Plasmon Polariton Imaging Characteristics of Near-Field Optical Fiber Probes

The influence of different near-field optical (near-field scanning optical microscopy) probes on the imaging of surface plasmon polaritons propagating on thin metal films is investigated. Metal-coated fiber probes exhibit a suppression of the measured plasmon signal close to the metal film surface and increased local scattering of the plasmon field. Purely dielectric fiber probes are shown to be largely free of these effects.     

Improved Absorbance and Near-Infrared Dispersion of AuGe Nanoparticles over Au Nanoparticles Prepared with Similar Thermal Annealing Environment

The difficulty in patterning the structures at sub-wavelength range leads to employ the bottom-up approach to form nanostructures of metals as well as dielectric components that disperse them in host media. The optical properties of nanoparticles are studied with UV-Vis 750 (lambda) NIR spectroscopy and fit with empirical relations. The refractive index is about the volume fraction of particles. The AuGe nanoparticles demonstrate improved absorbance, lower refractive index, and higher extinction than Au nanoparticles formed with similar thermal process. Surface plasmon resonance (SPR) phenomena are highly sensitive to the bonding between atoms, atomic structure, and the electronic configuration in atoms of the given material. If one takes into account the structure of materials, then the literature on eutectic alloys predicts that alloying gold with germanium (AuGe) with varying compositions will also change the x-ray diffraction peak positions of gold itself. The peak shift can be interpreted as the change in grain size or shift in grain boundaries implying a corresponding change in material’s atomic arrangement within lattice structure. As a result, there will be a change in the charge distribution of free electron cloud in original gold ultimately affecting a change in the plasmon resonance frequency and thereby modulating the various optical phenomena such as absorbance, reflectance, and refractive index. This alloying also brings a change in the dielectric constant of the material such that the plasmonic behavior may shift among different regions (UV, visible, NIR, MWIR, and LWIR). Metal semiconductor eutectic alloy which is widely popular as a soldering material would have scope in futuristic photonic applications due to its tuneable optical properties. In this work, we study the effects of Au and AuGe nanoparticle deposition on GaAs films grown by molecular beam epitaxy (MBE). Au and AuGe thin films (12-nm thick) were annealed in the temperature ranges of 400–800 and 300–700 °C, respectively, to form Au and AuGe nanoparticles. The formation of these nanoparticles was confirmed by scanning electron microscopy (SEM) measurements. Optical absorption spectroscopy measurements showed plasmon resonance peaks at around 670 and 535 nm for the AuGe-deposited 300 °C-annealed sample and Au-deposited 600 °C-annealed sample on sapphire, respectively, thereby confirming the plasmonic effect. Correlation of Raman spectroscopy measurement results with X-ray diffraction measurement results reveal that the transverse optical mode intensity and full width at half maximum of the GaAs (400) peak increased with an increase in annealing temperature, indicating degradation of the crystalline properties of GaAs film at higher annealing temperatures. The highest increments of the photoluminescence (PL) intensities in comparison to that of the bare GaAs film were observed to be 37 and 77% for the Au-deposited 600 °C-annealed and AuGe-deposited 300 °C-annealed samples, respectively. These enhancements of PL spectra are an indication of the significant scattering of photons by Au and AuGe nanoparticles, and they are attributed mainly to the contribution of the local surface plasmon resonance of these nanoparticles. A comparative analysis of PL enhancements revealed that AuGe nanoparticles induced a greater enhancement than Au nanoparticles. The calculated activation energies of the Au-deposited 600 °C-annealed sample, AuGe-deposited 300 °C-annealed sample, and bare GaAs sample were around 18, 24, and 33 meV, respectively. We found one-order increment in peak responsivity of AuGe plasmonic-based trilayer InAs quantum dot detector in comparison to as-grown detector at 80 K. Therefore, this study is expected to be very useful in the realization of high-performance plasmonic-based optoelectronic and sensing devices.     

Enhancing LSPR Sensitivity of Au Gratings through Graphene Coupling to Au Film

A particular interesting plasmonic system is that of metallic nanostructures interacting with metal films. As the localized surface plasmon resonance (LSPR) behavior of gold nanostructures (Au NPs) on the top of a gold thin film is exquisitely sensitive to the spacer distance of the film-Au NPs, we investigate in the present work the influence of a few-layered graphene spacer on the LSPR behavior of the NPs. The idea is to evidence the role of few-layered graphene as one of the thinnest possible spacer. We first show that the coupling to the Au film induces a strong lowering at around 507 nm and sharpening of the main LSPR of the Au NPs. Moreover, a blue shift in the main LSP resonance of about 13 nm is observed in the presence of a few-layered graphene spacer when compared to the case where gold nanostructures are directly linked to a gold thin film. Numerical simulations suggest that this LSP mode is dipolar and that the hot spots of the electric field are pushed to the top corners of the NPs, which makes it very sensitive to surrounding medium optical index changes and thus appealing for sensing applications. A figure of merit of such a system (gold/graphene/Au NPs) is 2.8, as compared to 2.1 for gold/Au NPs. This represents a 33 % gain in sensitivity and opens-up new sensing strategies.     

Optimization of Surface Plasmon Resonance Biosensor with Ag/Au Multilayer Structure and Fiber-Optic Miniaturization

In this paper, we report a novel wavelength interrogation-based surface plasmon resonance (SPR) system, in which a film of three Ag layers and three Au layers are alternately deposited on a Kretschmann configuration as sensing element. This multilayer film shows higher sensitivity for refractive index (RI) measurement by comparing with single Au layer structure, which is consistent with its theoretical calculation. A sensitivity range of 2056–5893 nm/RIU can be achieved, which is comparable to RI sensitivities of other wavelength-modulated SPR sensors. Compared with Ag film, this Ag/Au multilayer arrangement offers anti-oxidant protection. This SPR biosensor based on a cost-effective Ag/Au multilayer structure is applicable to the real-time detection of specific interactions and dissociation of low protein concentrations. To extend the application of this highly-sensitive metal film device, we integrated this concept on an optical fiber. The range of RI sensitivities with Ag/Au multilayer was 1847–3309 nm/RIU. This miniaturized Ag/Au multilayer-based fiber optic sensor has a broad application in chemical and biological sensing.     

Dispersion and Damping of Gold Surface Plasmon

High-resolution electron energy loss spectroscopy was used to investigate the surface plasmon dispersion in (111)-oriented Au films grown on Cu(111). The measured dispersion of the plasmon mode was positive, as found for Ag. The centroid of the induced charge associated to the plasmon field lies well inside the jellium edge. The damping relation of the Au surface plasmon presented a critical wave vector of 0.11 Å^?1. For higher values of the parallel momentum transfer, the line width of Au surface plasmon considerably increased as a consequence of the opening of a new decay channel via single-particle transitions.     

Surface-Enhanced Raman Scattering (SERS) on 1D Nano-gratings

Surface-enhanced Raman scattering (SERS) enhancement factor (EF) is among the major applications of surface plasmon polaritons (SPP’s). In this work, the SERS EF of 1D rectangular and sinusoidal-shaped gold (Au) grating structures has been designed and optimized on Au film using COMSOL multiphysics (5.3a) RF module taking glass as substrate. The 1D grating models are simulated by variation in slit width ranging 200–600 nm while other parameters including periodicity of 700 nm and Au film thickness of 50 nm remained fixed. In order to study the several phenomena including enhanced optical transmission and SERS EF, the transmission and electric field spectra have been obtained from both types of grating structures. In agreement with fundamental plasmonic mode, the slit width of two-thirds of the periodicity found to be optimum for SERS EF. Remarkable value of SERS EF is obtained in the case of a sinusoidal Au grating device (6.4 × 10⁹) which is calculated to be five times that of the rectangular grating (1.2 × 10⁹). These devices are also the fingerprints of molecules, hence find applications in biosensing, pollution control, and chemical and food industry.

     

Blue-Shifted SPR of Au Nanoparticles with Ordering of Carbon by Dense Ionization and Thermal Treatment

Thin films of carbon-containing Au nanoparticles (NPs), prepared by the co-sputtering using a neutral Ar atom beam, were irradiated by 120 MeV Ag ions and also annealed, separately, at increasing temperatures in inert atmosphere. The surface plasmon resonance (SPR) band of the nanocomposite film was observed to be blue shifted (～50 nm) in both cases, with increasing fluence and temperature. The structural changes of Au NPs embedded in amorphous carbon matrix were investigated using X-ray diffraction and transmission electron microscopy. A growth of Au NPs was observed with increasing fluence and also with increasing temperature. A percolation of Au NPs was observed at 500 °C. A growth of Au NPs with ion irradiation is explained in the framework of a thermal spike model. Raman spectroscopy revealed the ordering of a-C thin films with increasing fluence and temperature, which is ascribed to a change of refractive index and the blue shift of the SPR band.     

A novel ultrahigh-resolution surface plasmon resonance biosensor with an Au nanocluster-embedded dielectric film

The detection performance of conventional surface plasmon resonance (SPR) biosensors is limited to a 1 pg/mm(2) surface coverage of biomolecules, and consequently, such sensors struggle to detect the interaction of small molecules in low concentrations. The present study is attempted to propose the use of a novel SPR biosensor with Au nanoclusters embedded in a dielectric film to achieve a 10-fold improvement in the resolution performance. A co-sputtering method utilizing a multi-target sputtering system is used to fabricate the present dielectric films (SiO(2)) with embedded Au nanoclusters. It is shown that the sensitivity of the developed SPR biosensor can be improved by adjusting the size and volume fraction of the embedded Au nanoclusters in order to control the surface plasmon effect. The present gas detection and DNA hybridization experimental results confirm that the proposed Au nanocluster-enhanced SPR biosensor provides the potential to achieve an ultrahigh-resolution detection performance of approximately 0.1 pg/mm(2) surface coverage of biomolecules.     

Large and Ultrafast Optical Response of a One-Dimensional Plasmonic–Photonic Cavity

The resonant coupling of a localized surface plasmon mode and a cavity mode in a photonic crystal has been recently shown to strongly tailor the stationary optical response of gold nanoparticles. Here, we demonstrate that this can be further exploited for controlling light on an ultrashort time scale. The stationary and ultrafast optical responses of such a plasmonic–photonic cavity are investigated numerically. We show that the transient photo-induced change of the optical transmittance of a bare nanocomposite thin film can be amplified up to 60 times once resonantly coupled to the cavity mode in the hybrid device, despite the degradation of this mode due to absorption losses. In addition, different all-optical, ultrafast, efficient, and reversible photonic functions (increase or decrease of the signal intensity, transient spectral shift of the cavity mode) can be achieved depending on the spectral position of the transmitted mode tuned by varying the angle of incidence. The transient modification of the signal intensity is predicted to reach about 300 % after a subpicosecond rise time when the defect mode matches the plasmon resonance.     

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.     

Spectrally Tunable Optical Transmission of Titanium Nitride Split Ring Resonators

In this paper, the optical properties of titanium nitride split ring resonators as an intermetallic metamaterial nanostructure were studied. Our simulation shows the presence of plasmon and LC resonances in the transmission spectrum of a cell consists of four u-shape split ring resonators. The effect of different parameters of resonator such as size, periodic constant, and the material between arms in addition to the polarization of incident beam was examined on the resonance behavior of the system. Also, the optical properties of a cell consist of four complementary split ring resonators within titanium nitride thin film were investigated. An excited mode was observed at λ = 840 nm that was attributed to the plasmon resonance. Changing the arrangement and configuration of the system from C _1v to C _2v symmetry led to the presence of the LC mode beside the plasmon mode in the transmission spectrum. Also, we explored a connection between the complementary split ring resonators and orderly perforated surface plasmon systems. It was determined that a transition occurred from resonator-type to surface plasmon behavior by increasing the size of resonator above 170 nm.     

Double-Layered Metal Nano-Strip Antennas for Sensing Applications

A coupled plasmonic system based on double-layered metal nano-strips for sensing applications is investigated by means of mode analysis and two-dimensional finite-difference time-domain simulations. The nano-strips act as optical antennas through constructive interference of short-range surface plasmon polaritons, thus increasing their scattering cross-section and optical field enhancement. Near-field modulation by optical trapped metal nanoparticles (NPs) is also demonstrated. Our results reveal that the device exhibits a refractive index sensitivity of ～200 nm/RIU, and a maximum surface-enhanced Raman scattering (SERS) factor of 10⁹–10¹⁰ from metal NPs trapped in the near-field region. The proposed device shows reasonable figure-of-merit and is ready for integration with common optofluidic biosensors.     

Dielectric Nanocup Coating Effect on the Resonant Optical Properties of Individual Au Nanosphere

By finite element method (FEM), dielectric nanocup coating effect on the resonant optical properties of individual Au nanosphere was investigated. It is demonstrated not deleterious to the sensing signals of the nanosphere. The proposed nanocomposite provides an interesting localized surface plasmon resonance (LSPR) sensor with quadratic response, which refractive index (RI) sensitivity is revealed to increase with the RI both of its surrounding and local environment. The differences between the LSPR peak positions of the nanocomposite measured from far-field and near-field spectra are discussed, too. It is believed to shed light on the future applications in surface enhanced Raman spectroscopy, biochemical sensing, and detections.     

Numerical Simulation of Extinction Spectra of Plasmonically Coupled Nanospheres Using Discrete Dipole Approximation: Influence of Compositional Asymmetry

We demonstrate plasmon coupling phenomenon between equivalent (homodimer) and non-equivalent (heterodimer) spherical shape noble metal nanoparticle (Ag, Au and Al). A systematic comparison of surface plasmon resonance (SPR) and extinction properties of various configurations (monomer, homodimer and heterodimer) has been investigated to observe the effect of compositional asymmetry. Numerical simulation has been done by using discrete dipole approximation method to study the optical properties of plasmonically coupled metal nanoparticles (MNPs). Plasmon coupling between similar nanoparticles allows only higher wavelength bonding plasmon mode while both the plasmon modes lower wavelength antibonding mode as well as higher wavelength bonding mode in the case of heterodimer. Au monomer of radius 50 nm shows resonance peak at 518 nm while plasmon coupling between Au-Au homodimer results in a spectral red shift around 609 nm. Au-Ag plasmonic heterodimer (radius 50 nm) reveals two resonant modes corresponding to higher energy antibonding mode (422 nm) as well as lower energy bonding mode (533 nm). Further, we have shown that interparticle edge-to-edge separation is the most significant parameter affecting the surface plasmon resonances of MNPs. As the inter particle separation decreases, resonance wavelength shows red spectral shift which is maximum for the touching condition. It is shown that plasmon coupling is a reliable strategy to tune the SPR.

     

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.     

Supramolecular architectures for the functionalization of solid surfaces

Surface plasmon optical techniques are described as sensitive tools that allow for the on-line characterization of supramolecular biofunctional architectures at solid/solution interfaces. After a short introduction into the fundamentals of surface plasmon optics the observation of the build up of a functional bio-interface by the self-assembly process of long chain thiolates at an Au surface is described. Criteria are developed for tailoring the SAM architectures optimized for maximum protein binding from solution by specific bio-recognition reactions. SPM is employed to image the selective binding of streptavidin to a functionalized SAM laterally patterned by UV-photolithographic techniques.     

Nanostructuring of Continuous Gold Film by Laser Radiation Under Surface Plasmon Polariton Resonance Conditions

The physical mechanisms of metallic nanoparticles formation by laser technology were studied. The system air/Au film/glass was irradiated by laser at the conditions of surface plasmon resonance. A surface electromagnetic wave was excited in Kretchmann configuration by the fundamental and second harmonics of the Q-switched YAG/Nd⁺³ laser with pulse power density close to the threshold of melting. Nanostructuring of Au film was observed only for the second harmonic (λ = 0.532 μm) irradiation at the surface plasmon polariton resonance (SPR) conditions. Estimations were done using the interference model of the differently directed plasmon polariton waves excited by a surface electromagnetic wave on the metal surface. It was shown that a regular pattern of locally heated spots can be formed in a metallic film by pulsed laser irradiation. The spatial distribution of this pattern is close to the period of interference. The observed effect of laser nanofragmentation is explained by the self-organization of plasmon polariton subsystem in the process of Au nanoparticles formation at high laser intensity levels. These methods open new possibilities for nanostructured surfaces formation utilizing simple self-organization processes.     

A New Route to Glucose Sensing Based on Surface Plasmon Resonance Using Polyindole

In the present study, we report the first polyindole-modified metal (Au) as a glucose sensor utilizing surface plasmon resonance (SPR) technique. Polyindole (PIn) was deposited by spin coating to modify the surface of the gold disk. Sensor surface was prepared by immobilizing glucose oxidase on the polyindole-modified gold disk. Different concentrations of glucose were taken to analyze the sensor response. A change in refractive index of the film was observed due to the chemical reactions of glucose with glucose oxidase. The response of the sensor is fast and highly sensitive to low concentrations of glucose and the sensitivity increases in the range of 0.075–0.5 μM. The use of Au/polyindole (PIn/Au) substrates for SPR-based study of bio-molecular sensing has been demonstrated.     

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.     

Influence of Plasma Polymerized Dielectric Buffer Layer and Gold Film on the Excitation of Long-Range Surface Plasmon Resonance

Recently, long-range surface plasmon resonance (LRSPR) sensor has attracted a great deal of attention as a potentially non-destructive and label-free technique for cellular studies in real time. Thus, much effort has been placed on the fabrication and optimization of multilayered structure required for the excitation of LRSPR. In this work, a detailed study about the influence of both plasma polymerized dielectric buffer layer (DBL) and thin gold film on the excitation of LRSPR was performed. The DBLs of different thicknesses were deposited directly onto SF11 glass slides by radio frequency plasma polymerization (pp) of perfluorooctyl ethylene (PFOE). Thereafter, Au films of different thicknesses were thermally evaporated onto the ppPFOE layers. Atomic force microscopy (AFM) results suggest that the resulting SF11/ppPFOE/Au structure has a smooth surface regardless of Au film’s thickness. LRSPR measurements indicate that the excitation of LRSPR relies not only on the thickness of the ppPFOE buffer layer, but also on the thickness and optical property of thin Au film. Theoretical simulation based on Fresnel’s equation allows for the determination of both the thickness and optical constant of each layer supporting the LRSPR, and also enables us to predict the optimum combination of ppPFOE and Au film in a LRSPR sensor. The performance of various LRSPR sensors to monitor the bulk refractive index variation has also been investigated.