Cooperative effect of Au and Pt inside TiO(2) matrix for optical hydrogen detection at room temperature using surface plasmon spectroscopy

Metal (Au, Pt, Au@Pt) and metal oxide (TiO(2)) nanoparticles are synthesized with colloidal techniques and subsequently used as nanocrystal inks for thin films deposition. The optical properties of Au colloids are strongly influenced by both Pt and TiO(2) interfaces: while platinum causes a damping and a blue-shift of the Au Surface Plasmon Resonance (SPR) peak as a consequence of the metal-metal interaction, the anatase matrix is responsible for the red shift of the plasmon frequency due to the increased refractive index. By a careful tailoring of the nanoparticles synthesis, high quality, scattering-free films composed of an anatase matrix embedding Au, Pt and Au@Pt colloids are deposited at room temperature and stabilized at 200 °C. Room temperature exposure of these films to hydrogen leads to optical changes. In the case of Au, there is a slow blue shift of the surface plasmon band, resulting in a wavelength dependent optical response. Much faster but smaller optical changes occur for titania films containing Pt. When both metals are present, the optical response of the gold is much faster. This is attributed to spillover of hydrogen atoms from platinum to gold. This synergy enables enhanced optical sensing of hydrogen at room temperature by combining the low temperature dissociation of H(2) on Pt with the intensive surface plasmon response of the gold nanocrystals.     

Au nanoparticles embedded inverse opal photonic crystals as substrates for upconversion emission enhancement

Photonic crystals (PCs) with periodic dielectric structures are capable to control the propagation of photons when photon energy is in the region of photonic band gap. The upconversion luminescence (UCL) of nanocrystals coated on the PCs surface can be enhanced by the PCs effects. While surface plasmon resonance (SPR) of noble metal nanoparticles (NPs) is being extensively applied to enhance the UCL properties of nanocrystals. However, the PCs or SPR effect are developed separately for the UCL enhancement. In this work, we present a facile preparation method of the Au NPs embedded inverse opals, which was used as substrates to improve the UCL properties of NaYF₄:Yb³⁺, Er³⁺ NPs. The significant luminescence enhancement of NaYF₄:Yb³⁺, Er³⁺ upconverting NPs was obtained by the coupling between the SPR of Au NPs and PCs effects from Au NPs embedded inverse opals substrates. The finding demonstrated that the Au NPs embedded inverse opals as substrates may be useful for the enhanced UCL of other phosphors, producing novel photonic devices.     

Development of an electrochemical‐surface plasmon dual biosensor based on carboxylated conducting polymer thin films

A biosensing platform based on the covalent attachment of biomolecules on electropolymerized carboxylated conducting polymers, poly(3‐aminobenzoic acid) and poly(3‐pyrrole carboxylic acid), were developed for the selective simultaneous detection of two biomolecules using electrochemical‐surface plasmon resonance (EC–SPR) spectroscopy. The surface morphology of the developed biosensors was studied by scanning electron microscopy and atomic force microscopy. The EC–SPR dual biosensor was developed for the label‐free, simultaneous, and selective detection of glucose and human immunoglobulin G (IgG). A change in current density was clearly observed after the injection of glucose, whereas a change in SPR reflectivity was clearly observed after the injection of human IgG. The present work demonstrates the potential of this biosensing platform for real sample analysis in the future. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45641.     

表面等离子体共振技术对过氧化氢的检测

表面等离子体激元共振技术是一种通过观察芯片金属薄膜表面厚度变化产生信号的光学技术,具有实时、灵敏度高、免标记等优点,本文通过辣根过氧化物酶的酶催化作用对过氧化氢进行实时快速检测。信号强度与过氧化氢浓度呈线性关系,辣根过氧化物酶共价结合至金膜表面保持了酶的活性。和其它方法相比较,该方法为过氧化氢的检测提供了一种选择。     

Investigations of electrochemical polymerization processes of thin poly(pyrrole) films and its application to anion sensor based on surface plasmon resonance

A study of the response behavior of anion to surface plasmon resonance (SPR) based sensor, in which a Poly(pyrrole) (Ppy) modified thin gold film was used as a sensor chip is described. In situ surface plasmon resonance and electrochemical methods were used to investigate the electropolymerization and doping/dedoping processes of thin Ppy film. The electropolymerization of pyrrole was carried out under cyclic voltammetric conditions, and simultaneously monitored by in situ SPR. It has revealed that the transition between the reduced state and oxidized state of the Ppy, corresponding to the doping/dedoping of anions, can lead to very distinct changes in SPR signal at a fixed angle of incident laser beam. Furthermore, it has demonstrated that the concentration, the charge and size of anions, as well as the film thickness play important roles in the ingress/egress process of anions. Based on this, this combination of experimental approaches can be used to detect Cl⁻. SPR signal exhibited a good linear relationship with the concentration of Cl⁻.     

Strong coupling between surface plasmon polaritons and Sulforhodamine 101 dye

We demonstrate a strong coupling between surface plasmon polaritons and Sulforhodamine 101 dye molecules. Dispersion curves for surface plasmon polaritons on samples with a thin layer of silver covered with Sulforhodamine 101 molecules embedded in SU-8 polymer are obtained experimentally by reflectometry measurements and compared to the dispersion of samples without molecules. Clear Rabi splittings, with energies up to 360 and 190 meV, are observed at the positions of the dye absorption maxima. The split energies are dependent on the number of Sulforhodamine 101 molecules involved in the coupling process. Transfer matrix and coupled oscillator methods are used to model the studied multilayer structures with a great agreement with the experiments. Detection of the scattered radiation after the propagation provides another way to obtain the dispersion relation of the surface plasmon polaritons and, thus, provides insight into dynamics of the surface plasmon polariton/dye interaction, beyond the refrectometry measurements.PACS: 42.50.Hz, 33.80.-b, 78.67.-n     

Effects of annealing on bandgap and surface plasmon resonance enhancement in Au/SnO2 quantum dots

Au/SnO₂ quantum dots (AuSQDs) were synthesized, and the effects of annealing on their structural and optical properties were examined. Significant changes were observed in the bandgap and surface plasmon resonance (SPR) of the AuSQDs after thermal treatment at different temperatures (400, 500, and 600 °C). The properties of the as-prepared and annealed samples were characterized via X-ray diffraction analysis, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy, and diffuse reflectance spectroscopy. Annealing reduced the bandgap from 3.03 to 2.33 eV and increased the crystallinity while maintaining an average crystallite size below 10 nm. XPS valence band (VB) profiles provided information regarding the VB edge potentials, which helped to determine the conduction band edge potentials. An enhancement in the SPR of the Au nanoparticles was observed for AuSQD-500, which had the smallest bandgap among the samples investigated.     

Reflectance and SERS from an ordered array of gold nanorods

The optical properties of arrays of Au nanorods were studied by specular reflectance spectroscopy. The spectra were dominated by the surface plasmon modes of the Au nanoarrays superimposed on the effects of interference through the films. The longitudinal plasmon resonance moved to longer wavelength as the aspect ratio of the nanorods increased. The reflectance spectra were modelled by applying the Maxwell-Garnett approximation to a uniaxial thin film (composite Au/alumina) and this yielded a good match to the experimental data. SERS spectra on the Au nanorod arrays were recorded at different externally applied potentials and significant differences with respect to an electrochemically roughened Au electrode were revealed. These have been attributed to the nature of the composite nanoarrays, both their nanostructuring into rods and the regular arrangement of these rods.     

Determining surface plasmon resonance response factors for deposition onto three-dimensional surfaces

Intrinsic sorption rates of ligand/receptor binding have been measured by surface plasmon resonance (SPR) using response factors for deposition of proteins or smaller molecules on planar surfaces. In this study, generalized expressions for SPR response factor and effective refractive index are developed to measure rates of analyte sorption onto 3-D surfaces. The expressions are specialized for two limiting cases of immediate practical interest and broad applicability: analyte deposition onto a homogeneous anisotropic porous media and deposition onto close-packed solid spheres adjacent to the sensor surface. These new equations specify media capacity, characteristic size and analyte concentration that are necessary to obtain identifiable responses from interaction with anisotropic porous media or chromatographic resin. These developments are illustrated by comparing response factors for Adenovirus type 5 on planar surfaces, porous media and adsorptive spheres.     

Enhancing performance of a miniaturized surface plasmon resonance sensor in the reflectance detection mode using a waveguide-coupled bimetallic chip

The characteristics of a waveguide-coupled bimetallic (WcBiM) chip in a miniaturized surface plasmon resonance (SPR) sensor and its detection capability for a low molecular weight biomolecule were investigated. The configuration of the WcBiM chip was gold (Au)/waveguide (ZnS-SiO₂)/silver (Ag). In the intensity measurement mode, the sensitivity could be improved by reducing the full width at half maximum (FWHM) of the reflectance curve. The FWHM of the WcBiM chip is narrower than that of the Au chip, which suggests that the slope of the reflectance curve for the WcBiM chip is steeper. In order to generate enhanced resolution, the reflectance should be monitored at the specific angle where the slope is the steepest in the reflectance curve. For the detection of biotin that is a low molecular weight biomolecule, streptavidin was formed on the SPR sensor chip surface. The response of the SPR to biotin at various concentrations was then acquired. The sensitivities of the WcBiM chip and the Au chip were 0.0052%/(ng/ml) and 0.0021%/(ng/ml), respectively. The limit of detection of the biotin concentration for both the WcBiM and Au chips was calculated. The values were 2.87 ng/ml for the WcBiM chip and 16.63 ng/ml for the Au chip. Enhancement of the sensitivity in the intensity detection mode was achieved using the WcBiM chip compared with the Au chip. Therefore, sufficient sensitivity for the detection of a disease-related biomarker is attainable with the WcBiM chip in the intensity measurement mode using a miniaturized SPR sensor.     

Rutile TiO2(101) based plasmonic nanostructures

TiO₂/Ag and TiO₂/Au nanocrystalline multilayer thin films were deposited using pulsed laser deposition technique. Investigations have been made to understand the influence of different phases of TiO₂ on the surface plasmon characteristics of the thin films. Rutile phase of TiO₂ is found to be a good host matrix for both Ag and Au nanoparticles. Compared to silver, gold nanoparticles are found to enhance the photocatalytic activity of the films by exhibiting a broad and intense absorption with a significant shift to longer wavelength region.     

Surface Plasmon Resonance from Bimetallic Interface in Au–Ag Core–Shell Structure Nanowires

Transverse surface plasmon resonances (SPR) in Au–Ag and Ag–Au core–shell structure nanowires have been investigated by means of quasi-static theory. There are two kinds of SPR bands resulting from the outer surface of wall metal and the interface between core and wall metals, respectively. The SPR corresponding to the interface, which is similar to that of alloy particle, decreases and shifts obviously with increasing the wall thickness. However, the SPR corresponding to the outer surface, which is similar to that of pure metal particle, increases and shifts slightly with increasing the wall thickness. A mechanism based on oscillatory surface electrons under coulombic attraction is developed to illuminate the shift fashion of SPR from bimetallic core–shell interface. The net charges and extra coulombic force in metallic wall affect the SPR energy and the shift fashion.     

Electrochemical Formation of CdSe Monolayers on the Low Index Planes of Au

The electrochemical analog of atomic layer epitaxy (ALE) is being studied. ALE is a method for growing thin films of materials using a cycle of surface limited reactions. The surface limited reactions control the deposition by limiting the growth to an atomic layer at a time. In electrochemistry, a surface limited deposition is generally referred to as underpotential deposition (UPD), and UPD is used to form the atomic layers in electrochemical ALE (ECALE). The work presented here is an atomic level study of the deposition of the first few monolayers of CdSe via ECALE: by the alternated UPD of atomic layers of Se and Cd on the low index planes of Au. UPD of Se resulted in the formation of ordered structures on each of the low index planes of Au, as observed by low energy electron diffraction (LEED) and scanning tunneling microscopy (STM). The subsequent UPD of Cd resulted in CdSe deposits which exhibited 1:1 stoichiometry, as determined by coulometry and Auger electron spectroscopy (AES). The following LEED patterns were observed for the CdSe monolayers: Au(111)(√7×√7)R19.1°, Au(111)(3×3), Au(110)(2×3), and the Au(100)(√2×2√2)R45°. Similar LEED patterns were observed on each surface for deposits formed using up to three ECALE cycles. In situ STM studies of Cd deposition on Se-covered Au(111) indicated the formation of a (3×3) structure, consistent with LEED results, and with previous TEM studies. The same LEED patterns were also observed for CdSe monolayers where Cd was deposited as the first atomic layer. AES indicated that the element deposited first remained on the bottom, and that deposited second remained on top.     

Unobstructed electron transfer on porous polyelectrolyte nanostructures and its characterization by electrochemical surface plasmon resonance

Thin organic films with desirable redox properties have long been sought in biosensor research. We report here the development of a polymer thin film interface with well-defined hierarchical nanostructure and electrochemical behavior, and its characterization by electrochemical surface plasmon resonance (ESPR) spectroscopy. The nano-architecture build-up is monitored in real time with SPR, while the redox response is characterized by cyclic voltammetry in the same flow cell. The multilayer assembly is built on a self-assembled monolayer (SAM) of 1:1 (molar ratio) 11-ferrocenyl-1-undecanethiolate (FUT) and mercaptoundecanoic acid (MUA), and constructed using a layer-by-layer deposition of cationic poly(allylamine hydrochloride) (PAH) and anionic poly(sodium 4-styrenesulfonate) (PSS). Electron transfer (ET) on the mixed surface and the effect of the layer structures on ET are systematically studied. Under careful control, multiple layers can be deposited onto the 1:1 FUT/MUA SAM that presents unobstructed redox chemistry, indicating a highly ordered, extensively porous structure obtained under this condition. The use of SPR to trace the minute change during the electrochemical process offers neat characterization of local environment at the interface, in particular double layer region, allowing for better control over the redox functionality of the multilayers. The 1:1 SAM has a surface coverage of 4.1 ± 0.3 × 10⁻¹⁰ mol cm⁻² for ferrocene molecules and demonstrates unperturbed electrochemistry activity even in the presence of a 13 nm polymer film adhered to the electrode surface. This thin layer possesses some desirable properties similar to those on a SAM while presenting ∼15 nm exceedingly porous structure for high loading capacity. The high porosity allows perchlorate to freely partition into the film, leading to high current density that is useful for sensitive electrochemical measurements.     

Fibrinogen and lysozyme adsorption on amorphous carbon film surface detected by multilayer device from the back side of the film

To develop hydrogenated amorphous carbon (a-C:H) as a biocompatible coating, a-C:H was studied in terms of its protein adsorption during the initial process of cell adsorption. A multilayer surface plasmon resonance (SPR) device consisting of an a-C:H layer on Au was built in the Kretschmann configuration to detect protein adsorption on an a-C:H film surface. From the dependence of reflectivity on the laser incident angle, SPR angle was determined to the incident angle in which the light intensity was reduced drastically. The proteins considered were lysozyme (Lyz) and fibrinogen (Fib). The SPR angle increased from 58.09 to 58.69° upon the adsorption of Lyz when the nonadsorbed Lyz was removed after introduction of 20 μM Lyz-containing solution. Upon the adsorption of Fib, the SPR angle increased from 60.95 to 61.76° when the nonadsorbed Fib were removed after the introduction of 0.4 μM Fib-containing solution. The shift in the SPR angle was small for both cases. Obtained results suggested that the number of adsorbed Lyz was higher than that of adsorbed Fib.     

基于表面等离子体共振效应的Ag(Au)/半导体纳米复合光催化剂的研究进展

由具有表面等离子体共振(surface plasmon resonance,SPR)效应的贵金属(Ag、Au等)纳米粒子和半导体纳米结构组成的纳米复合光催化剂具有优异的可见光光催化活性,成为新型光催化材料的研究热点之一。本文综述了Ag(Au)/半导体纳米复合光催化剂的制备方法、基本性质以及光催化应用方面的一些重要研究进展;重点介绍了Ag(Au)等纳米粒子的表面等离子共振增强可见光催化活性的机理,以及Ag(Au)纳米粒子与不同类型半导体复合的光催化剂的光催化性能,其中所涉及的半导体包括金属氧化物、硫化物和其他一些半导体;本领域未来几年的研究热点将集中于新型高效的Ag(Au)/半导体纳米复合光催化剂的微结构调控及其用于可见光驱动有机反应的机理研究。本文为基于SPR效应构建Ag(Au)/半导体纳米复合光催化剂的研究提供了有力的参考依据,并且指出Ag(Au)/半导体纳米复合光催化剂的研究是发展可见光高效光催化剂的重要方向。     

Seed-mediated electrochemical growth of gold nanostructures on indium tin oxide thin films

Two-dimensional gold nanostructures (Au NSs) were fabricated on amine-terminated indium tin oxide (ITO) thin films using constant potential electrolysis. By controlling the deposition time and by choosing the appropriate ITO surface, Au NSs with different shapes were generated. When Au NSs were formed directly on aminosilane-modified ITO, the surface roughness of the interface was largely enhanced. Modification of such Au NSs with n-tetradecanethiol resulted in a highly hydrophobic interface with a water contact angle of 144°. Aminosilane-modified ITO films further modified with colloidal Au seeds before electrochemical Au NSs formation demonstrated interesting optical properties. Depending on the deposition time, surface colors ranging from pale pink to beatgold-like were observed. The optical properties and the chemical stability of the interfaces were characterized using UV-vis absorption spectroscopy. Well-defined localized surface plasmon resonance signals were recorded on Au-seeded interfaces with λ_max = 675 ± 2 nm (deposition time 180 s). The prepared interfaces exhibited long-term stability in various solvents and responded linearly to changes in the corresponding refractive indices.     

A Surface Plasmon Resonance Optical Fibre Sensor for Testing Detergent Cleaning Efficiency

The objective of this paper is to report a feasibility study on the use of optical fibre and surface plasmon resonance (SPR) for determining detergent efficiency. The concept presented comprises a miniaturised dip‐sensor for enabling automated on‐line testing. In this way, the effect of formulation, concentration and temperature on the cleaning behavior of various surfactants and commercial cleaners is investigated. For this purpose, the decladded core of an optical fibre was sputtered with gold and afterwards coated with defined layers of stearic acid or animal fat to obtain a kind of model soil. The deposition of stearic acid was performed using a Langmuir–Blodgett through, and the sensor followed on‐line the deposition of the respective monolayers by UV/VIS spectroscopy, appearing as a distinct and constant shift in wavelength. Moreover, functional coatings were applied above the gold layer to achieve a variation of the hydrophilicity of the sensor surface. The SPR sensor proved to be easy to use, accurate and flexible. It offers a new solution that could replace the existing methods for detergency sensing and with a customised design it could be a useful industry tool since the small size of the dip sensor promises massive testing. The experiment also showed that functionalising the sensing zone could act as a way to mimic the potential substrates for cleaning.     

Effects of substrate annealing on the gold-catalyzed growth of ZnO nanostructures

The effects of thermal substrate pretreatment on the growth of Au-catalyzed ZnO nanostructures by pulsed laser deposition are investigated. C-plane sapphire substrates are annealed prior to deposition of a thin Au layer. Subsequent ZnO growths on substrates annealed above 1,200°C resulted in a high density of nanosheets and nanowires, whereas lower temperatures led to low nanostructure densities. Separate Au film annealing experiments at 700°C showed little variation in the size and density of the Au catalyst droplets with substrate annealing temperature. The observed variation in the density of nanostructures is attributed to the number of surface nucleation sites on the substrate, leading to a competition between nucleation promoted by the Au catalyst and surface nucleation sites on the rougher surfaces annealed below 1,200°C.     

Au and Co3O4 anchored Bi2WO6 with enhanced electron paramagnetic resonance,surface plasmon resonance,nonlinear and magnetic properties

The combination of surface plasmon resonance (SPR) effect with hetero-p–n structure shows promising benefits to optical linear and nonlinear properties. In this study, Au nanoparticles (NPs) decorated p–n hetero-structured Co₃O₄/Bi₂WO₆ composite was synthesized and characterized in terms of the optical linear and nonlinear and magnetic properties, morphology, electron transition, charge transfer, energy band gap, polarizability, SPR effect, and oxygen vacancies using scanning electron microscopy, X-ray photoelectron spectroscopy, electron paramagnetic resonance spectroscopy, Z-scan, ultraviolet–visible spectra, and vibrating sample magnetometer. The combination of Co₃O₄ provided active 3d electrons transition and charge transfer which increased carriers’ concentration and reduced the energy band gap. Au SPR enhanced the internal polarization and strengthened the built-in electric field, yielding strong nonlinear behavior. In addition, magnetic Co₃O₄ endowed sample with room-temperature ferromagnetism which was obviously strengthened by Au NPs. The obtained sample is promising for laser and photonics applications.