Kazunari Shinbo

Grating-coupled surface plasmon enhanced short-circuit current in organic thin-film photovoltaic cells.

In this study, we demonstrate the fabrication of grating-coupled surface plasmon resonance (SPR) enhanced organic thin-film photovoltaic cells and their improved photocurrent properties. The cell consists of a grating substrate/silver/P3HT:PCBM/PEDOT:PSS structure. Blu-ray disk recordable substrates are used as the diffraction grating substrates on which silver films are deposited by vacuum evaporation. P3HT:PCBM films are spin-coated on silver/grating substrates. Low conductivity PEDOT:PSS/PDADMAC layer-by-layer ultrathin films deposited on P3HT:PCBM films act as the hole transport layer, whereas high conductivity PEDOT:PSS films deposited by spin-coating act as the anode. SPR excitations are observed in the fabricated cells upon irradiation with white light. Up to a 2-fold increase in the short-circuit photocurrent is observed when the surface plasmon (SP) is excited on the silver gratings as compared to that without SP excitation. The finite-difference time-domain simulation indicates that the electric field in the P3HT:PCBM layer can be increased using the grating-coupled SP technique.

In situ Electrochemical-Transmission Surface Plasmon Resonance Spectroscopy for Poly(pyrrole-3-carboxylic acid) Thin-Film-Based Biosensor Applications

In this study, we describe the combination of transmission surface plasmon resonance (TSPR) and electrochemical techniques for the application to biosensors with conducting polymers. Electropolymerization was employed to construct poly(pyrrole-3-carboxylic acid) (PP3C) film on a gold-coated grating substrate using pyrrole-3-carboxylic acid (P3C) monomer solution in 0.5 M H(2)SO(4). In situ electrochemical-transmission surface plasmon resonance (EC-TSPR) measurements were carried out to study the kinetic and electroactivity properties of PP3C film. Immobilization of antihuman IgG on the activated surface and the binding process of human IgG and antihuman IgG in neutral solution could be detected in situ by EC-TSPR measurement. The surface modification steps on the PP3C layer led to an increase in intensity of the transmission peak. The performance, sensitivity, and utility of EC-TSPR spectroscopy showed obvious advantages for the detection of binding process with the simple experimental setup, and could be applied to the study of biomolecular interactions in various systems.

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 650–800xa0nm. 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.

Distance-Dependent Surface Plasmon Resonance Coupling Between a Gold Grating Surface and Silver Nanoparticles

In this study, we achieved an enhancement of the transmission surface plasmon resonance (T-SPR) intensity by depositing silver nanoparticles (AgNPs) onto a gold grating substrate. The T-SPR spectrum of the gold grating substrate with AgNPs showed a strong and narrow SPR peak located between 650 and 800xa0nm; the maximum SPR excitation was observed at a 35° angle of incidence. We controlled the distance between the gold grating surface and the AgNPs by using layer-by-layer (LbL) ultrathin films of poly(diallydimethylammonium chloride) (PDADMAC) and poly(sodium 4-styrenesulfonate) (PSS) to study the distance dependence of the coupling effect between the AgNPs and the gold grating substrate. The distance-dependent T-SPR response of peak position and intensity showed distinctive changes when the intermediate layer was 10 bilayers (∼17xa0nm) thick. The strongest coupling surface plasmon excitation between the AgNPs and the gold grating substrate was obtained at this layer spacing. Furthermore, we explored the potential of the developed system as a switchable pH sensor. The T-SPR spectrum sensitively changed as the pH switched from acidic (pH 2) to alkaline (pH 12) conditions by the swelling/shrinking of the poly(allylamine hydrochloride) (PAH)/PSS LbL film, respectively, which was deposited between the AgNPs and the gold grating.

Fabrication of a Quartz-Crystal-Microbalance/Surface-Plasmon-Resonance Hybrid Sensor and Its Use for Detection of Polymer Thin-Film Deposition and Evaluation of Moisture Sorption Phenomena

We fabricated a hybrid sensor utilizing quartz crystal microbalance (QCM) and surface plasmon resonance (SPR) spectroscopy. We confirmed its effectiveness by observing QCM frequency shifts and SPR wavelength changes for two processes: deposition of various transparent polymer thin films and moisture sorption. For thin-film deposition, the relationship between the QCM frequency and SPR wavelength was found to depend on the refractive index of the film material. For moisture sorption, the direction of SPR wavelength shift depended on the film thickness. This was estimated to be caused by film swelling and decrease in refractive index induced by moisture.

Microfluidic transmission surface plasmon resonance enhancement for biosensor applications

The microfluidic transmission surface plasmon resonance (MTSPR) constructed by assembling a gold-coated grating substrate with a microchannel was employed for biosensor application. The transmission surface plasmon resonance spectrum obtained from the MTSPR sensor chip showed a strong and narrow surface plasmon resonance (SPR) peak located between 650 and 800 nm. The maximum SPR excitation was observed at an incident angle of 35°. The MTSPR sensor chip was employed for glucose sensor application. Gold-coated grating substrates were functionalized using 3-mercapto-1-propanesulfonic acid sodium salt and subsequently functionalized using a five-bilayer poly(allylamine hydrochloride)/poly(sodium 4-styrenesulfonate) to facilitate the coupling/decoupling of the surface plasmon and to prepare a uniform surface for sensing. The detection limit of our developed system for glucose was 2.31 mM. This practical platform represents a high possibility of further developing several biomolecules, multiplex systems, and a point-of-care assay for practical biosensor applications.

Transmission light property due to grating-coupled long-range surface plasmon resonance

Transmission light property due to surface plasmon resonance (SPR) was investigated for glass substrate/500-nm-thick fluoropolymer (CYTOP) with a grating structure/thin metal film/mixed solution of water and glycerol system. Transmission light peaks were observed due to grating-coupled SPR, with a remarkable peak intensity when pure water exists as an ambient dielectric. CYTOP exhibits a refractive index close to that of water, and the remarkable peak intensity was attributed to long-range SPR. The monitoring of polyelectrolyte layer-by-layer film deposition using transmission light was also investigated.

Vapor Sorption to Polyvinyl Alcohol Thin Film Observed Using a Hybrid Sensor of Quartz-Crystal-Microbalance and Surface-Plasmon-Resonance

A quartz-crystal-microbalance (QCM) and surface-plasmon-resonance (SPR) hybrid sensor was prepared, and the sorptions of water and ethanol vapors to polyvinyl alcohol (PVA) films were observed in situ. The shift of the SPR wavelength depended on the PVA film thickness as well as the sorbed vapor. It was estimated to be due to the film swelling induced by the vapor sorption and the relationship between the film thickness and the penetration depth of evanescent wave.

In Situ Study of Electropolymerized Poly(3-aminobenzoic acid) Thin Film on BD-R and DVD-R Grating Substrates by Electrochemical-Transmission Surface Plasmon Resonance Spectroscopy

The electropolymerization process and doping/dedoping properties of poly(3-aminobenzoic acid) (PABA) thin films on gold-coated commercial BD-R and DVD-R grating substrates were simultaneously studied by the combination of electrochemical technique and transmission surface plasmon resonance (TSPR) spectroscopy. The optical property as a function of the applied potentials and time dependence during electropolymerization were studied. The obtained TSPR wavelength scan spectra after electropolymerization showed that the maximum wavelength slightly shifted to longer wavelength indicating the increase of film thickness. In addition, the change during construction of PABA-based immunosensor for label-free detection of human immunoglobulin G can be observed.

Electrochemically Fabricated Pyrrole Copolymer Thin Films and Their Electroactivity in Neutral Aqueous Solution

The functionalized pyrrole copolymers were fabricated by electropolymerization of pyrrole (Py) and functionalized pyrrole monomers, pyrrole-3-carboxylic acid (P3C) and 4-(3-pyrrole) butyric acid (PBA). The electrochemical behavior and doping/dedoping properties of the obtained copolymer thin films were investigated by cyclic voltammetry (CV) in neutral phosphate-buffered saline (PBS) solution. Moreover, the functionalized pyrrole copolymer films were characterized by UV-vis absorption spectroscopy and atomic force microscopy (AFM). The obtained copolymer thin films showed good stability and electroactivity in neutral PBS solution. The presented functionalized pyrrole copolymer thin films may possess potential applications to study in various systems of the biosensors.