高次機能調和材料創成の原子・分子プロセッシング

2003 Fiscal Year Annual Research Report

• Project/Area Number: 09CE2005
• Research Institution: Osaka University
• Principal Investigator: 川合 知二 大阪大学, 産業科学研究所, 教授 (20092546)
• Co-Investigator(Kenkyū-buntansha): 岩崎 裕 大阪大学, 産業科学研究所, 教授 (00029901) ; 谷村 克己 大阪大学, 産業科学研究所, 教授 (00135328) ; 弘津 禎彦 大阪大学, 産業科学研究所, 教授 (70016525) ; 吉田 博 大阪大学, 産業科学研究所, 教授 (30133929) ; 朝日 一 大阪大学, 産業科学研究所, 教授 (90192947)
• Keywords: 機能調和材料 / 原子・分子プロセッシング / 生体指向デバイス / エネルギー変換材料 / ナノ加工 / ナノ計測 / 機能調和型センサ・メモリ / マテリアルデザイン

Research Abstract

昨年度(平成14年度)の成果にもとづき、"高次機能調和材料"として具体的に以下に示す材料開発を行い、又、それを実現するためのプロセッシングの開発を行った。研究体制は、生体指向高感度センサ・メモリ材料開発グループ、エネルギー・環境調和材料開発グループ、極微プロセッシンググループの3グループから構成される。
1:〔生体指向高感度センサ・メモリ材料〕:これまでの透明磁性半導体のマテリアル・デバイスデザイン、ワイドギャップ室温発光強磁性半導体の創製、シリコン表面上の生体分子の微細パターニングプロセスの開発などの成果を更に発展させて、生体指向高感度デバイスへ展開するためのマテリアル・デバイスのデザイン、材料創製、特性評価、デバイス作製の研究を進めた。
平成15年度の実施計画を以下に示す。
1)光/磁性機能調和材料のデバイス化を進めた(川合)。2)半導体をベースにしたマルチイオンイメージセンサ、及び、エリプソメトリセンシング手法を駆使したバイオ化学情報の2次元可視化・バイオチップへの展開をはかった(岩崎)。3)多結晶AlGaNによる電界電子放射特性の高性能化、遷移金属/希土類添加窒化物磁性半導体によるスピン機能調和デバイスの創製、窒化物磁性半導体量子ドット形成による新機能の創製を行った(朝日)。4)第一原理計算に基づいて、(Ga,Cr)Nおよび(Ga,Mn)Nまた(Zn,V)O,(Zn,Cr)O,(Zn,Mn)Oのスピングラスから強磁性ハーフメタル透明強磁性転移を用いた量子スウィッチングデバイスのデザインと4d,5d遷移金属ドーピングによる巨大磁気光学効果を用いた高次機能調和デバイスデザインを完了した(吉田)。
2:〔エネルギー・環境調和材料〕:21世紀のエネルギー・環境問題を解決するためのひとつの方策として、光エネルギーの効率的利用とエネルギーの高効率的使用を可能にし、人と環境にやさしい"高次機能調和材料"の創製と高効率エネルギー変換・物質合成プロセスの開発を目指した。昨年度に得た成果を更に発展させ、光合成材料の開発と光電荷分離・輸送系、エネルギー変換系の構築、並びに超分子やタンパク、酵素、固定化触媒も利用する環境に優しい物質変換プロセスの開発を推進した。
平成15年度の実施計画を以下に示す。
1)らせんキラルな有機金属高分子の光および電気的機能を探索し、外部刺激応答性分子素子を創製した(高橋)。2)DNAの光増感-電子酸化反応によるDNAの超寿命電荷分離を実現するため、DNA中の電荷移動過程を解明した(真嶋)。3)基質結合型異物排出タンパクの構造を解き、異物認識機構を解明した。異物排出タンパクの発現制御機構を網羅的に解析した(山口)。4)界面活性モノマーやジアルキルジスルフィドの自己組織化を利用して構築したナノ粒子の機能化により回収再利用可能な不斉触媒や固体電解質を創製した(笹井)。
3:〔極微プロセッシング〕:本グループでは、高次機能調和型センサ・メモリの開発のため、半導体表面の無欠陥・完全化を行い、表面上の特定原子種の選択除去によるナノスケール・パターンニング加工法を確立し、メモリ材料としてのナノ薄膜構造、ナノ粒子構造を電子線ナノ構造解析により調べ、それらの構造制御法を確立することを目的とした。
平成15年度の実施計画を以下に示す。
1)Si、InP等の表面励起プロセシングの完全化と高速化、および新規の誘起構造創製法を確立する為、励起源として波長可変フェムト秒パルスレーザーと低速高分解能電子ビーム、および、両者を協調的に併用した表面励起プロセシングの研究を行った(谷村)。2)相変態型Ge-Sb-Teアモルファス・メモリ薄膜材料の局所構造、電子状態、ならびに、極限ナノサイズ・ハード磁性FePt規則合金粒子の構造を電子線ナノ構造解析により行い、これらの構造制御へのフィードバックを行った(弘津)。

Research Products

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• [Publications] T.Kanki: "Nanoscale observation of room-temperature ferromagnetism on ultrathin (La,Ba)MnO_3 films"Appl.Phys.Lett.. 83. 1184-1186 (2003)
• [Publications] Y.G.Park: "CuPc/PbZr_<0.2>Ti_<0.8>O_3/(La,Ba)MnO_3 field effect transistor heterpjunction photomemory"Solid State Electronics. 47. 2221-2224 (2003)
• [Publications] D.H.Kim: "Investigations on the nature of observed ferromagnetism and possible spin polarization in Co-doped anatase TiO_2 thin films"J.Appl.Phys.. 93. 6125-6132 (2003)
• [Publications] T.Kanki: "Magneto-transport properties of La_<0.8>Ba_<0.2>MnO_3/Antiferromagnetic LaMO_3 (M=Cr,Fe) perovskite tri-layered films"J.Appl.Phys.. 93. 4718-4721 (2003)
• [Publications] Y.Yamamoto: "Appearance of magnetic blocking temperature in zinc magnesium ferrite thin flms"J.Magn.Magn.Mat.. 261. 263-268 (2003)
• [Publications] D.-W.Kim: "Influence of microstructures on exchange bias behaviors of La_<0.7>Sr_<0.3>MnO_3/La_<0.33>Ca_<0.67>MnO_3 bilayers"Solid State Commun.. 125. 305-309 (2003)
• [Publications] M.Taniguchi: "Electrical Properties of Poly(dA)-Poly(dT) and Poly(dG)-Poly(dC) DNA Doped with Iodine Molecules"Jpn.J.Appl.Phys.. 42. 215-216 (2003)
• [Publications] H.Hashimoto: "MBE growth and properties of GaCrN"J.Crystal Growth.. 251. 327-330 (2003)
• [Publications] H.Katayama-Yoshida: "Materials design for semiconductor spintronics by ab initio electronic -structure calculation [Invited Paper]"PhysicaB. 327. 337-343 (2003)
• [Publications] H.Katayama-Yoshida: "Engineering of nested Fermi surface and transparent conducting p-type Delafossite CuAlO_2 : Possible Lattice Instability or Transparent Superconductivity?"Solid State Communications. Vol.126. 135-139 (2003)
• [Publications] K.Sato: "Curie temperatures of III-V diluted magnetic semiconductors calculated from first-principles in mean field approximation [Invited Paper]"J.Supercond.Inc.Novel Magnetism. 16. 31-35 (2003)
• [Publications] H.Katayama-Yoshida: "Spin and Charge Control Method of Ternary II-VI and III-V Magnetic Semiconductors for Spintronics : Theory vs. Experiment [Invited Paper]"J.Phys.Chem.Solid. 64. 1447-1452 (2003)
• [Publications] T.Koyanagi: "Materials Design for the Fabrication Transparent Conducting Oxides of p-type Delafossite CuAlO_2 by Super-cell FLAPW Method"J.Phys.Chem.Solid. 64. 1443-1446 (2003)
• [Publications] Y.Yamazaki: "A Structural study of CN treated amorphous silicon"Solid State Commun.. 126. 597-600 (2003)
• [Publications] H.Katayama-Yoshida: "Materials design for semiconductor spintronics by ab initio electronic-structure calculation [Invited Paper]"Physics B. 327. 337-343 (2003)
• [Publications] H.Nakayama: "Direct Conversion of graphite into diamond through electronic excited states [Invited Paper]"J.Phys, : Condens.Matter.. 15. R1077-R1091 (2003)
• [Publications] K.Yamauchi: "Charge and Spin States of Transition-Metal Atoms in a Hemoprotein based on the Extended Haldane-Anderson Model"J.Phys.Soc.Japan. 72. 2029-2032 (2003)
• [Publications] M.Seike: "Materials Design of 4d-Transition-Metal-Doped Transparent and Half-Metallic Ferromagnets with K2S-Based Diluted Magnetic Semiconductors"Jpn.J.Appl.Phys.Let.. 42. L1061-L1063 (2003)
• [Publications] Van An Dinh: "Tc-Enhanced Codoping Method for GaAs-Based Dilute Magnetic Semiconductors"Jpn.J.Appl.Phys.. 42. L888-L891 (2003)
• [Publications] H.Katayama-Yoshida: "Theoretical Aspect of Doping of Photovoltaic Materials[Invited Paper]"Mat.Res.Soc.Symp.Proc.. 763・B1.1. 3-12 (2003)
• [Publications] H.Asahi: "New III-V-based magnetic semiconductors and quantum nano-structures"J.Korean Phys.Soc.. 42. S499-S503 (2003)
• [Publications] M.Hashimoto: "Magnetic and optical properties of GaMnN grown by ammonia source molecular beam epitaxy"J.Cryst.Growth. 252. 499-504 (2003)
• [Publications] M.Hashimoto: "MBE growth and properties of GaCrN"J.Cryst.Growth. 251. 327-330 (2003)
• [Publications] H.J.Lee: "Gas source MBE growth of TlInGaAs/InP laser diodes and their room temperature operation"J.Cryst.Growth. 251. 800-803 (2003)
• [Publications] Y.-K.Zhou: "Room Temperature Ferromagnetism in III-V-Based Diluted Magnetic Semiconductor GaCrN Grown by ECR Molecular-Beam Epitaxy"Journal of Superconductivity : Incorporating Novel Magnetism. 16・1. 37-40 (2003)
• [Publications] H.Asahi: "New III-V-based magnetic semiconductors and their optical and magnetic properties"Proc.of SPIE. 4999. 221-228 (2003)
• [Publications] S.Nishida: "Electric field emission from nitride semiconductor grown on Mo substrate"Phys.Stat.Sol.(c). 0・7. 2416-2419 (2003)
• [Publications] M.Hashimoto: "Structural and magnetic properties of rare-earth-doped diluted magnetic semiconductor GaGdN"Phys.Stat.Sol.(c). 0・7. 2650-2653 (2003)
• [Publications] Y.K.Zhou: "Optical and magnetic properties of DyN/GaN superlattice"Phys.Stat.Sol.(b). 240・2. 440-442 (2003)
• [Publications] H.Tanaka: "Magnetic properties of rare-earth-doped semiconductor GaEuN"Phys.Stat.Sol.(c). 0・7. 2864-2868 (2003)
• [Publications] M.Hashimoto: "Magnetic properties of Eu-doped GaN grown by plasma-assisted molecular beam epitaxy"Jpn.J.Appl.Phys.. 42・10A. L1112-L1115 (2003)
• [Publications] A.Imada: "Reduced temperature-dependence of refractive-index in T1InGaAs quaternary alloys grown on InP substrates"J.Appl.Phys.. 94・10. 6976-6978 (2003)
• [Publications] A.Fujiwara: "Observation of small temperature variation of longitudinal-mode peak wavelength in TlInGaAs/InP laser diodes"Jpn.J.Appl.Phys.. 42・11B. L1359-L1361 (2003)
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• [Publications] Yu.Ermolenko: "The double K^+/Ca^<2+> sensor based on laser scanned silicon transducer (LSST) for multi-component analysis"Talanta. 59. 785-795 (2003)
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• [Publications] S.Kodera: "Detection of protein-protein interactions on SiO_2/Si surfaces by spectroscopic ellipsometry"Analytical Biochemistry. 321. 65-70 (2003)
• [Publications] Yu.Mourzina: "K^+-selective field-effect sensors as transducers for bioelectronic applications"Electrochimica Acta. 48. 3333-3339 (2003)
• [Publications] T.Yoshinobu: "Portable light-addressable potentiometric sensor (LAPS) for multisensor applications"Sensors and Actuators B. 95. 352-356 (2003)
• [Publications] A.B.Md.Ismai: "Investigation on light-addressable potentiometric sensor as a ppossible cell-semiconductor hybrid"Biosensors and Bioelectronics. 18. 1509-1514 (2003)
• [Publications] A.Poghossian: "Flow-velocity microsensors based on semiconductor field-Effect structures"Sensors. 3. 202-212 (2003)
• [Publications] K.Sudoh: "Step dynamics in faceting on vicinal Si(113) surfaces"J.Phys.Condens.Matter.. 15. S3241-A3253 (2003)
• [Publications] S.Antoranz Contera: "Ambient STM and in-situ AFM study of nitrite reductase proteins adsorbed on gold and graphite"Ultramicroscopy. 97. 65-72 (2003)
• [Publications] H.Iwasaki: "Nanolithography on SiO_2/Si with a scanning tunnelling microscope"Nanotechnology. 14. R55-R62 (2003)
• [Publications] F.Takei: "Preparation and photochemical properties of polyisocyanides with regularly arranged porphyrin pendant"Chem.Lett.. 32. 506-507 (2003)
• [Publications] N.Hida: "Synthesis and property of helical-chiral polyisocyanides bearing ferrocenyl groups as pendants"Angew.Chem.Int.Ed.. 42. 4349-4352 (2003)
• [Publications] K.Shiga: "Chiroptical properties of helical poly(aryl isocyanide)s bearing μ-substituted azobenzene moiety"Trans.Mater.Res.Soc.Jpn.. 28. 557-560 (2003)
• [Publications] K.Onitsuka: "A divergent approach to the precise synthesis of giant organometallic dendrimers using platinum-acetylides as building blocks"Chem.Commun. 2003. 280-281 (2003)
• [Publications] K.Onitsuka: "Metallodendrimers composed of organometallic building blocks"Top.Curr.Chem.. 228. 36-63 (2003)
• [Publications] K.Kawai: "Formation of prene dimer radical cation in DNA reflecting DNA dynamics in the time range of 1 μs to 1 ms"J.Am.Chem.Soc.. 125・4. 912-915 (2003)
• [Publications] A.Ouchi: "A two-color laser photolysis methods for determining reaction rates of short-lived intermediates by product analysis : applictaion to the o-inodimethane problem"J.Am.Chem.Soc.. 125・4. 912-915 (2003)
• [Publications] X.Cai: "Naphthalene in the higher triplet excited state"Chem.Commun.. 2003・2. 222-223 (2003)
• [Publications] X.Cai: "Sensitized reactions of benzophenone in the higher triplet excited state"Chem.Phys.Lett.. 371・1-2. 68-73 (2003)
• [Publications] T.Takada: "Hole transfer in DNA : DNA as a scaffold for hole transfer between two organic molecules"Tetrahedron Lett.. 44. 3851-3854 (2003)
• [Publications] K.Kawai: "Kinetics of weak distance dependent hole transfer in DNA by adenine hopping mechanism"J.Am.Chem.Soc.. 125・23. 6842-6843 (2003)
• [Publications] F.Takei: "Preparation and photochemical properties of polyisocyanides with regularly arranged porphyrin pendants"Chem.Lett.. 32・6. 506-507 (2003)
• [Publications] M.Hara: "Three-color three-laser photochemistry of di(p-methoxyphenyl)methyl chloride"J.Phys.Chem.A. 107・24. 4778-4783 (2003)
• [Publications] H.Harada: "Ionization and hragmentation of some chlorinated compounds and dibenzo-p-dioxin with an intense femtosecond laser pulse at 800 nm"J.Phys.Chem.A. 107・34. 6580-6586 (2003)
• [Publications] X.Cai: "Transient phenomena of dibenz[a,h]anthracene in the higher triplet excited states"Tetrahedron Lett.. 44・32. 6117-6120 (2003)
• [Publications] M.Endo: "Photoisomerization of 2'-deoxyribofuranosyl and ribofuranosyl 2-phenylazoimidazole"Tetrahedron Lett.. 44・36. 6903-6906 (2003)
• [Publications] X.Cai: "Rapid cleavage of naphthylmethy1-O bond in the higher triplet excited states"Chem.Commun.. 2003. 2604-2605 (2003)
• [Publications] X.Cai: "Benzophenones in the higher triplet excited states"Photochem.Photobiol.Sci.. 2. 1209-1214 (2003)
• [Publications] M.Endo: "Tandem double helix nano-structures using interstrand crosslinked DNA with maleimide linkers"Angew.Chem.Int.Ed.Engl.. 2003. 5744-5747 (2003)
• [Publications] M.Endo: "Control of a double helix assembly by use of crosslinked oligonucleotides"J.Am.Chem.Soc.. 125. 13654-13655 (2003)
• [Publications] K.Kawai: "Long-lived charge-separated state leading to DNA damage through hole transfer"J.Am.Chem.Soc.. 125. 16198-16199 (2003)
• [Publications] K.Kawai: "Effects of base pairing on the one-electron reduction rate of cytosine"Chem.Commun.. 2003. 2840-2841 (2003)
• [Publications] T.Tachikawa: "One-electron oxidation of aromatic sulfides adsorbed on the surface of TiO_2 particles studied by time-resolved diffuse reflectance spectroscopy"Chem.Phys.Lett.. 382. 618-625 (2003)
• [Publications] K.Kawai: "Excess electron transfer in DNA studied by pulse radiolysis and γ-radiolysis of naphthalimide and iodouridine containing ODN"J.Phys.Chem.B. 107・46. 12838-12841 (2003)
• [Publications] T.Takada: "Kinetics of multi-step hole transfer in DNA by monitoring the transient absorption of pyrene radical cation"J.Phys.Chem.B. 107・50. 14052-14057 (2003)
• [Publications] 川井清彦: "ピレン修飾DNAを用いたDNA中のホール移動"有機合成化学協会誌. 61・6. 614-619 (2003)
• [Publications] M.L.Patil: "Design and synthesis of novel spiro pyridinium and quinolinium salts"Heterocycles. 61. 581-586 (2003)
• [Publications] S.Takizawa: "Metal-bridged polymers as insoluble multicomponent asymmetric catalysts with high enantiocontrol : An approach for the immobilization of catalysts without using any support"Angew.Chem., Int.Ed.. 42・46. 5711-5714 (2003)
• [Publications] K.Marubayashi: "Monolayer-protected Au cluster (MPC)-supported Ti-BINOLate complex"Org.Lett.. 5・23. 4409-4412 (2003)
• [Publications] S.Takizawa: "Synthesis of novel chiral spiro bis(pyrazole) ligands"Heterocycles. 60・11. 2551-2556 (2003)
• [Publications] T.Sekiguti: "Polymer supported bisBINOL ligands for the immobilization of multicomponent asymmetric catalysts"Org.Lett.. 5・15. 2647-2650 (2003)
• [Publications] C.Muthiah: "Enantioselective synthesis of α-methylene-γ-butyrolactones using chiral Pd(II)-SPRIX catalyst"Tetrahedron Lett.. 44・28. 5201-5204 (2003)
• [Publications] D.Jayaprakash: "Enantioselective epoxidation of α,β-unsaturated ketons using polymer-supported lanthanoid-BINOL complexes"Tetrahedron : Asymmetry. 14・11. 1587-1592 (2003)
• [Publications] D.Jayaprakash: "Catalytic asymmetric epoxidation of α,β-unsaturated ketons using polymeric BINOL"J.Mol.Catal.A : Chem. 196・1-2. 145-149 (2003)
• [Publications] T.Arai: ""Catalyst analogue" : A concept for constructing multicomponent asymmetric catalysts (MAC) using a polymer support"Angew.Chem., Int.Ed.. 42・19. 2144-2147 (2003)
• [Publications] M.A.Arai: "Synthesis of new chiral bis(isoxazoline) ligands containing spiro[5.5]undecane skelton"Chirality. 15・1. 101-104 (2003)
• [Publications] T.Shinohara: "The first enantioselective intramolecular amino-carbonylation of alkynes promoted by Pd(II)-spiro bis(isoxazoline) catalyst"Tetrahedron Lett.. 44・4. 711-714 (2003)
• [Publications] T.Shinohara: "Synthesis and character of new bis(isoxazoline) ligands"Heterocycles. 59・2. 587-593 (2003)
• [Publications] M.Sasaki: "Cloning of rat ABCA7 and its preferential expression in platelets"Biochem Biophys Res Commun. 304. 777-782 (2003)
• [Publications] N.Kobayashi: "Membrane topology of ABC-type macrolide antibiotic exporter MacB in Escherichia coli"FEBS Lett. 546. 241-246 (2003)
• [Publications] K.Nishino: "Roles of TolC-dependent multidrug transporters of Escherichia coli in resistance to beta-lactams"Antimicrob Agents Chemother. 47. 3030-3033 (2003)
• [Publications] H.Hirakawa: "B-lactam resistance modulated by the overexpression of response regulators of two-component signal transduction systems in Escherichia coli"J Antimicrob Chemother. 52. 576-582 (2003)
• [Publications] S.Murakami: "Multidrug-exporting secondary transporters"Curr Opin Struct Biol. 13. 443-452 (2003)
• [Publications] N.Tamura: "Mechanisms of drug/H^+ antiport : complete cysteine-scanning mutagenesis and the protein engineering approach"Curr Opin Chem Biol. 7. 570-579 (2003)
• [Publications] 村上聡: "多剤排出トランスポーターAcrBの結晶構造解析"構造生物学. 4. 155-160 (2003)
• [Publications] 村上聡: "大腸菌多剤排出トランスポーターAcrBの結晶構造解析"放射光. 16. 204 (2003)
• [Publications] 村上聡: "大腸菌多剤排出トランスポーターAcrBの結晶構造解析"日本結晶学会誌. 45. 256-261 (2003)
• [Publications] T.Fujita: "Identification of a tissue-non-specific homologue of axonal fasciculation and elongation protein zeta-1"Biochem.Biophys.Res.Commun.. 313. 738-744 (2003)
• [Publications] X.Zhang: "Overexpression of Nell-1, a craniosynostosis-associated gene, induces apoptosis in osteoblasts during craniofacial development"J.Bone and Mineral Res.. 18. 2126-2134 (2003)
• [Publications] 近藤昭彦: "中空バイオナノ粒子によるピンポイントドラッグデリバリーシステム"化学工学. 67. 686-688 (2003)
• [Publications] C.Ogino: "Phospholipase D from Streptoverticillium cinnamoneum : protein engineering and application for phospholipid production"J.Mol.Cat.. B23. 107-115 (2003)
• [Publications] K.Kataoka: "Alteration of substrate specificity of leucine dehydrogenase by site-directed mutagenesis"J.Mol.Cat.. B23. 299-309 (2003)
• [Publications] D.Sun: "Chemical and kinetic reaction mechanisms of quinohemoprotein amine dehydrogenase from Paracoccus denitrificans"Biochemistry. 42. 10896-10903 (2003)
• [Publications] 田中秀和, 川合知二(分担執筆): "基礎から学ぶナノテクノロジー:ナノ加工技術 〜先端・新機能デバイスの創製〜"化学同人. 276 (2003)
• [Publications] 田中秀和, 川合知二(分担執筆): "ナノテクノロジーハンドブック"オーム社. 992 (2003)
• [Publications] 朝日一(分担執筆): "新訂版・薄膜作製応用ハンドブック"エヌ・ティ・エス. 1330 (2003)
• [Publications] 弘津禎彦: "ナノメタルの最新技術と応用開発(Advanced Technology and Application of Nano Metals)第4章 分析・解析技術"シーエムシー出版. 300 (2003)
• [Publications] T.Majima: "Charged Particle and Photon Interactions with Matter : Chemical, Physicochemical, and Biological Consequences with Applications"Marcel Dekker(in press). (2004)
• [Publications] K.Kawai, T.Majima: "Electron Transfer in DNA for Topics in Current Chemistry"Springer-Verlag(in press). (2004)
• [Publications] S.Gonda, H.Asahi (分担執筆): "Encyclopedia of Nanoscience and Nanotechnology"Marcel Dekker, Inc.(in press). (2004)