Efficient Extraction of Fluorescence Emission Utilizing Multiple Surface Plasmon Modes from Gold Wire Gratings

We demonstrate directional enhanced fluorescence emission from fluorophores located above gold wire gratings. In contrast to previous studies on corrugated films, efficient coupling was recorded for multiple plasmon modes associated with both the active and substrate side of the wires. This difference is likely due to the subtle differences in how light interacts with corrugated films versus metal films with periodic subwavelength slots. For corrugated films, coupling between modes on opposite sides of the grating are out of phase, and therefore plasmon modes on the opposite side of the grating are only weakly excited. For wire gratings, transmission and reflection features have been modeled well with a dynamical diffraction model that includes surface plasmons, which allows for efficient coupling to surface plasmon modes on both sides of the grating. We also compared the two mechanisms for fluorescent enhancement, namely the intense electromagnetic field associated with surface plasmons and excited fluorophores radiating via surface plasmon modes. We found the latter mechanism clearly dominant.     

A disposable polymer sensor chip combined with micro-fluidics and surface plasmon read-out

This paper describes a new type of disposable polymeric sensor chip based on the grating coupling of surface plasmon modes combined with a micro-fluidic channel system. A specifically designed silicon stamp with nano-structure (grating) on the micro-structures (micro-channel) was fabricated by combining a holographic method and photolithography. By using such a stamp the micro-channels, the grating coupler and the gold which was first thermally evaporated onto the stamp were transferred to the polymeric substrate successfully in one step. It is demonstrated that the grating profile in the micro-channels allowed a very efficient coupling of the laser light to the surface plasmons propagating at the bottom of the micro-channels. The transferred gold exhibits properties of a freshly cleaned surface, and the self-assembly of a functional thiol derivative (mercapto-PEG) onto the sensor chip can be monitored by surface plasmon spectroscopy. The results obtained in this sensor chip show no difference from those obtained on a regular grating-coupled SPR sensor chip.     

Narrowband Light Total Antireflection and Absorption in Metal Film–Array Structures by Plasmonic Near-Field Coupling

We study the cooperative effects between plasmon gap modes and optical cavity modes of a novel triple-layer structure consisting of double continuous gold films separated by a gold nanosphere array. Narrowband near-perfect antireflection of optical field is achieved for the first time due to the strong near-field light–matter interaction within the deep sub-wavelength gaps between adjacent nanospheres combined with the spatial field confinement effects of the optical cavity built by the double gold films. The coexistence cooperation of near-field dipole plasmon resonances and spatial optical field confinement presents more efficient light modification than that of the individual subsystem and may open a new approach to manage light flow. By varying the period of nanosphere array, the diameter of nanospheres, and the distance between the array and the film, optical behaviors of the proposed structure can be tuned in a wide range. High environmental sensitivity and large figure of merit factor are obtained using this structure as the detecting substrate. Furthermore, ultra-compact structure and high conduction suggest the proposed structure being a good candidate for potential applications in highly integrated optoelectronic devices, such as plasmonic filters and sensors.     

Experimental Study on Localized Surface Plasmon Mode Hybridization in the Near and Mid Infrared

We investigate plasmon excitations within a regular grating of double-layered gold/insulator nanoparticles in the infrared and visible spectral region. Provided a flat gold film as substrate, strong coupling between the localized surface plasmon modes and their image-like excitations in the metal is observed. The interaction results in a strong red shift of the plasmon mode as well as the splitting of the modes into levels of different angular momenta, often referred to as plasmon hybridization. The diameters of the nanoparticles are designed in a way that the splitting of the resonances occurs in the spectral region between 0.1 and 1 eV, thus being accessible using an infrared microscope. Moreover, we investigated the infrared absorption signal of gratings that contain two differently sized nanoparticles. The interaction between two autonomous localized surface plasmon excitations is investigated by analyzing their crossing behavior. In contrast to the interaction between localized surface plasmons and propagating plasmon excitations which results in pronounced anticrossing, the presented structures show no interaction between two autonomous localized surface plasmons. Finally, plasmon excitations of the nanostructured surfaces in the visible spectral region are demonstrated through photographs acquired at three different illumination angles. The change in color of the gratings demonstrates the complex interaction between propagating and localized surface plasmon modes.     

Surface Plasmon Polariton Excitation in Metallic Layer Via Surface Relief Gratings in Photoactive Polymer Studied by the Finite-Difference Time-Domain Method

We performed numerical investigations of surface plasmon excitation and propagation in structures made of a photochromic polymer layer deposited over a metal surface using the finite-difference time-domain method. We investigated the process of light coupling into surface plasmon polariton excitation using surface relief gratings formed on the top of a polymer layer and compared it with the coupling via rectangular ridges grating made directly in the metal layer. We also performed preliminary studies on the influence of refractive index change of photochromic polymer on surface plasmon polariton propagation conditions.     

A molecular ruler based on plasmon coupling of single gold and silver nanoparticles

Forster Resonance Energy Transfer has served as a molecular ruler that reports conformational changes and intramolecular distances of single biomolecules. However, such rulers suffer from low and fluctuating signal intensities, limited observation time due to photobleaching, and an upper distance limit of approximately 10 nm. Noble metal nanoparticles have plasmon resonances in the visible range and do not blink or bleach. They have been employed as alternative probes to overcome the limitations of organic fluorophores, and the coupling of plasmons in nearby particles has been exploited to detect particle aggregation by a distinct color change in bulk experiments. Here we demonstrate that plasmon coupling can be used to monitor distances between single pairs of gold and silver nanoparticles. We followed the directed assembly of gold and silver nanoparticle dimers in real time and studied the kinetics of single DNA hybridization events. These "plasmon rulers" allowed us to continuously monitor separations of up to 70 nm for >3,000 s.     

Tuning the Propagation Constant by the Anticrossing Bandgap Prism Coupling Technique

A novel plasmonic structure based on an anticrossing bandgap prism coupling technique is proposed. The study has been carried out using photonic crystals based on diffraction gratings (bounded by dielectrics with identical dielectric functions) together with a high refractive index prism to couple the long-range surface plasmon polaritons to photons. We analyse the structure and demonstrate the ability for tuning the propagation constants of plasmon modes by changing the thickness of the gold grating. The comparison to non-bandgap techniques is studied, and the influence of the plasmonic configuration on the plasmon propagation constant is discussed as well. Experimental measurements were also carried out to confirm the validity of our model.     

Near-Field Imaging of Surface Plasmon Polaritons Excited by Chains of Gold Nanodiscs

We present a study of the near-field pattern created by chains of gold nanodiscs situated on a gold thin film and illuminated at oblique incidence. Each disc generates surface plasmon polaritons that propagate on the gold surface. The created waves interfere between them and with the illuminating beam. We observed that when the discs are separated by a distance smaller than the half wavelength, the chain behaves like a continuous ridge. When the discs separation increases, a complex periodic pattern appears and extends up to several wavelengths from the chain. For some specific separation distances, a directional emission of surface plasmon is also observed. The experimental results are in good agreement with numerical simulations performed by considering each disk as an independent dipole-like surface plasmon source.     

Design Analysis of Refractive Index Sensor with High Quality Factor Using Au-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Grating on Aluminum

We propose a surface plasmon resonance (SPR)-based refractive index sensor using gold-alumina grating over aluminum film for biosensing. Conventional SPR sensor based on gold grating exhibits broader SPR dips whereas that based on aluminum grating exhibits narrow reflection dip. A narrow reflection dip is desirable as it provides good resolution and improves the accuracy of measurement. Aluminum is less stable and generally is not preferred for an SPR-based sensor. It is more prone to being oxidized, which reduces the sensitivity and increases the width of the reflection dip of the sensor. While gold cannot provide narrow SPR reflection dips, but is used as an SPR active metal due to its more chemical stability. In order to improve the accuracy of gold grating-based sensor while taking care of oxidation problem of aluminum, in this paper, we propose a gold grating over aluminum film for SPR-based sensor and show that this configuration improves the sensitivity and the detection accuracy of the conventional sensor. Moreover, the oxidation problem is reduced to some extent as a part of aluminum is covered with gold. In order to completely avoid the oxidation of aluminum, we further propose to cover the exposed part of the aluminum with alumina and show that this configuration further improves the accuracy by reducing the width of the SPR reflection dip without affecting the sensitivity significantly. Numerical simulations show that sensitivity of proposed sensor is 270.33°/RIU with quality factor of more than 267.65 RIU^?1.     

Nanogold-plasmon-resonance-based glucose sensing

Noble metal nanoparticles are well known for their strong interactions with light through the resonant excitations of the collective oscillations of the conduction electrons on the particles, the so-called surface plasmon resonances. The close proximity of two nanoparticles is known to result in a red-shifted resonance wavelength peak, due to near-field coupling. We have subsequently employed this phenomenon and developed a new approach to glucose sensing, which is based on the aggregation and disassociation of 20-nm gold particles and the changes in plasmon absorption induced by the presence of glucose. High-molecular-weight dextran-coated nanoparticles are aggregated with concanavalin A (Con A), which results in a significant shift and broadening of the gold plasmon absorption. The addition of glucose competitively binds to Con A, reducing gold nanoparticle aggregation and therefore the plasmon absorption when monitored at a near-red arbitrary wavelength. We have optimized our plasmonic-type glucose nanosensors with regard to particle stability, pH effects, the dynamic range for glucose sensing, and the observation wavelength to be compatible with clinical glucose requirements and measurements. In addition, by modifying the amount of dextran or Con A used in nanoparticle fabrication, we can to some extent tune the glucose response range, which means that a single sensing platform could potentially be used to monitor microM --> mM glucose levels in many physiological fluids, such as tears, blood, and urine, where the glucose concentrations are significantly different.     

Investigation of Plasmonic Resonances in Mismatched Gold Nanocone Dimers

The plasmonic properties of two closely adjacent gold nanocones of different sizes have been investigated. The plasmon modes of the first nanocone couple with the plasmon modes of the second one due to which a broad peak and a narrow peak emerges in the extinction spectrum, which can be categorized as bright and dark plasmon modes. The destructive interference of the two modes results in a sharp Fano dip in the spectrum. Several configurations of the conical nanodimer have been considered, which suggests that the plasmon coupling in the nanocone dimer is not only dependent on the interparticle distance and size of the nanoparticles but also on their spatial arrangement. The localized high near-field energy in the nanodimer can be used for surface-enhanced Raman spectroscopy applications.     

In Situ Monitoring of the 2D Aggregation Process of Thiol-Coated Gold Nanoparticles Using Interparticle Plasmon Coupling

Near-field plasmon coupling between neighboring gold nanoparticles, measured by polarized optical waveguide lightmode spectroscopy, is employed to study the surface self-assembly of alcanethiol-capped gold nanoparticles during solvent evaporation. The waveguide used is a monomode optical fiber half-coupler. The sample is deposited on the surface of the waveguide and absorption spectra are continuously collected during the solvent evaporation process with a temporal resolution of 0.2 s. The absorption spectra show a progressive red shift of the plasmon peak caused by increasing interparticle near-field coupling. This shift can be used to determine the distance between particles by comparison to theoretical values calculated using the discrete dipoles approximation. The technique is demonstrated for the assembly of 10 nm gold particles capped with thiol ligands of two different lengths. Interestingly, in the case of dodecanethiol-capped particles, the extinction spectrum not only shifts to longer wavelengths, but also changes in shape during the drying process. About half a second before the solvent completely evaporates, the spectrum broadens as a second component appears. This feature is tentatively attributed to the formation of a significant population of particle clusters as a result of incomplete screening of van der Waals attractions by the shorter ligand.     

Fabrication and characterization of patterned immobilization of quantum dots on metallic nano-gratings

Surfaces featuring nano-structures and biochemical patterns are increasingly developed as novel and superior substrates for biosensors and assays. Metallic periodic nano-structures have been studied for their unique optical properties and in particular their ability to support surface plasmon waves. Here we present a new nano-structuring approach based on gentle metal lift-off process coupled with self-assembled surface chemistry for the fabrication of a zeroth-order 400nm period metallic grating with differentiated surface chemistries on the mesas and troughs. The approach, using terminated self-assembled monolayers, creates versatile functionalized substrates allowing the precise deposition of complex biomolecular structures. We use this technique to perform the guided deposition of a three-dimensional polyelectrolyte multilayer structure and the patterned adsorption of quantum dots. Finally, we demonstrate that scanning near-field optical microscopy, used in conjuncture with atomic force microscopy and scanning electron microscopy, is an ideal tool for the characterization of this nano-structured surface as it provides a complete chemical, topographical and optical image of the surface. This ability to pattern and locally measure the surface properties is likely to have an important impact on the design of novel and optimized biointerfaces and transducers for biosensors.     

One Dimensional Plasmonic Grating: High Sensitive Biosensor

We report a simple 1D grating device fabrication on ～50 nm gold (Au) film deposited on glass, which is employed as a high performance refractive index (RI) sensor by exploiting the surface plasmon polaritons (SPP) excited by the grating device along the Au/analyte interface. A finite element analysis (FEA) method is employed to maximize the sensitivity of the sensor for a fixed period and thickness of a gold film and its close correspondence with experiment has given the insight for high sensitivity and enhanced transmission. Significantly, in the context of economic design and performance, it is shown that an optimally designed and fabricated 1D grating can be as sensitive as 524 nm/RIU (linearity RI?=?1.33303 to 1.47399), which is remarkably higher than existing reports operating in a similar wavelength region.     

Grating-based surface plasmon resonance detection of core-shell nanoparticle mediated DNA hybridization

In this report, we have investigated enhanced surface plasmon resonance (SPR) detection of DNA hybridization using gold core - silica shell nanoparticles in localized plasmonic fields. The plasmonic fields were localized by periodic linear gratings. Experimental results measured for hybridization of 24-mer single-stranded DNA oligomers suggest that core-shell nanoparticles (CSNPs) on gratings of 400 nm period provide enhanced optical signatures by 36 times over conventional thin film-based SPR detection. CSNP-mediated DNA hybridization produced 3 times larger angular shift compared to gold nanoparticles of the same core size. We have also analyzed the effect of structural variation. The enhancement using CSNPs was associated with increased surface area and index contrast that is combined by improved plasmon coupling with localized fields on gratings. The combined approach for conjugated measurement of a biomolecular interaction on grating structures is expected to lower the limit of detection to the order of a few tens of fg/mm(2).     

Features of the Secondary Emission Enhancement Near Plasmonic Gold Film

Plasmonic gold films (PGF) prepared by vacuum deposition of gold onto quartz slides possess unique property to enhance electromagnetic signal in the near field. Spectral tuning of PGF’s plasmon band to resonance with the electronic spectra of adsorbed molecules provides selective enhancement of fluorescence or surface-enhanced Raman scattering in the far field. Plasmon-enhanced fluorescence (PEF) of mitoxantrone (mitox) as a function of the distance between gold surface and adsorbed molecules for different polarization and incidence angle of exciting light is analyzed in this work. Spectrophotometric data reveal that probability of localized plasmon excitation in gold grains increases with growth of incidence angle for s-polarized and decrease for p-polarized excitation. This fact correlates well with oblate shape of gold particles detected by Atomic force microscope. However, the fluorescence intensity of dyes deposited at fixed distance from gold surface increase with angle of incidence of p-polarized light more noticeably than for s-polarized one. Nevertheless, the behavior of mitox PEF signal upon p-polarized laser excitation and different angle of incidence are similar in appearance to such phenomenon as selective photoelectric effect. According to this observation, the near-field interactions between plasmons and molecule as possible mechanism of PEF is discussed.     

Optical Near-Field Enhancement with Graphene Bowtie Antennas

In this paper, the optical near-field enhancement of graphene bowtie antennas is numerically investigated at terahertz frequencies using boundary element method. The enhanced field intensity at the gap region is a result of the mutual coupling between two triangular elements upon the excitation of graphene plasmons. Firstly, wide plasmon frequency tunability is demonstrated by changing the chemical potential of graphene without the need to alter the antenna geometry. Secondly, by varying the tip angle and radius of curvature of the graphene antennas, the field intensity enhancement at the gap center of the two-element antennas is systematically studied. It is found that graphene bowtie antennas with two round-cornered equilateral triangles have superior performance to other two-element antennas, such as ribbon pair, sharp-cornered bowtie, and disk pair antennas. Last but not least, by applying a moderate chemical potential of 0.4 eV to graphene bowtie antennas, we found that the field intensity enhancement at gap center is about 220 times as much as using gold of comparable sizes. In short, graphene bowtie antennas of rounded corners give rise to considerable near-field enhancement and are promising for a wide range of applications such as molecular sensing at terahertz frequencies.

     

Application of surface plasmon coupled emission to study of muscle

Muscle contraction results from interactions between actin and myosin cross-bridges. Dynamics of this interaction may be quite different in contracting muscle than in vitro because of the molecular crowding. In addition, each cross-bridge of contracting muscle is in a different stage of its mechanochemical cycle, and so temporal measurements are time averages. To avoid complications related to crowding and averaging, it is necessary to follow time behavior of a single cross-bridge in muscle. To be able to do so, it is necessary to collect data from an extremely small volume (an attoliter, 10(-18) liter). We report here on a novel microscopic application of surface plasmon-coupled emission (SPCE), which provides such a volume in a live sample. Muscle is fluorescently labeled and placed on a coverslip coated with a thin layer of noble metal. The laser beam is incident at a surface plasmon resonance (SPR) angle, at which it penetrates the metal layer and illuminates muscle by evanescent wave. The volume from which fluorescence emanates is a product of two near-field factors: the depth of evanescent wave excitation and a distance-dependent coupling of excited fluorophores to the surface plasmons. The fluorescence is quenched at the metal interface (up to approximately 10 nm), which further limits the thickness of the fluorescent volume to approximately 50 nm. The fluorescence is detected through a confocal aperture, which limits the lateral dimensions of the detection volume to approximately 200 nm. The resulting volume is approximately 2 x 10(-18) liter. The method is particularly sensitive to rotational motions because of the strong dependence of the plasmon coupling on the orientation of excited transition dipole. We show that by using a high-numerical-aperture objective (1.65) and high-refractive-index coverslips coated with gold, it is possible to follow rotational motion of 12 actin molecules in muscle with millisecond time resolution.     

Transmission Surface Plasmon Resonance Signal Enhancement via Growth of Gold Nanoparticles on a Gold Grating Surface

We developed a novel technique for increasing the sensitivity of transmission surface plasmon resonance (T-SPR) signals. T-SPR spectroscopy was performed by irradiating, with white light, a gold grating substrate whose surface was nanostructured by growing gold nanoparticles (AuNPs). AuNPs were grown directly on the substrate surface by alcohol reduction and their growth was observed at various stages by UV–visible spectroscopy and standard Kretschmann-type SPR spectroscopy. For comparison, normal gold film with smooth surface was examined under similar condition. The T-SPR results show a possibility of hybrid excitation of both localized and propagating surface plasmon. Significantly, T-SPR spectra of the gold grating substrate obtained during AuNP growth show stronger and narrower peaks in the range 650–800 nm. The maximum T-SPR excitation was at an incident angle of 35°. A layer-by-layer system of 5,10,15,20-tetrakis (1-methyl-4-pyridinio)porphyrin tetra(p-toluenesulfonate) molecules and sodium copper chlorophyllin molecules was used to verify the enhancement of the developed system. We believe that the AuNPs/Au grating for T-SPR devices will provide enhanced signals for detecting nanometer order materials and for high-sensitive sensor applications.     

Visualization of Near-Field Enhancements of Gold Triangles by Nonlinear Photopolymerization

We report in this paper the near-field distribution in the case of gold triangle arrays by means of two-photon polymerization for a dipole and a quadrupole plasmon mode. In order to link the finite difference in the time domain (FDTD) simulations of the triangle array and the experimental results, extinction spectra for both cases in air and SU-8 environments are shown. In case of the 40-nm thick gold triangles with 85-nm side-length, we show that the calculated and experimentally obtained near-field for the excited dipole mode has the same distribution along the polarization of the exciting laser beam. In case of bigger triangles of 540-nm side-length a quadrupole mode is excited, which leads to a rotation of the near-field distribution by 90° referred to the polarization of the beam. This effect is also shown in the FDTD simulations.