研究者業績

小林 範久

コバヤシ ノリヒサ  (Norihisa KOBAYASHI)

基本情報

所属
千葉大学 大学院工学研究院 教授 (副研究院長・副学部長)
学位
工学博士(早稲田大学)

J-GLOBAL ID
201901008572789116
researchmap会員ID
B000349601

外部リンク

論文

 133
  • Kyoka Tachibana, Yuki Kojima, Hyuma Masu, Nobuyuki Ichikuni, Hikaru Takahashi, Kota Akiyama, Kazuki Nakamura, Norihisa Kobayashi, Shuji Ichikawa, Yukishige Kondo, Yuya Oaki, Jun Matsui, Shuji Okada, Takashige Omatsu, Keiki Kishikawa, Michinari Kohri
    ACS Applied Materials & Interfaces 2024年9月14日  
  • Shota Tsuneyasu, Shunsuke Kimura, Koshin Enomoto, Kazuki Nakamura, Norihisa Kobayashi
    Solar Energy Materials and Solar Cells 269 112753-112753 2024年6月  
  • Ziying Li, Nana Hitomi, Hideyuki Tanaka, Hitomi Ohmagari, Kazuki Nakamura, Miki Hasegawa, Norihisa Kobayashi
    Materials Advances 5(5) 1897-1902 2023年11月14日  
    Circularly polarized luminescence (CPL) has significantly increased the interest in biological fields. In this research, a water-soluble Eu(iii) complex with a helical complex structure, EuLCOOH, was incorporated in chiral DNA in aqueous solutions. The photoluminescence performance of this DNA/EuLCOOH hybrid system was investigated. Compared to EuLCOOH alone, emission intensity and emission lifetime were effectively improved in the presence of DNA. The major binding between EuLCOOH and DNA was proven to be the electrostatic interaction. Owing to this interaction, the chiral environment provided by DNA successfully induced CPL from EuLCOOH
  • Ryoto Yabuta, Norihisa Kobayashi, Kazuki Nakamura
    Physical Chemistry Chemical Physics 25(38) 25979-25984 2023年7月25日  
    This study investigates the electrochemical modulation of luminescence color, i.e., electrofluorochromism, of an Eu complex in a polyether solvent. The electrofluorochromic (EFC) reaction of the Eu complex occurred via a reversible redox reaction between Eu3+ and Eu2+. Initially, the intrinsically stable Eu3+ complex showed intense red photoluminescence (PL) induced by f-f transitions. After the electrochemical reduction of Eu3+ to Eu2+, broad blue PL was observed attributed to the d-f transitions in the Eu2+ complex. This distinct blue luminescence from the Eu2+ complex was attributed to the effective stabilization of the Eu2+ state by the polyether solvent. The dynamic EFC reaction that changes the valence state of the Eu ion can be potentially applied to novel chemical sensors, security devices, and display devices.
  • Zhuang Liang, Maiko Tozawa, Kazuki Nakamura, Norihisa Kobayashi
    ITE Transactions on Media Technology and Applications 11(4) 131-137 2023年  
    We have demonstrated a multicolor electrochromic device (ECD) with a novel architecture. Different typical ECDs featuring commonly two flat transparent electrodes, a double electrical layer electrode is applied to the device as the counter electrode. By this architecture, even two EC molecules with different polarities mixed in the same ECD can display their unique color, respectively. This paper reports the effect of several commonly-used quaternary ammonium salts as electrolytes on color properties of the ECD featuring a hybrid capacitor architecture. The aim is to select the suitable electrolyte to fabricate multicolor ECD with excellent color performance. Among them, the electrolyte tetraethylammonium tetrafluoroborate performs most satisfactorily attributed to its small ion size and high conductivity. This novel, easily-fabricated, and high EC performance multicolor device provides an opportunity that will develop color ECDs and expand the potential of EC technology.
  • Ziying Li, Kazuki Nakamura, Norihisa Kobayashi
    Bulletin of the Chemical Society of Japan 96(8) 816-823 2023年  
    A solvent-free mechanochemical treatment is used to synthesize an Eu(III) hybrid material containing Eu(D-facam)3 and tetramethylammonium acetate (TMAOAc), mechEu(D-facam)3TMAOAc. The synthesis method is efficient and the reaction occurs within 10 s. Mechanochemically prepared mechEu(Dfacam)3-TMAOAc is proven to be a bimetallic compound, in which TMAOAc functions as a bridging molecule between multiple Eu(III) complexes. Compared with Eu(D-facam)3mechEu(D-facam)3-TMAOAc exhibits ultra-high luminescence, excellent circular polarization activity and thermal stability.
  • Nakamura, K., Yanagawa, N., Kobayashi, N.
    Materials 15(15) 2022年7月  
  • 中村 一希, 木村 俊輔, 小林 範久
    日本画像学会誌 61(3) 280-285 2022年6月10日  
  • Maiko Tozawa, Kazuki Nakamura, Norihisa Kobayashi
    Proceedings of the International Display Workshops 29 837-838 2022年  
    We have already reported a novel multicolor electrochromic (EC) device by introducing a porous counter electrode having high capacitance. In this paper, we investigated the effect of electrolyte species on electric double layer capacitance and coloration properties of the EC device.
  • Hao Wang, Takanori Sugita, Shunsuke Kimura, Kazuki Nakamura, Norihisa Kobayashi
    Proceedings of the International Display Workshops 29 824-827 2022年  
    The novel Electrochromic(EC) system that utilizing electrodeposition of silver can express various optical properties such as mirror, black, and transparent in a single device. It is expected to be used as an advanced reflective electrochromic display. In this research, the citric acid was added to the electrolyte of the device as an capping agent to simply enhance the reflectance of the EC device.
  • Shun Uji, Kazuki Nakamura, Norihisa Kobayashi
    Proceedings of the International Display Workshops 29 820-821 2022年  
    We have studied Ag deposition-based electrochromic (EC) device that can represent various optical states. In this study, dark-field microscopy (DFM) was applied to in situ observation of localized surface plasmon resonance (LSPR) of Ag electrodeposits. Light scattering spectra obtained DFM provided detailed information on the LSPR.
  • Li, Z., Nakamura, K., Kobayashi, N.
    Journal of Materials Chemistry C 11(1) 2022年  
  • Shunsuke Kimura, Hikaru Wakatsuki, Kazuki Nakamura, Norihisa Kobayashi
    Electrochemistry 90(4) 2022年  
    Silver deposition-based electrochromic (EC) device enabled various optical states by using either the electrodeposition of silver thin films or silver nanoparticles on an indium tin oxide electrode. These optical states, including chromatic colors such as cyan, magenta, yellow, and green, are based on absorption by the localized surface plasmon resonance of silver nanoparticles. However, an ideal counter-reaction material that does not affect the color representation by silver nanoparticles and does not dissolve the deposited silver has not been reported. To achieve both color retention and chromatic color representation, MnO2 was utilized as the counter electrode material. The EC properties of the novel device with the MnO2 counter electrode were investigated in terms of charge density and its ability to change color. The novel EC device achieved both representations of chromatic color and retained its color without power supply
  • Kazuki Nakamura, Namiko Yanagawa, Norihisa Kobayashi
    Journal of the Society for Information Display 30(1) 15-23 2022年1月  
    Electrochemical switching of luminescence color, that is, electrofluorochromism, has received increasing attention because of its extensive applications. In this study, we investigate the combination of a luminescent EC molecule and a blue luminescent molecule to achieve electrochemical control of luminescence color by controlling the energy transfer through an electrochromic reaction. We employed a functional leuco dye (Yellow-1), which shows yellow coloration and green emission by electrochemical oxidation, and 2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BBT), which shows strong blue luminescence upon photoexcitation. Using this combination, the blue photoluminescence of the BBT molecule can be electrochemically modulated by the EC reaction of the Yellow-1 molecule, allowing the control of the luminescence color between blue and green emissions through electrochemical reactions.
  • Ziying Li, Haruki Minami, Kazuki Nakamura, Norihisa Kobayashi
    Chemphyschem : a European journal of chemical physics and physical chemistry 22(24) 2496 2021年12月13日  
    The front cover artwork is provided by the group of Norihisa Kobayashi and Kazuki Nakamura at Chiba University. The image shows the drastic luminescence enhancement and induced circular polarization of Eu(D-facam)3 in the presence of tetramethylammonium acetate. Read the full text of the Article at 10.1002/cphc.202100609.
  • Ziying Li, Haruki Minami, Kazuki Nakamura, Norihisa Kobayashi
    ChemPhysChem 22(24) 2511-2516 2021年12月13日  
    The effect of a series of tetramethylammonium salts with different counter anions on the photophysical properties of a chiral Eu(III) complex (Eu(D-facam)3) was investigated. Anion-dependent luminescence of the Eu(III) complex was observed, and particularly in the presence of acetate ions, an outstanding luminescence enhancement (>300 times) and induced circularly polarized luminescence (glum=−0.63) were obtained. The energy transfer process was then evaluated using key photophysical parameters, and it was found that the sensitisation efficiency of the Eu(III) complex significantly increased in the presence of tetramethylammonium acetate (TMAOAc). The interactions between Eu(D-facam)3 and TMAOAc were confirmed by luminescence analysis, circular dichroism spectroscopy, Fourier transform infrared spectroscopy and mass spectral measurements.
  • Kazuki Nakamura, Namiko Yanagawa, Norihisa Kobayashi
    Proceedings of the International Display Workshops 27 729-730 2021年12月9日  
    We have reported photo-and electrochemical-functional materials enabling the dual reflective and emissive function by combining electrochromic materials and luminescent materials. In this study, for achieving electrochemical control of luminescence color, we combined various functional molecules such as electrochromic molecules, luminescent molecules. As a result, luminescence colors were successfully controlled through inter-molecular energy transfer between luminescent molecules and electrochromic molecules.
  • Norihisa Kobayashi, Kazuki Yoshimura, Aline Rougier
    Solar Energy Materials and Solar Cells 222 2021年4月  
  • Ryuki Ozawa, Haruki Minami, Kazuki Nakamura, Norihisa Kobayashi
    Journal of Materials Chemistry C 9(7) 2252-2257 2021年2月21日  
    Electrochemiluminescence (ECL), a light-emitting phenomenon induced by electrochemical redox reactions, has the potential for applications in lightweight and flexible light-emitting devices. Previously, an ultrafast ECL response below 100 mu s was successfully obtained under an applied AC voltage by introducing Ru(bpy)(3)(2+), an orange ECL material, onto a DNA-modified electrode. This study introduced blue-luminescent 9,10-diphenylanthracene (DPA) into an ECL device consisting of the DNA/Ru(bpy)(3)(2+) hybrid electrodes. Consequently, blue ECL from DPA was obtained from the DNA/Ru(bpy)(3)(2+) hybrid electrode at a lower applied voltage than that required to induce the redox reactions of DPA itself. This lower-voltage-drivable blue ECL was attributed to triplet-triplet energy transfer from Ru(bpy)(3)(2+) in the DNA/Ru(bpy)(3)(2+) hybrid electrode followed by a triplet-triplet annihilation upconversion reaction of DPA in the electrolyte solution. Moreover, ultrafast-response, electrochemically triggered blue luminescence from DPA was successfully observed.
  • Shota Tsuneyasu, Masashi Kawara, Koshin Enomoto, Kazuki Nakamura, Norihisa Kobayashi
    Advanced Materials Technologies 6(1) 2021年1月  
    © 2020 Wiley-VCH GmbH This paper demonstrates a novel display device with four optical states: transparent, mirror, black coloration, and orange light emission. The device is constructed by sandwiching a gel electrolyte containing silver ions and a ruthenium (II) complex between a pair of indium tin oxide electrodes. The electrochemiluminescent orange emission from the ruthenium (II) complex is obtained by applying alternative current (AC) voltage. In contrast, the application of direct current (DC) voltage results in the mirror state due to silver electrodeposition. Moreover, the DC application of a higher voltage results in the device exhibiting the black state owing to the distribution of size and roughness of the silver nanoparticles (NPs) on the indium tin oxide electrode. Both the reflective states reverted to their initial transparent state, owing to the dissolution of silver deposits during the DC application of oxidative voltage of silver NPs.
  • Shunsuke Kimura, Tomoko Sugita, Kazuki Nakamura, Norihisa Kobayashi
    Nanoscale 12(47) 23975-23983 2020年12月21日  査読有り責任著者
    <p>Ag deposition-based EC device represents various colors by localized surface plasmon resonance. Four vivid chromatic colors of magenta, cyan, yellow, and green color was represented by precise control of electrodeposition proces of Ag nanoparticles.</p>
  • Minami, H., Itamoto, N., Watanabe, W., Li, Z., Nakamura, K., Kobayashi, N.
    Scientific Reports 10(1) 18917-1-18917-8 2020年12月1日  査読有り責任著者
    <title>Abstract</title> DNA-based materials have attracted much attention due to their unique photo-functional properties and potential applications in various fields such as luminescent and biological systems, nanodevices, etc. In this study, the photophysical properties of a chiral Eu(III) complex, namely (Eu(<italic>D</italic>-facam)3), within DNA films were extensively investigated. The enhancement of photoluminescence (more than 25-folds increase of luminescence quantum yield) and degree of circularly polarization in luminescence (<italic>g</italic>lum = − 0.6) was observed upon interaction with DNA. Various photophysical analyses suggested that the emission enhancement was mainly due to an increase of the sensitization efficiency (high <italic>η</italic>sens) from the ligands to Eu(III) and suppression of the vibrational deactivation upon immobilization onto the DNA molecule. From CD and VCD measurements, it was suggested that the coordination structure of Eu(<italic>D</italic>-facam)3 was affected by the interaction with DNA, suggesting that the structural change of Eu(<italic>D</italic>-facam)3 contributed to the improvement of its luminescent properties.
  • Haruki Minami, Mayu Miyazato, Ziying Li, Kazuki Nakamura, Norihisa Kobayashi
    Chemical Communications 56(88) 13532-13535 2020年11月14日  査読有り責任著者
    © 2020 The Royal Society of Chemistry. Drastic enhancements in both emission intensity and circular polarization of a Eu(iii) complex were achieved in 1-butanol solution in the presence of alkylammonium ions.
  • Kenichiro Omoto, Toyotaka Nakae, Masaki Nishio, Yoshinori Yamanoi, Hidetaka Kasai, Eiji Nishibori, Takaki Mashimo, Tomohiro Seki, Hajime Ito, Kazuki Nakamura, Norihisa Kobayashi, Naofumi Nakayama, Hitoshi Goto, Hiroshi Nishihara
    Journal of the American Chemical Society 142(29) 12651-12657 2020年7月22日  査読有り
    © 2020 American Chemical Society. We describe here the preparation of soft crystals using disilanyl macrocycle C4 possessing four p-phenylenes circularly connected by four flexible disilane bonds. Single crystals of C4 exhibited a reversible thermal single-crystal-to-single-crystal (SCSC) phase transition behavior between two crystal phases accompanied by remarkable mechanical motion (thermosalient effect), as revealed by thermal analyses and X-ray diffraction measurements. Detailed structural analyses implied that flexibility of the parallelogram disilanyl architecture and molecular packing mode via weak intermolecular interactions facilitated a concerted structural transformation (parallel crank motion) of macrocycles in the crystal, thus resulting in the SCSC phase transition accompanied by anisotropic shrinking/elongation of the cells to induce the thermosalient effect. This work explores a new area of organosilicon chemistry and presents the potential utility of disilanyl macrocycles as soft crystals.
  • 南 晴貴, 高橋 亮太, 中村 一希, 小林 範久
    日本画像学会誌 59(3) 330-340 2020年6月10日  査読有り
    生体高分子であるDNAは,様々な機能分子をその構造中に取り込むことで 「DNAソフトクリスタル」ともいうべき構造体の形成が期待される.本総説では,DNAとルテニウム (Ru(II)) 錯体との相互作用による組織体の形成とその特徴的な光学特性,および電気化学素子への展開について解説する.透明電極上に成膜したサケの精巣由来のDNA膜に,電気化学発光体として知られるRu(bpy)32+を電気泳動によって導入し,DNA/Ru(bpy)32+ハイブリッド膜を作成した.このハイブリッド膜にはDNAとRu(bpy)32+から構成される特徴的なメゾスコピック構造体の形成が認められた.このDNA/Ru(bpy)32+ハイブリッド膜を修飾した電極を用いて交流駆動型電気化学発光素子を作成したところ,驚くべきことにサブミリ秒以下 (駆動周波数:10kHz) という,従来系では到底達成できなかった大幅な高速応答化を実現した.さらに,DNAとキラルRu(II)錯体の複合によってエナンチオ選択的発光増強が認められたことから,DNA/Ru(bpy)32+ハイブリッド材料を組み込んだ電気化学発光素子によって円偏光発光のような特徴的なキラル光学特性の実現可能性が示唆された.
  • Shunsuke Kimura, Kazuki Nakamura, Norihisa Kobayashi
    Solar Energy Materials and Solar Cells 205 2020年2月  査読有り
    © 2019 This article describes the design of a silver electrodeposition-based electrochromic (EC) device with excellent image retention properties by using the counter electrode reaction of Prussian blue (PB). We demonstrated silver electrodeposition-based EC device enabled various optical states without dyes and pigments. These optical states were explained by localized surface plasmon resonance (LSPR) absorption of silver nanoparticles electrodeposited on an indium tin oxide (ITO) electrode. However, the color retention property of the device was inadequate because of the presence of Cu2+ ions, which function as redox reaction materials at the counter electrode. That is, Cu2+ in the electrolyte oxidizes the silver deposits on the electrode, resulting in a lack of image retention property. To improve both the redox reactivity of the counter electrode and color retention property, here we utilized PB as the counter electrode material. We discuss the device properties of the silver electrodeposition-based EC device with the PB counter electrode in terms of charge density or its ability to change color. The device achieved both longer retention time in the colored state and reversibility. It has an advantage of maintaining the coloring state without electric power for practical applications.
  • Lijuan Liang, Wenjuan He, Rong Cao, Xianfu Wei, Sei Uemura, Toshihide Kamata, Kazuki Nakamura, Changshuai Ding, Xuying Liu, Norihisa Kobayashi
    Molecules 25(3) 2020年1月23日  査読有り
    © 2020 by the authors. Organic nonvolatile transistor memory with synthetic polypeptide derivatives as dielectric was fabricated by a solution process. When only poly (γ-benzyl-l-glutamate) (PBLG) was used as dielectric, the device did not show obvious hysteresis in transfer curves. However, PBLG blended with PMMA led to a remarkable increase in memory window up to 20 V. The device performance was observed to remarkably depend on the blend ratio. This study suggests the crystal structure and the molecular alignment significantly affect the electrical performance in transistor-type memory devices, thereby provides an alternative to prepare nonvolatile memory with polymer dielectrics.
  • Zhuang Liang, Kazuki Nakamura, Norihisa Kobayashi
    Solar Energy Materials and Solar Cells 200 2019年9月15日  査読有り
    © 2019 Elsevier B.V. With the progress and development of electrochromic (EC)technologies in various applications, the demand for multicolor EC devices (ECDs)has been increasing, and it has a huge connection with the expansion of the market. This paper reports on a novel multicolor ECD with a simple hybrid capacitor architecture (glass/ITO/multi-EC gel/carbon/glass), containing both anodic and cathodic EC materials. By employing the carbon capacitor electrode having porous morphology and large surface area as a counter electrode, even large charge amount consumed by multiple redox pairs’ cathodic materials was adequately compensated. The successful fabrication of the device, consequently, it provides four well-defined colors (white, green, yellow, and red)in one single device.
  • 中村 一希, 小林 範久
    電気化学 87(Summer) 123-128 2019年6月5日  
  • Zhuang Liang, Kazuki Nakamura, Norihisa Kobayashi
    Proceedings of the International Display Workshops 3 1422-1424 2019年  
    We have already reported a novel multicolor electrochromism in a single device by introducing a porous counter electrode having high capacitance. In this paper, we investigated effect of capacitance properties of counter electrode into coloration properties of 10-methylphenothiazine molecule.
  • Shunsuke Kimura, Kazuki Nakamura, Norihisa Kobayashi
    Proceedings of the International Display Workshops 3 1418-1421 2019年  
    Prussian blue modified electrode was introduced into Ag deposition-based electrochromic (EC) device as the counter-reaction material for charge compensation of Ag redox. We discuss the bi-stability of the optical states and desirable features of Prussian blue film for metal deposition based EC device.
  • Norihisa Kobayashi
    RSC Smart Materials 2019-January(33) 475-493 2019年  査読有り
    © The Royal Society of Chemistry 2019. Electrochromism (EC) is defined as a reversible color change by electrochemical redox reaction and has several features such as color variation, memory property and so on. Multifunctional electrochromic materials which control multiple colors, various color density and specular reflection are expected to be potential candidates for energy saving light-modulation devices such as smart windows and novel reflective display devices such as e-paper. In this chapter, we discuss reversible electrodeposition. Electrodeposition is one of the electrochromic mechanisms for inorganic materials because the color of the electrode is varied by electrochemical reductive metal deposition and electrochemical oxidation of the metal deposit. Color change to opaque, black or specular color on the electrode surface is easily acceptable in electrodeposition. However, electrodeposition is also an attractive method to create multi-colors because metal nanoparticles deposited on the electrode exhibit various optical states based on their localized surface plasmon resonance (LSPR). LSPR bands of metal nanoparticles are affected by their size and shape. The control of LSPR, therefore, must enable dramatic color changes on the surface where nanoparticles are deposited. We have focused on several aspects of electrodeposition from the view point of multi-color representation and discussed the mechanism and a wide range of its applications.
  • Haruki Minami, Takuya Ichikawa, Kazuki Nakamura, Norihisa Kobayashi
    Chemical Communications 55(84) 12611-12614 2019年  査読有り
    This journal is © The Royal Society of Chemistry. Electrochemically triggered upconverted luminescence through triplet-triplet energy transfer (TTET) and subsequent triplet-triplet annihilation upconversion (TTA-UC) is observed for the first time in the electrochemiluminescence properties of a Ru(bpy)32+/DPA-containing electrochemical device.
  • Kenji Kanazawa, Kazuki Nakamura, Norihisa Kobayashi
    ChemistrySelect 3(33) 9672-9680 2018年9月7日  査読有り
    © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim A europium(III) [Eu(III)] complex and a viologen derivative were covalently immobilized on a porous titanium(IV) dioxide (TiO2) electrode by the interaction of carboxyl and phosphate groups with the surface, demonstrating electrochemically induced photoluminescence and coloration switching. The modulation of emission and coloration using the functional Eu(III)-viologen modified TiO2 electrode was achieved by an electrochemical reaction between TiO2 and the viologen derivative. Luminescence control was induced via electron and energy transfer from the Eu(III) complex to TiO2 and the linked viologen derivative. The dual functional electrode showed a high on-off emission contrast (81:1), short response time (off: 2.5 s at −0.8 V, on: 5 s at 0 V), and high stability (over 150 cycles) for both emission and coloration control.
  • Norihisa Kobayashi, Haruki Minami, Kazuki Nakamura
    Nanophotonics 7(8) 1373-1385 2018年7月17日  査読有り
    © 2018 Norihisa Kobayashi et al., published by De Gruyter, Berlin/Boston. In this review, we describe the investigation of a ruthenium [Ru(II)] complex-based, AC voltage-driven, electrochemiluminescent (ECL) device first. The ECL turn-on response time and intensity were dramatically improved by introducing the AC method. The turn-on response time was speeded up by increasing the applied frequency: 4 ms response time was achieved at 200 Hz, which was much faster than when using the DC method (1.5 s). We also introduced rutile-type titanium dioxide nanoparticles (TiO2 NPs) in a Ru(II) complex-based AC-ECL device. The ECL intensity and the lifetimes of the ECL device with TiO2 NPs were greatly improved compared to those of the device without nanoparticles. Then we tried to improve photoelectrochemical properties of the Ru(II) complex by combining it with DNA molecules. We fabricated a novel DNA/Ru(bpy)32+ hybrid film that could immobilize the ECL-active Ru(bpy)32+ onto the electrode surface through electrophoretic migration. The hybrid film contained unique micrometer-scale aggregates of Ru(bpy)32+ in the DNA matrix. Surprisingly, by using the DNA/Ru(bpy)32+ hybrid film for the ECL device, luminescence could be obtained at frequencies as high as 10kHz, which corresponds to a response time shorter than 100μs.
  • Shunsuke Kimura, Ryo Onodera, Kazuki Nakamura, Norihisa Kobayashi
    MRS Communications 8(2) 498-503 2018年6月1日  査読有り
    © Copyright Materials Research Society 2018. Ag deposition-based multicolor electrochromic (EC) device we reported can switch various optical states among transparent, black, silver, cyan, magenta, and yellow by only using electrochemical deposition of Ag. However, the EC device had poor color retention property under open-circuit state because of dissolution of deposited Ag metal by Cu2+ ions, which is essential because it acts as redox material at counter electrode. Here, we introduced an anion exchange membrane to separate Cu2+ from the Ag deposit. The improved device achieved longer retention time of colored state. It is effective to maintain the coloring state without electric power for practical application.
  • Lijuan Liang, Yabo Fu, Lianfang Li, Huan Zheng, Xianfu Wei, Yen Wei, Norihisa Kobayashi
    Applied Sciences (Switzerland) 8(6) 2018年5月29日  査読有り
    In recent years, biopolymers are highly desired for their application in optic electronic devices, because of their unique structure and fantastic characteristics. In this work, a non-volatile memory (NVM) device based on the bio thin-film transistor (TFT) was fabricated through applying a new RNA-CTMA (cetyltrimethylammonium) complex as a gate dielectric. The physicochemical performance, including UV, CD spectral, thermal stability, surface roughness, and microstructure, has been investigated systematically. The RNA-CTMA complex film exhibits strong absorption with a well-defined absorption peak around 260 nm, the RMS roughness is ~2.1 nm, and displayed excellent thermal stability, up to 240 °C. In addition, the RNA-CTMA complex-based memory device shows good electric performance, with a large memory window up to 52 V. This demonstrates that the RNA-CTMA complex is a promising candidate for low cost, low-temperature processes, and as an environmentally friendly electronic device.
  • Nakamura Kazuki, Minami Haruki, Sagara Amika, Itamoto Natsumi, Kobayashi Norihisa
    JOURNAL OF MATERIALS CHEMISTRY C 6(16) 4516-4522 2018年4月28日  査読有り
  • Lijuan Liang, Xuying Liu, Masayuki Kanehara, Norihisa Kobayashi, Takeo Minari
    Organic Electronics: physics, materials, applications 55 75-81 2018年4月1日  査読有り
    Printing device arrays of the non-volatile memory transistors is highly desired in the roll-to-roll manufacturing of integrated circuits. Here, we demonstrate the utilization of an insulating biomacromolecule of DNA in the printed transistor memory. A new DNA derivative was synthesized via an ion-exchange reaction in the aqueous solution. Homogeneous molecular orientation in DNA derivative was achieved through a solution process in butanol, which can be employed as the dielectric with a densely packed structure and a good insulating property. The engineered DNA derivative enables to fabricate integrated organic thin-film transistor (OTFT) memories on a large-area flexible substrate in ambient atmosphere. Combining the results of low-frequency dependence of capacitance and a retention time of more than 100 s, this solution-processed DNA-complex was revealed to be a ferroelectric-like dielectric. The printed memories exhibit hole mobility of 0.65 cm2V−1s−1 and a large memory window up to 13 V, which is enough for a plenty of applications. Therefore, this approach is promising for printing large-scale flexible OTFT memories and for realizing various integrated electronics.
  • Ryotaro Kimura, Ayako Tsuboi, Kazuki Nakamura, Norihisa Kobayashi
    Solar Energy Materials and Solar Cells 177 128-133 2018年4月  査読有り
    © 2017 Elsevier B.V. Electrochromic-based optical modulation devices have attracted much interest because of potential application for electric papers and smart windows. We have reported Ag deposition-based optical modulation device which showed reversible changes of optical states between clear transparent and silver-mirror. In the device, formation of silver halide complexes greatly affected the optical states of silver electrodeposit. In this research, the effects of silver halide complexes were investigated by changing halide anion species in terms of the optical properties of the EC devices. The stability of the silver halide complex induced change in reduction voltage to form silver nanoparticles. Diffusion coefficients and electrode reaction rates also have effects on morphology of deposited Ag nanoparticles and resulting optical properties.
  • Lijuan Liang, Yabo Fu, Dongdong Wang, Yen Wei, Norihisa Kobayashi, Takeo Minari
    Applied Sciences (Switzerland) 8(1) 2018年1月10日  査読有り
    Recently, biological materials such as DNA molecules, proteins, and albumen have been extensively investigated for various applications, as they are environmentally friendly and exhibit novel optical and electronic properties. Especially, over the last decades, DNA-lipid complex have been frequently reported as components of optical electronic devices. In this mini-review, the physicochemical performance of DNA-lipid complex is introduced, and then the related research progress in electronic devices such as organic thin film transistors and other optical-electrical devices are discussed. Finally, the challenges and prospects of other possible applications are also presented.
  • Kazuki Nakamura, Haruki Minami, Amika Sagara, Natsumi Itamoto, Norihisa Kobayashi
    Journal of Materials Chemistry C 6(16) 4516-4522 2018年  査読有り
    © 2018 The Royal Society of Chemistry. DNA-based functional materials are of great interest in electrical and optical device applications. In this paper, novel DNA-based photo-functional materials were fabricated by associating a DNA-lipid complex with a luminescent Eu(iii) complex. Interactions between DNA-lipid and Eu(iii) complexes were investigated by photophysical measurements in both solution and film states. The emission properties of the Eu(iii) complex were improved by association with the DNA-lipid complex in the film state. The emission intensity, quantum yield, and thermal stability of the Eu(iii) complex hosted by the DNA-lipid matrix were superior to those of the complex in a conventional poly(methyl methacrylate) matrix. Furthermore, the Eu(iii) complex in the DNA-lipid film showed circularly polarized luminescence through excitation of the ligand moiety. The chiral environment of the DNA matrix provides optical chirality to the interacting Eu(iii) complex.
  • Zhuang Liang, Masahiro Yukikawa, Kazuki Nakamura, Norihisa Kobayashi
    Physical Chemistry Chemical Physics 20(30) 19892-19899 2018年  査読有り
    © the Owner Societies 2018. Despite the application of electrochromic (EC) technologies in various optical modulating devices, the challenge to achieve multicolour EC behavior in a single device still remains. However, because almost all EC materials exhibit a single colour change, only a few organic materials are able to undergo multiple colour switching within a single device. The development of multicolour EC applications is therefore highly limited. In this research, we fabricated an EC device (ECD) with the simple hybrid capacitor architecture, i.e. with a flat ITO electrode as the working side and an ITO particle-modified electrode as the counter side. We also employed an electrolyte containing both anodic and cathodic EC materials consisting of small organic molecules. In this novel ECD, each EC material successfully undergoes individual colour switching from light yellow to light green and magenta. The mechanism of a multicolour system represents a significant breakthrough towards a full-colour ECD, thereby expanding the potential of EC technology.
  • Kenji Kanazawa, Kazuki Nakamura, Sei Uemura, Norihisa Kobayashi
    Journal of Photopolymer Science and Technology 31(3) 353-362 2018年  査読有り
    © 2018SPST. An electroswitching device that enables modulation of both photoluminescence and coloration was obtained. The device consisted of luminescent lanthanide(III) complex Eu(hfa)3(TPPO)2 (photoluminescence material) and an diheptyl viologen HV2+ (electrochromic material). Coloration and emission control were achieved by only electrochemical reactions of HV2+. The coloration of the device was controlled by HV2+ electrochromism. Photoluminescence control was also achieved by the HV2+ electrochromism via intermolecular energy transfer from the excited states of Eu(III) ions to colored HV+∙. However, there were some problems that the response time of switching between emission and coloration was quite slow (approximately 15 minutes), and the representation stability of switching between emission and coloration was low. These problems would be caused by absence of counter electrode reaction material against HV2+ redox. In order to improve the response time of the cell and decrease the driving voltage for dual-mode representation, we introduced prussian blue (PB) modified electrode as an electrochromical counter redox material.
  • Shota Tsuneyasu, Ryota Takahashi, Haruki Minami, Kazuki Nakamura, Norihisa Kobayashi
    SCIENTIFIC REPORTS 7 2017年8月  査読有り
    Electrochemiluminescence (ECL) refers to light emission induced by an electrochemical redox reaction. The stability, emission response, and light intensity of the ECL device are known to be improved by using an alternating current (AC) voltage. In this paper, an AC-driven ECL device is fabricated with DNA/Ru(bpy)(3) (2+) hybrid film-modified electrode. The Ru(bpy)(3) (2+) complex exhibits significant electrochemical reactivity in the DNA/Ru(bpy)(3) (2+) hybrid film prepared by electrochemical adsorption. The hybrid film contains unique micrometre-scale aggregates of Ru(bpy)(3) (2+) in DNA matrix. The physicochemical properties of the hybrid film and its AC-driven ECL characteristics in the electrochemical device are studied. Orange-coloured ECL is observed to be emitted from only the aggregated structures in the hybrid film at the high AC frequency of 10 kHz, which corresponds to a response time shorter than 100 mu s.
  • Kenji Kanazawa, Yuta Komiya, Kazuki Nakamura, Norihisa Kobayashi
    Physical chemistry chemical physics : PCCP 19(26) 16979-16988 2017年7月5日  査読有り
    The electroresponsive switching of red photoluminescence based on the electrochemical coloration of cyan-magenta-green (CMG) viologen components was achieved by combining a luminescent Eu3+ chelate and viologen derivatives, resulting in CMG coloration in a single cell. The cell coloration was controlled by an electrochromic (EC) reaction, which also modulated the photoluminescence of the Eu3+ chelate with high contrast, by transferring energy from the excited state of the Eu3+ ion to the colored states of EC molecules. Cyclic voltammograms, photoluminescence spectra, absorption spectra, luminescence quantum yields, and luminescence lifetimes were measured to clarify the differences between the luminescence quenching and energy transfer efficiencies for each C, M, and G coloration associated with the electrochromism. Thus, the spectral overlap between the luminescence band of the Eu3+ chelate and the absorption band of the colored EC molecules was proven to affect the efficiency of luminescence modulation.
  • Shota Tsuneyasu, Takuya Ichikawa, Kazuki Nakamura, Norihisa Kobayashi
    CHEMELECTROCHEM 4(7) 1731-1735 2017年7月  査読有り
    Electrochemiluminescence (ECL) is a phenomenon in which light is emitted from excited species generated by electrochemical reactions at electrodes. Alternating-current-driven ECL (AC-ECL) devices show good brightness and fast ECL response in comparison to direct-current-driven ECL devices. In this report, we focus on the ECL intensity and long-term stability of blue-light-emitting AC-ECL systems. We used a mixed solvent of propylene carbonate and toluene (volume ratio = 1: 1) to achieve stable blue ECL from 9,10-diphenylanthracene (DPA) molecules. We analyzed the electrochemical, optical, and AC-ECL properties of DPA in this mixed solvent to investigate the effect of the stabilities of redox species on AC-ECL properties. We found that the composition of the electrolyte solution affects the stability of these species. We conclude that stability of generated active species is required to achieve good performance in blue AC-ECL devices.
  • Shota Tsuneyasu, Yuichi Watanabe, Kazuki Nakamura, Norihisa Kobayashi
    SOLAR ENERGY MATERIALS AND SOLAR CELLS 163 200-203 2017年4月  査読有り
    The in situ electrode potentials of anodes and cathodes in electrochromic (EC) devices were investigated. The solution-based 2-electrode EC device was fabricated with electrolyte solutions containing anodic and cathodic EC molecules. The electrochemical reaction in a 2-electrode EC device was controlled by the electrode reaction when electroactive molecules in smaller concentrations were used. In addition, the electrode showing less electrochemical activity in the EC device was subjected to larger overpotential under the application of a driving voltage, leading to the promotion of the redox reaction at the electrode. The results showed that the electrode potentials of the device were spontaneously regulated to facilitate both electrode reactions. It is very important to know the potential at each electrode in order to understand the reaction in detail in the 2-electrode EC device.
  • Lijuan Liang, Lian Fang Li, Yasushi Mitsumura, Kazuki Nakamura, Sei Uemura, Toshihide Kamata, Yen Wei, Norihisa Kobayashi
    JOURNAL OF PHOTOPOLYMER SCIENCE AND TECHNOLOGY 30(4) 513-517 2017年  査読有り
    Recently, DNA-CTMA lipid complex as the environmentally-friendly materials has been investigated extensively in novel functional optical and electronic devices. We have previously reported that the hysteresis mechanism of the nonvolatile transistor memory device in lower temperature region from-150 similar to -20 degrees C (L. Liang et al. Organic Electronics 28, 2016, 294-298). In this study, the hysteresis mechanism in the high temperature region range from 25 similar to 150 degrees C has been investigated through studying the temperature dependence of transfer characteristics, X-ray diffraction patterns (XRD), differential scanning calorimetry (DSC) as well as the dielectric performance of DNA-CTMA complex. The result indicates that the dipoles inside the DNA-CTMA stacking crystalline structure contribute to the appearance of hysteresis in bio-OTFT device at the high temperature.

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