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Theerasak JUAGWON Chutiparn LERTVACHIRAPAIBOON Kazunari SHINBO Keizo KATO Toemsak SRIKHIRIN Tanakorn OSOTCHAN Akira BABA
In this work, we report the in situ growth of gold nanoparticles (AuNPs) for the improvement of a transmission surface plasmon resonance (T-SPR) sensor to detect human immunoglobulin G (IgG). Human IgG was immobilized on an activated self-assembled monolayer of 11-mercaptoundecanoic on a gold-coated grating substrate. The T-SPR system was also used to monitor the construction of sensor chips as well as the binding of IgG and anti-IgG conjugated with AuNPs. After specific adsorption with IgG, the T-SPR signal was further enhanced by the in situ growth of AuNPs bound with anti-IgG. Using AuNP conjugation and in situ growth of bound AuNPs, the sensitivity of the IgG immunosensor was improved by two orders of magnitude compared with that without conjugated AuNPs.
Masahiro MINAGAWA Hidetsugu TAMURA Ryo SAKIKAWA Itsuki IKARASHI Akira BABA Kazunari SHINBO Keizo KATO Futao KANEKO
We fabricated organic field-effect transistors (OFETs) having a thin layer of molybdenum trioxide (MoO$_3$), a Lewis acid, and evaluated their electrical characteristics. The insertion of a thin MoO$_3$ layer reduces the on/off ratio but improves the apparent mobility of the charge carriers. To identify the dominant mechanism responsible for this effect, we characterized devices having a 69-nm-thick pentacene layer with a 1-nm-thick MoO$_3$ layer either between the gold source and the drain electrodes or only directly under these electrodes. The former device exhibited a low on/off ratio, whereas the latter device exhibited an on/off ratio comparable to those of conventional pentacene OFETs without a thin MoO$_3$ layer, suggesting that the formation of charge-transfer (CT) complexes immediately above the conduction channel is the critical mechanism. CT complexes at the pentacene/MoO$_3$ interface immediately above the conduction channel contribute to the formation of an effective channel for off-currents as well as drain currents. Moreover, we also attempted to improve the on/off ratio by using a cloth to rub the surface of a thin MoO$_3$ layer immediately above the conduction channel to create what we believe to be a profile with abrupt changes in height in the direction of the drain current conduction in OFETs. Consequently, it was found that such a rubbed MoO$_3$ layer had a surface with a scratched pattern, and the on/off ratio of the OFET was improved, indicating that controlling the CT complex formation by patterning a MoO$_3$ layer can reduce the off-current in OFETs having a pentacene/MoO$_3$ active layer.
Kazunari SHINBO Yuta HIRANO Masayuki SAKAI Masahiro MINAGAWA Yasuo OHDAIRA Akira BABA Keizo KATO Futao KANEKO
A half-cylindrical BK-7 prism/dielectric film with a grating/Ag film/fluorescent polymer film structure was prepared, and its surface plasmon (SP) excitation property was investigated. It was confirmed experimentally that SP excitations are possible in this structure by using prism and grating couplings. The SP excitation property depended on the direction of the grating vector. Furthermore, intense photoluminescence was observed when the SPs were simultaneously excited at the Ag/polymer interface by prism coupling and at the Cytop/Ag interface by grating coupling.
Kazunari SHINBO Eigo SAKAI Futao KANEKO Keizo KATO Takahiro KAWAKAMI Toyoyasu TADOKORO Shinichi OHTA Rigoberto C. ADVINCULA
Organic light emitting diodes (OLEDs) containing nanostructured cathode buffer layers were fabricated, and their electrical and emitting properties were investigated. The OLEDs have an ITO anode/CuPc/TPD/Alq3/buffer layer/Al cathode structure with the buffer layers made from nanostructured alternating layers Alq3 and Al. The driving voltage and the efficiency of the devices were improved by insertion of the buffer layer. It was estimated that some modulations of the Schottky barrier at the Alq3 and the Al cathode interface were induced due to the insertion of the buffer layer and it caused an enhancement of electron injection from the Al cathode.
Keisuke KAWACHI Kazunari SHINBO Yasuo OHDAIRA Akira BABA Keizo KATO Futao KANEKO
A quartz-crystal-microbalance (QCM) and surface-plasmon-resonance (SPR) hybrid sensor was prepared, and the depositions of polymer electrolytes layer-by-layer (LbL) films were observed in situ. The estimated thicknesses obtained from the QCM method were different from those obtained from the SPR method. This was estimated to be caused by film swelling and water contained in the film.
Futao KANEKO Akira BABA Kazunari SHINBO Keizo KATO
In this review, we introduce a variety of surface sensitive techniques for the study of organic thin films, and applications to organic devices. These studies include surface plasmon emission light, organic thin film transistors, combination of quartz crystal microbalance and optical waveguide spectroscopy, evaluation of alignment of liquid crystal molecules at surfaces, and biosensor applications.
Yusuke AOKI Keizo KATO Kazunari SHINBO Futao KANEKO Takashi WAKAMATSU
Attenuated total reflection (ATR) properties and scattered light properties were measured for Ag thin films and arachidic acid (C20) Langmuir-Blodgett (LB) ultrathin films on the Ag thin films to obtain the information about their complex dielectric constants and surface roughness utilizing an excited surface plasmon polariton. The complex dielectric constants for the Ag thin films and the C20 LB films were obtained by fitting the calculated ATR curves to the experimental ones. The surface roughnesses of these films were estimated by the angular distribution of the scattered light assuming the Gaussian function as an autocorrelation function and a linear superposition of roughness spectra. The angular spectra strongly depended on the roughness parameters: the transverse correlation length σ and the surface corrugation depth δ. The experimental angular distributions were explained by some pairs of σ and δ. It was suggested that the surface roughness of the C20 LB films changed with the number of monolayers since the angular spectra varied with the number of the C20 LB monolayers on the Ag films. It is thought that the measurement of the scattered light is useful to evaluate surface roughnesses of LB ultrathin films.
Megumi HAFUKA Masahiro MINAGAWA Yasuo OHDAIRA Akira BABA Kazunari SHINBO Keizo KATO Futao KANEKO
Attenuated total reflection (ATR) property utilizing surface plasmon (SP) excitation was investigated for BK-7 prism/MgF2/Ag film/fluorescent organic dye film structure. In the structure, it is expected that SPs are excited at MgF2/Ag and Ag/dye film interfaces by Otto and Kretschmann configurations, respectively. In the experimental ATR curve, reflection dips for the SP excitations at the interfaces could be detected. Furthermore, SP emission lights were observed by irradiation of Ar ion laser beam from the dye film side. The SP emission light curve with two peaks was observed and it was also considered that the peaks corresponded to the SP excitation of Otto and Kretschmann configurations. The SP emission light spectra indicated the excited fluorescent dyes induced the SP emission lights. Intense emission light of Otto configuration was observed in this sample.
Tohru SHIMAOKA Hiroaki KOBAYASHI Kazuki YAMASHITA Yasuo OHDAIRA Kazunari SHINBO Keizo KATO Futao KANEKO
Molecular aligned naphthacene thins films were fabricated using vacuum evaporation and the rubbing method. The attenuated total reflection (ATR) and emission light properties from surface plasmon (SP) excitation due to molecular luminescence were investigated for these films. The long axis of the rod-like molecule was estimated to align perpendicular to the rubbing direction. The ATR and emission light properties depended on the molecular orientation.
Kazunari SHINBO Makoto IWASAKI Yasuo OHDAIRA Akira BABA Keizo KATO Futao KANEKO
Ridge optical waveguides (OWGs) of fluorinated polyimides were deposited on a quartz crystal microbalance (QCM), and a hybrid sensor employing the OWG spectroscopy and the QCM technique was prepared. A polyvinyl alcohol (PVA) film with CoCl2 was deposited on the OWG, and humidity sensing characteristics were investigated. White light was entered into the waveguide and the output light spectra was observed. The output light intensity markedly changed because of the chromism of CoCl2 by humidity sorption. During the output light measurement, the QCM frequency was monitored simultaneously. The humidity dependences of the QCM frequency and output light were also investigated in a range from 10% to 70%. Furthermore, the response to hydrofluoroether (HFE) was observed, and the change in the output light was hardly observed because CoCl2 does not exhibit chromism in HFE sorption.
Naraphorn TUNGHATHAITHIP Chutiparn LERTVACHIRAPAIBOON Kazunari SHINBO Keizo KATO Sukkaneste TUNGASMITA Akira BABA
We fabricated silicon nanowires (SiNWs) using a metal-catalyzed electroless etching method, which is known to be a low-cost and simple technique. The SiNW arrays with a length of 540 nm were used as a substrate of SiNWs/PEDOT:PSS hybrid solar cell. Furthermore, gold nanoparticles (AuNPs) were used to improve the light absorption of the device due to localized surface plasmon excitation. The results show that the short-circuit current density and the power conversion efficiency increased from 22.1 mA/cm2 to 26.0 mA/cm2 and 6.91% to 8.56%, respectively. The advantage of a higher interface area between the organic and inorganic semiconductors was established by using SiNW arrays and higher absorption light incorporated with AuNPs for improving the performance of the developed solar cell.
Hathaithip NINSONTI Weerasak CHOMKITICHAI Akira BABA Wiyong KANGWANSUPAMONKON Sukon PHANICHPHANT Kazunari SHINBO Keizo KATO Futao KANEKO
We report enhanced photocurrent properties of dye/Au-loaded titanium dioxide (TiO2) films on Au gratings. Au-loaded TiO2 nanopowders were first synthesized by a modified sol-gel method and then prepared by the impregnation method. We also fabricated dye-sensitized solar cells, which were composed of Au grating/Au-TiO2/TMPyP-SCC LbL (20 bilayers)/electrolyte/ITO substrates. Short-circuit photo-current measurements showed that Au-loaded TiO2 with grating-coupled surface plasmon excitation can enhance the short-circuit photocurrentof the fabricated cells.
Hathaithip NINSONTI Kazuma HARA Supeera NOOTCHANAT Weerasak CHOMKITICHAI Akira BABA Sukon PHANICHPHANT Kazunari SHINBO Keizo KATO Futao KANEKO
The fabrication of a grating structure formed by a solid-state electrolyte layer on a dye-TiO$_{2}$ film by the nanoimprinting technique using a polydimethylsiloxane (PDMS) stamp and its application in photoelectric conversion devices are described. The PDMS grating pattern is imprinted from blu-ray disc recordable. A silver electrode was deposited on the patterned solid-state electrolyte layers. Surface plasmon resonance (SPR) excitation was observed in the fabricated solar cells by irradiation with white light. The photoelectric conversion properties were measured to study the effect of the two types of SPR excitations, i.e., the propagating surface plasmon on the Ag grating surface and the localized surface plasmon from the Au nanoparticles on TiO$_{2}$.
Akira BABA Yohsuke SANO Yasuo OHDAIRA Kazunari SHINBO Keizo KATO Futao KANEKO
In this report, we demonstrate electrocatalytic oxidation properties of ascorbic acid at poly(3,4-ethylenedioxythiophene) (PEDOT) thin films in view of their potential application for bio-sensing devices. PEDOT thin films were deposited on gold thin films by electropolymerization of EDOT monomer in acetonitrile solvent. In-situ electrochemical-surface plasmon resonance spectroscopy (EC-SPR) was used to detect both electrochemical and optical signals upon an injection of ascorbic acid.
Kazunari SHINBO Hiroshi MIURA Yasuo OHDAIRA Akira BABA Keizo KATO Futao KANEKO
In this study, attenuated total reflection (ATR) utilizing surface plasmon (SP) excitation and SP emission lights were observed for the adsorption of polystyrene (PS) spheres and a water-soluble polymer. The PS spheres contained fluorescent dyes and exhibited red fluorescence. The ATR properties indicated film deposition with increasing number of adsorption cycles. The SP emission light induced by the fluorescent dye in the spheres was also measured, and an increase in the peak intensity, as well as an angle shift, was observed. Furthermore, the SP emission light spectra were investigated at various emission angles. The dispersion relation obtained from the SP emission light almost corresponded to that obtained from the ATR curves.
Kazunari SHINBO Takaaki EBE Futao KANEKO Keizo KATO Takashi WAKAMATSU
Short-circuit photocurrents (ISC) utilizing surface plasmon polariton (SPP) excitation were investigated for the merocyanine (MC) LB film photoelectric device. The device has a prism/MgF2/Al/MC LB film/Ag structure. In the attenuated total reflection (ATR) configuration, SPPs were resonantly excited at the interfaces between MgF2 and Al (MgF2/Al) and between Ag and air (Ag/air). The thickness and the dielectric constants of the layers were evaluated from the ATR measurements. Short-circuit photocurrents, ISCs, as a function of the incident angle of the laser beam were observed simultaneously during the ATR measurements. In the ISC curves, large and small peaks were observed, and the peak angles of the ISC almost corresponded to the dip angles of the ATR curves due to the SPP excitations. Electric fields and optical absorptions in the cell were calculated using the dielectric constants and the film thickness obtained from the ATR measurements. The calculated absorption in the MC layer as a function of the incident angle corresponded to the ISC curve. It was thought that the optical absorption in the MC layer affected directly to the profile of the ISC. Furthermore, the calculated absorption in the cell with the prism and the MgF2 layer exhibited much larger than that of the cell without them. It was estimated that the photocurrents were enhanced by the excitation of SPPs in the ATR configuration.
Takumi KOBAYASHI Masahiro MINAGAWA Akira BABA Keizo KATO Kazunari SHINBO
Improvement of the on/off ratio in organic field-effect transistors through the use of pentacene and molybdenum trioxide (MoO3) layers was attempted via the preparation of a discontinuous MoO3 layer using a mesh mask. We prepared three types of devices. Device A had a conventional top-contact structure with an n-type Si wafer and a 200-nm-thick SiO2 film onto which we deposited a 70-nm-thick pentacene film and a 30-nm-thick layer of Au top electrodes. Devices B and C had a similar structure to device A but received a continuous and a discontinuous MoO3 layer, respectively. The off current in Device B was remarkably high; in contrast, the off current in Device C was reduced and dependent on the separation of the MoO3 layer. It was deduced that the high resistance of the area without MoO3 contributed to the reduced off current.