes. With precise control over the nanodisk diameter, the plasmon resonance is tuned systematically through the modes, with the coupling strength to both modes varying as a function of the plasmon frequency, and with strong coupling to both modes achieved simultaneously for a range of diameters. This work may aid further studies into manipulation of the ground-state chemical landscape of molecules by perturbing multiple vibrational modes simultaneously and increasing the coupling strength in sub-diffraction limited volumes.
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…
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…
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. Incorpo…
The behavior of Fano resonance and the reversal of near field optical binding force of dimers over different substrates have not been studied so far. In this work, we observe that if the closely located plasmonic cube homodimers over glass or high permittivity dielectric substrate are illuminated with plane wave polarized parallel to dimer axis, no reversal of optical binding force occurs. But if we apply the same set-up over a plasmonic substrate, stable Fano resonance occurs along with the reversal of near field binding force. It is observed that during such Fano resonance stronger coupling …
The plasmonic response of nanoparticles is exploited in many subfields of science and engineering to enhance optical signals associated with probes of nanoscale and subnanoscale entities. We develop a numerical algorithm based on previous theoretical work that addresses the influence of a substrate on the plasmonic response of collections of nanoparticles of spherical shape. Our method is a real space approach within the quasi-static limit that can be applied to a wide range of structures. We illustrate the role of the substrate through numerical calculations that explore single nanospheres an…
In this letter, a plasmonic dark field microscopy taking advantages of the polymer loaded surface plasmon polariton waveguide (PLSPPW) is experimentally demonstrated. The dye molecules (Rhodamine 6G, Rh6G) are doped in the PLSPPW to launch the plasmonic waves or guided waves. Due to the localized property of these waves, the near-field optical energy on the surface of PLSPPW can be scattered into the far-field only in the presence of the objects. The scattering signals then form the dark-field image of the objects. The proposed technique just utilizes a chip-scale integrated plasmonic multilay…
We report systematic studies of plasmonic and photonic guiding modes in large-area chemical-vapor-deposition-grown graphene on nanostructured silicon substrates. Light interaction in graphene with substrate photonic crystals can be classified into four distinct regimes depending on the photonic crystal lattice constant and the various modal wavelengths (i.e. plasmonic, photonic and free-space). By optimizing the design of the substrate, these resonant modes can magnify the graphene absorption in infrared wavelength, for efficient modulators, filters, sensors and photodetectors on silicon photo…
An efficient numerical method based on half-space Green function and spherical harmonics expansion is used to study the light scattering from coupled multiple nanospheres on a substrate. The ellipsometric spectra for various geometries of coupled Au nanospheres are calculated and analyzed to realize the effects of plasmonic coupling of closely-spaced nanospheres. With only a few parameters to describe the distribution of various coupled nanosphere clusters embedded in a random distribution of nanospheres, the calculated ellipsometric spectra can fit the experimental data very well. This illust…
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）
Chemical synthesized silver nanowires have been proved to be the efficient architecture for Plasmonic waveguides, but the high propagation loss prevents their widely applications. Here, we demonstrate that the propagation distance of the plasmons along the Ag NW can be extended if the Ag NW was placed on a dielectric multilayer substrate containing a photonic band gap, but not placed on a commonly used glass substrate. The propagation distance at 630 nm wavelength can reach 16 um even that the Ag NW is as thin as 90 nm in diameter. Experimental and simulation results further show that the pola…
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…
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…
We have developed an efficient numerical method to investigate light scattering from plasmonic nanospheres on a substrate covered by a shell, based on the half-space Greens function approach. We use this method to study optical scattering from DNA molecules attached to metallic nanoparticles on a substrate and compare with experiment. We obtain fairly good agreement between theoretical predictions and the measured ellipsometric spectra. The metallic nanoparticles were used to detect the binding with DNA molecules in a microfluidic setup via spectroscopic ellipsometry (SE), and a detectable cha…
Over the last decade, plasmonic antireflecting nanostructures have been extensively studied to be utilized in various optical and optoelectronic systems such as lenses, solar cells, photodetectors, and others. The growing interest to all-dielectric photonics as an alternative optical technology along with plasmonics motivates us to compare antireflection properties of all-dielectric and plasmonic nanoparticle coatings based on silver and crystalline silicon. Our results of numerical simulations for periodic arrays of spherical nanoparticles on top of amorphous silicon show that both silicon an…
Plasmon-free surface-enhanced Raman scattering (SERS) substrates have attracted tremendous attention for their abundant sources, excellent chemical stability, superior biocompatibility, good signal uniformity, and unique selectivity to target molecules. Recently, researchers have made great progress in fabricating novel plasmon-free SERS substrates and exploring new enhancement strategies to improve their sensitivity. This review summarizes the recent developments of plasmon-free SERS substrates and specially focuses on the enhancement mechanisms and strategies. Furthermore, the promising appl…
Investigating the cellular internalization pathways of single molecules or single nano-objects is important to understanding cell-matter interactions and to applications in drug delivery and discovery. Imaging and tracking the motion of single molecules on cell plasma membrane require high spatial resolution in three dimensions (3D). Fluorescence imaging along the axial dimension with nanometer resolution has been highly challenging but critical to revealing displacements in trans-membrane events. Here, utilizing a plasmonic ruler based on the sensitive distance dependence of near-infrared flu…
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…
Dark plasmonic modes have interesting properties, such as a longer lifetime and a narrower linewidth than their radiative counterpart, as well as little to no radiative losses. However, they have not been extensively studied yet due to their optical inaccessibility. Using electron-energy loss (EEL) and cathodoluminescence (CL) spectroscopy, the dark radial breathing modes (RBMs) in thin, monochrystalline gold nanodisks are systematically investigated in this work. It is found that the RBMs can be detected in a CL set-up despite only collecting the far-field. Their visibility in CL is attribute…
High-quality factor plasmonic devices are crucial components in the fields of nanophotonics, quantum computing and sensing. The majority of these devices are required to be fabricated on non-lattice matched or transparent amorphous substrates. Plasmonic devices quality factor is mainly defined by ohmic losses, scattering losses at grain boundaries, and in-plane plasmonic scattering losses of a metal - substrate system. Here, we demonstrate the deposition technique to e-beam evaporate ultralow-loss silver thin films on transparent lattice-mismatched substrates. The process is based on evolution…
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 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 plasmon resonances (modes) of a metal nanostructure can be defined as a dipole, a quadrupole, or high-order modes depending on the surface charge distribution induced by the incident field. In a non-symmetrical environment or clusters, the modes can hybridize and exhibit different behavior and properties. In this work, we study experimentally and numerically the substrate-induced hybridization of plasmonic modes of a silver nanocylinder. The applications of plasmonic nanoparticles such as refractive index sensing and enhanced spectroscopies often rely on the sustained mode spectral positio…
In this paper, we study a plasmonic horn nanoantenna on a metal-backed substrate. The horn nanoantenna structure consists of a two-wire transmission line (TWTL) flared at the end. We analyze the effect of the substrate thickness on the nanoantenna's radiation pattern, and demonstrate beam steering in a broad range of elevation angles. Furthermore, we analyze the effect of the ground plane on the impedance matching between the antenna and the TWTL, and observe that the ground plane increases the back reflection into the waveguide. To reduce the reflection, we develop a transmission line model t…
Molecular beam epitaxy allows for the monolithic integration of wavelength-flexible epitaxial infrared plasmonic materials with quantum-engineered infrared optoelectronic active regions. We experimentally demonstrate a six-fold enhancement in photoluminescence from ultra-thin (total thickness of 1/32-th wavelength) long wavelength infrared (LWIR) superlattices grown on highly doped semiconductor designer metal virtual substrates when compared to the same superlattice grown on an undoped virtual substrate. Analytical and numerical models of the emission process via a Dyadic Greens function form…
Understanding the interaction between plasmonic nanoparticles and transparent conductive oxides is instrumental to the development of next-generation photovoltaic, opto-electronic and energy-efficient solid-state lighting devices. We investigated the optical response of hybrid media composed of gold nanoparticles deposited on aluminum-doped zinc oxide thin films with varying doping concentration by spectroscopic ellipsometry. The dielectric functions of bare AZO were addressed first, revealing doping-induced effects such as the band-gap shift and the appearance of free carriers. In the hybrid …
The properties of thermal radiation exchange between hot and cold objects can be strongly modified if they interact in the near field where electromagnetic coupling occurs across gaps narrower than the dominant wavelength of thermal radiation. Using a rigorous fluctuational electrodynamics approach, we predict that ultra-thin films of plasmonic materials can be used to dramatically enhance near-field heat transfer. The total spectrally integrated film-to-film heat transfer is over an order of magnitude larger than between the same materials in bulk form and also exceeds the levels achievable w…
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）
We propose a composite layered structure for tunable, low-loss plasmon resonances, which con- sists of a noble-metal thin film coated in graphene and supported on a hexagonal boron nitride (hBN) substrate. We calculate electron energy loss spectra (EELS) for these structures, and nu- merically demonstrate that bulk plasmon losses in noble-metal films can be significantly reduced, and surface coupling enhanced, through the addition of a graphene coating and the wide-bandgap hBN substrate. Silver films with a trilayer graphene coating and hBN substrate demonstrated sur- face plasmon-dominant spe…
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…
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）
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-…
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…
Donut-shaped laser radiation, carrying orbital angular momentum, namely optical vortex, recently was shown to provide vectorial mass transfer, twisting transiently molten material and producing chiral micro-scale structures on surfaces of different bulk materials upon their resolidification. In this paper, we show for the first time that nanosecond laser vortices can produce chiral nanoneedles (nanojets) of variable size on thin films of such plasmonic materials, as silver and gold films, covering thermally insulating substrates. Main geometric parameters of the produced chiral nanojets, such …
Plasmonics enables deep-subwavelength concentration of light and has become important for fundamental studies as well as real-life applications. Two major existing platforms of plasmonics are metallic nanoparticles and metallic films. Metallic nanoparticles allow efficient coupling to far field radiation, yet their synthesis typically leads to poor material quality. Metallic films offer substantially higher quality materials, but their coupling to radiation is typically jeopardized due to the large momentum mismatch with free space. Here, we propose and theoretically investigate optically thin…
Nanotechnology and the consequent emergence of miniaturized devices are driving the need to improve our understanding of the mechanical properties of a myriad of materials. Here we focus on amorphous polymeric materials and introduce a new way to determine the nanoscale mechanical response of polymeric thin films in the GHz range, using ultrafast optical means. Coupling of the films to plasmonic nanoantennas excited at their vibrational eigenfrequencies allows the extraction of the values of the mechanical moduli as well as the estimation of the glass transition temperature via time-domain mea…
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…
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…
We demonstrated a highly sensitive, waferscale, highly uniform plasmonic nanomushroom substrate based on plastic for nakedeye plasmonic colorimetry and surface enhanced Raman spectroscopy (SERS). We gave it the name FlexBrite. The dualmode functionality of FlexBrite allows for label-free qualitative analysis by SERS with an enhancement factor (EF) of 10^8 and labelfree quantitative analysis by naked eye colorimetry with a sensitivity of 611 nm RIU-1. The SERS EF of FlexBrite in the wet state was found to be 4.81 X 10^8, 7 times stronger than in the dry state, making FlexBrite suitable for aque…
For all applications of plasmonics to technology it is required to tailor the resonance to the optical system in question. This chapter gives an understanding of the design considerations for nanoparticles needed to tune the resonance. First the basic concepts of plasmonics are reviewed with a focus on the physics of nanoparticles. An introduction to the finite element method is given with emphasis on the suitability of the method to nanoplasmonic device simulation. The effects of nanoparticle shape on the spectral position and lineshape of the plasmonic resonance are discussed including retar…
Self-organized monocrystalline Au nanoparticles with potential applications in plasmonics are grown in a SrTiO$_3$ matrix by a novel two-step deposition process. The crystalline preferred orientation of these Au nanoparticles is investigated by synchrotron hard x-ray diffraction. Nanoparticles preferentially align with the (111) direction along the substrate normal (001), whereas two in-plane orientations are found with $[110]_{SrTiO_3} \: || \: [110]_{Au}$ and $[100]_{SrTiO_3} \: || \: [110]_{Au}$. Additionally, a smaller diffraction signal from nanoparticles with the (001) direction parallel…
