新高温超伝導酸化物の化学設計とプロセッシング・第2班(材料プロセス班)

1989 Fiscal Year Annual Research Report

• Project/Area Number: 01645004
• Research Institution: Tokyo University of Science
• Principal Investigator: 笛木 和雄 東京理科大学, 理工学部・工業化学科, 教授 (80010750)
• Co-Investigator(Kenkyū-buntansha): 岸尾 光二 東京大学工学部工業化学科, 講師 (50143392) ; 川合 知二 大阪大学産業科学研究所, 助教授 (20092546) ; 堂山 昌男 名古屋大学材料機能工学科, 教授 (40010748) ; 石田 洋一 東京大学生産技術研究所第4部, 教授 (60013108) ; 鯉沼 秀臣 東京工業大学工業材料研究所, 教授 (70011187)
• Keywords: 酸化物高温超伝導体 / 酸素ノンストイキオメトリー / 価数 / 超伝導薄膜 / ゾルーゲル法 / 臨界電流密度

Research Abstract

高温超伝導酸化物はドーピングと酸素処理によってCuの価数が変化し導電性や超伝導特性が決まるので、酸素ノンストイキオメトリの測定やCuの価数の決定は必要である。(La_<1-x>Mx)_2CuO_<4-δ>,(Nd_<1-x>Ce_x)_2CuO_<4-δ>,Bi_2Sr_2CaCu_2O_yについて酸素ノンストイキオメトリが決定された。またNd系ではCeやBiも複数の価数をとり得るので、個別の価数決定が必要で、選択的に起こる酸化還元反応を利用して個別決定に成功した。また超伝導体生成条件を示すTーlogPo_2状態図も作成された。固体電池を用いてBa_2HoCu_3O_<4-δ>の酸素ノンストイキオオメトリも決定され、また、LnーLn'ーSrーCuーO系のT,T'T"相の生成の結晶化学的研究も行われた。プロセッシングに関連しては Bi_2Sr_2CaCu_2O_yの単結晶(サイズ18×7×1mm^3)が自己フラックス法で作成された。また厚膜やフアイバーを作成を目指してゾルーゲル法の研究が進められた。この方法はいかなる形状のものもつくることができるという利点があるが、多量の溶媒を含むために、多孔質となり空洞を生成し易い欠点がある。分解反応の研究を通して改善策を見出しつつある。また泳動電着法により各種形状の超伝導体を作成している。薄膜製造プロセスではレーザーアブレーション法を用い人工的に層制御することに成功しており、またBi系薄膜を紫外光,オゾン,酸素プラズマで処理することによりTcが変わることも見出している。磁気シールド応用への基礎研究として、超伝導酸化物多結晶体に外部磁場を作用させた時の磁場の侵入状況を克明に追跡しており、Jcを高めるために異物を添加することも試みられている。Bi系酸化物の酸素吸脱着挙動の解明も進んでいる。

Research Products

• [Publications] 笛木和雄: "高温超伝導酸化物の化学" SUT BULLETIN. 9-18 (1990)
• [Publications] K.Fueki and Y.Idemoto: "High T_c Superconducting Oxides and Solid State Chemistry" Mol.Cryst.Liq.Cryst.(1990)
• [Publications] K.Fueki,Y.Idemoto and H.Ishizuka: "Oxygen Nonstichiometry of Y(Ba_<1-x>Sr_x)_2Cu_307-_δ" Physica C. (1990)
• [Publications] Y.Idemoto,K.Fueki and T.Shinbo: "Tーlog Po_2 Diagram and Copper Valence of Nd_<1.85>Ce0.15温CuO_<4-δ>" Physica C. (1990)
• [Publications] K.Kishio,K.Suzuki,T.Hasegawa,T.Yamamoto,K.Kitazawa and K.Fueki: "Study on Chemical Diffusion of Oxygen in Ba_2YCu_3O_<7-δ>." Journal of solid State Chemistry. 82. 192-202 (1989)
• [Publications] 元平直文,桑原和幸,長谷川哲也,岸尾光二,北沢宏一: "フローティングゾーン法によるBl_2Sr_2Ca_<n-1>Cu_nO_yの単結晶育成" 日本セラミックス協会学術論文誌. 97. 1009-1014 (1989)
• [Publications] T.Nonaka,M.Green,K.Kishio,T.Hasegawa,K.Kitazawa,K.Kaneko and K.Kobayashi: "BiーPbーSrーCaーCuーO Films Fabricated by Dip Coating Using the AlkoxideーAlkanolamine Method." Physica C. 160. 517-523 (1989)
• [Publications] K.Suzuki,K.Kishio,T.Hasegawa and K.Kitazawa: "Oxygen Nonstolchiometry of(Nd,Ce)_2CuO_<4-δ> System." Physica C. (1990)
• [Publications] K.Kishio,M.L.Green,K.Nakatani and K.Kitazawa: "Processing Effects on Microstructure, Flux Pinnimg and Critical Current Densitiy of Cuprate Supercondcutors." Mol.Cryst.Liq.Cryst.(1990)
• [Publications] 岸尾光二: "ノベルマテリアルーその原理と夢:酸化物超伝導体" 季刊化学総説. 5. 92-105 (1989)
• [Publications] N.Ohashi: "Preparation of(Nd,Sr,Ce)_2CuOx Type Compounds in a GdーLaーSrーCuーO System" Jpn.J.Appl.Phys.28. L1148-L1150 (1989)
• [Publications] N.Ohashi: "The Structural Feature and the Electrical Properties of the(Ln_<1-x-y>,Ln^1_x,Sr_y)_2CuO_<4-δ>T^*ーPhase Compounds" Physica C.
• [Publications] TaeーHyun SUNG: "Ba_2YCu_3O_<7-ν>の合成に対するBa塩の影響" 日本セラミックス協会学術論文誌. 97. 1039-1043 (1989)
• [Publications] Toshio Maruyama: "Phase Relation in BaBiO_<3-x> by Coulometric Titration Oxides" Solid State Ionics. 36. 121-126 (1989)
• [Publications] Tooru Atake: "Thermodynamic Studies of the HighーT_c Oxide Superconductor Ba_2T_mCu_3O_7" Thermochimica Acta. 139. 169-179 (1989)
• [Publications] Yasutoshi Saito: "電量滴定法による酸化物超伝導体Ba_2HoCu_3O_<7-y>の不定比性" 日本金属学会平成元年度秋期大会講演概要集. 635 (1989)
• [Publications] N.Ichinose: "Preparation and Superconducting Properties of the BiーSrーCaーCu System" Advances in Foeeites(Proc.ICFー5,India). 679-683 (1989)
• [Publications] 真岩宏司: "BiーPbーSrーCaーCuーO系超伝導厚膜の作成と評価" 粉体および粉末治金. 36. 518-522 (1989)
• [Publications] N.Ichinose: "Preparation of Superconducting Oxide Thick Films in the BiーSrーCaーCuーO System" Ferroelectrics. 92. 159-166 (1989)
• [Publications] N.Ichinose: "Superconducting Properties of BiーSrーCaーCuーO Single Crystals" Proc.First Inter Ceramic Sci,& Tech.Cong.
• [Publications] H.Maiwa: "Crystal Growth of the BiーSrーCaーCuーO Superconductor" 粉体および粉末治金.
• [Publications] N.Ichinose: "Preparation and Superconducting Properties of Thick Films in the BiーSrーCaーCuーO System with Addition of Pb" Proc.1989 Inter.Conf.on Chemical Congress of Pacific Basin Societies.
• [Publications] A.Kikuchi: "Influence of Cooling Rate on Superconducting Charactcristics of BiーSrーCaーCuーO Ceramics" Jpn.J.Appl.Phys.28. L371-L372 (1989)
• [Publications] A.Ito: "Influence of Intermediate Pressing on Superconducting Characteristics in BiーPbーSrーCaーCuーO System" Jpn.J.Appl.Phys.28. L380-L381 (1989)
• [Publications] M.Matsuda: "Effect of Annealing on Superconductivity in BiーPbーSrーCaーCuーO System." Jpn.J.Appl.Phys.28. L940-L942 (1989)
• [Publications] Y.Iwai: "Formation of the HighーT_c Phase of Bi_<1-x>Pb_x Sr_<0.90> Ca_<1.10> Cu_<1.50> O_υ(0≦X≦0.05)" Jpn.J.Appl.Phys.28. L1518-L1520 (1989)
• [Publications] 高田雅介: "セラミック超電導材料" 長岡技術科学大学研究報告. 99-106 (1989)
• [Publications] H.Yamanaka: "Preparation of superconducting BiーPbーSrーCaーCuーO Glass Ceramics with T_<c.zevo>=106k" Jpn.J.Appl.Phys.28. L2185-L2187 (1989)
• [Publications] N.Koura,H.Shoji,A.Morita: "Perparation of various shape surperconducting ceramics with various substrates by electrophoretic deposition method" Mol.Cryst.Lig.Cryst.
• [Publications] H.Shoji and N.Koura: "Preparation of various shap superconductor with various substrate by electrophoretic deposition methodーstudies on the electrolyte" Prating.
• [Publications] 小浦,南,出口: "泳動電着法を応用した各種形状・各種基板の超伝導体の作製ー下地金属の検討ー" 表面技術.
• [Publications] S.Hirano: "Synthesis of Ba_2YCu_3O_<7-δ> Superconductor Through Organometallic Route" Bull.Chem.Soc.Japan. 62. 888-892 (1989)
• [Publications] S.Hirano: "Preparation of Ba_2YCu_3O_<7-δ> Thin Films with Preferred Orientation through on Organometallic Route" J.Amer.Ceram.Soc.
• [Publications] S.Hirano: "Preparation of Superconducting BiーSrーCaーCuーO Filme with Preferred Orientation through a Metal Alkoxide Route" Jpn.J.Jap.Appl.Phys.
• [Publications] Haoren Zhuang: "Preparation of BiーPbーSrーCaーCuーO Superconducting Fibers by the SolーGel Method" Japanese Journal of Applied Physics. 28. L1805-L1808 (1989)
• [Publications] Haoren Zhuang: "Preparation of Superconducting BiーSrーCaーCuーO Ceramics by SolーGel Method" Journal of Materials Science.
• [Publications] Sumio Sakka: "Superconducting Oxides Prepared by SolーGel Process" In"Chemical Aspects of High Tc Superconductors"Proc.1989 International Chemical Congress of Pacific Basin Societies,Honolulu,1989.
• [Publications] 梅田鉄: "YBa_2Cu_3O_<7-υ> 超伝導体の前駆体としての金属酢酸塩ゲルの熱分解" 日本セラミックス協会学術論文誌.
• [Publications] 吉本護: "Superconductivity in a New Oxide System of EuーLaーCeーCuーO" Jpn.J.Appl.Phys.28. L1115-L1117 (1989)
• [Publications] 竹内功: "Oxygen Control in Bi_2Sr_2CaCu_2O_x Superconducting Thin Films by Activated Oxygens" Jpn.J.Appl.Phys.29. L70-L72 (1990)
• [Publications] 鯉沼秀臣: "Superconductivity in EuーLaーCeーCuーO system" Molecular Crystals and Liquid Crystals. Feb. (1990)
• [Publications] 吉本護: "Preparation of CeーDoped Thin Films of LnーCuーO systems by Sputtering" Molecular Crystals and Liquid Crystals. Feb. (1990)
• [Publications] 竹内功: "Oxygen Control and Carrier Property in Bi_2Sr_2Ca,Cu_2O_x Superconducting Thin Films" Molecular Crystals and liquid Crystals. Feb. (1990)
• [Publications] T.Kawai: "Effect of Alkaline Netal Substitution to BiーSrーCaーCuーO Superconductor" Physica C. 161. 561-566 (1989)
• [Publications] H.Tabata: "Formation of the HighーTc Phase of the Superconducting BiーSrーCaーCuーO Thin Film by Laser Ablation" Jpn.J.Appl.Phys.28. L430-L433 (1989)
• [Publications] M.Kanai: "Low Temperature Formation of Multiーlayered Bi(Pb)ーSrーCaーCuーO Thin Films by Successive Deposition by Laser" Appl.Phys.Lett.54. 1802-1804 (1989)
• [Publications] H.Tabata: "Tailored Thin Films of Superconducting BiーSrーCaーCu Oxide Prepared by Excimer Laser Ablation Technique." Jpn.J.Appl.Phys.28. L823-L826 (1989)
• [Publications] Tomoji.Kawai: "Basic Structures of High Tc Oxide Superconductors" Progress in High Tc Superconductivity. 15. 201-207 (1989)
• [Publications] 川合知二: "高温超伝導体のレーザーアブレーションと薄膜形成" 光化学. 13. 88-93 (1989)
• [Publications] 石田洋一: "超伝導内部界面の原子構造" 表面科学. 10. 856-862 (1989)
• [Publications] 石田洋一: "高温超伝導セラミック焼結体結晶粒界の高分解能電顕解析" 材料科学. 25. 284-289 (1989)
• [Publications] Y.Takahashi: "Preferential Growth of〔001〕Twist Boundaries in BSCCO" Appl.Phys.Lett.55. 486-488 (1989)
• [Publications] 高橋裕: "電子顕微鏡によるYBa_2Cu_3O_<7-x>およびBi(Pb)ーSrーCaーCuーOを超伝導酸化物中の転位の解析" 日本金属学会誌. 53. 494-501 (1989)
• [Publications] Y.Takahashi: "Transmission Electron Micrscopy of Grain Boundaries in Oxide Superconductors" MRS International Meeting on Advanced Materials. 6. 297-302 (1989)
• [Publications] Y.Ishida: "High Resolution Electron Microscopy of Ceramic Interfaces" J.Electron Microscopy Technique. 12. 244-251 (1989)
• [Publications] N.Miura etal.: "Oxygen AdsorptionーDesovption Behavior and Superconducting Properties of HighーT_c Bi(Pb)ーSrーCaーCuーO" Jpn.J.Appl.Phys. 28. L1112-L1114 (1989)
• [Publications] N.Miura etal.: "Effects of Oxygen SorptionーDesorption on Superconductivity of HighーT_c Bi(Pb)ーSrーCaーCuーO" Mol.Cryst.Liq.Cryst.
• [Publications] K.Ishikawa,H.Matsuoka,M.Matsui,M.Doyama: "Superconductivity and Magnetic Properties of YBa_2(Cu_<1-x>M_x)_3O_y,(M=Fe,Co,Ni)" Proceedings of the MRS International Meeting on Advanced Materials. 6. 347-352 (1989)
• [Publications] S.Ninagawa,M.Matsui,H.Matsuoka,M.Doyama: "Superconducting Properties and Crystal Structure of(Y_<1-x>Ce_x)Ba_2Cu_3O_y" Proceedings of the MRS International Meeting on Advanced Materials. 6. 542-545 (1989)
• [Publications] M.Matsui,K.Ishikawa,H.Matsuoka,M.Doyama,K.Nishiyama,K.Nagami: "Magnetic Ordering in Superconducting YBa_2(Cu_<1-x>Fe_x)_3O_y Oxide" Journal of Nuclear Materials. (1990)
• [Publications] H.Ito,M.Matsui,M.Doyama: "Preparation of High T Phase of BiーSrーCaーCuーO by the Addition of Ca_2Pbδ_4" Proceeding of the 2nd International Symposium on Superconductivity(ISS'89),Tsukuba,1989. (1990)
• [Publications] M.Doyama,M.Matsui,H.Matsuoka,K.Ishikawa,E.Hayashi,K.Nishiya,K.Nagamine: "Magnetic Phase Diagram of YBa_2(Cu_<1-x>Fe_x)_3O_y and YBa_2(Cu_<1-x>Co_x)_3O_y" Proceeding of the International Conference of MRS(MRS'89)Boston,1989. (1990)
• [Publications] Naoki Yamamoto et al.: "Superspace Group Analysis of the Modulated Structure in Superconductor BiーSrーCaーCuーO" Jpn.J.Appl.Phys.28. L598-L601 (1989)
• [Publications] Yoshihiko Hirotsu et al.: "Modulated Structure of the HighーTc Superconductor BiーPbーCaーSrーCuーO Studied by HighーResolution Electron Microscopy and Electron Diffraction" Jpn.J.Appl.Phys.28. L1783-L1786 (1989)
• [Publications] Yoshihiko Hirotsu et al.: "Modulated Structures of Biーbased HighーTc Superconducting Oxides" 2nd In,ternational Symposium on Superconductivity,Tsukuba,Nov.14ー17'89 Proceedings.
• [Publications] Mamoru Ishii et al.: "Magnetic Shielding Properties of YBa_2Cu_3O7_<-δ> Superconductor" Jpn.J.Appl.Phys.29.
• [Publications] Hajime Suzuki et al.: "Thin Film Structure of YBa_2Cu_3O7_<-δ> on(001)MgO Substrate Studied by TEM" Jpn.J.Appl.Phys.
• [Publications] Yoshihiko Hirotsu et al.: "Structure Modes of Incommensurate Modulation in BiーPbーSrーCaーCuーO Superconductor" Jpn.J.Appl.Phys.
• [Publications] K.Kishio,T.Hasegawa,K.Suzuki,K.Kitazawa and K.Fueki: "High Temperature Superconductors:Relationships Between Properties.Structure,and SolidーState Chemistryー1989" Materials Research Soclety, 91-97 (1989)
• [Publications] 北沢宏一、岸尾光二: "高温超電導データブックII" 丸善, 1-6 (1989)
• [Publications] Yasutoshi Saito: "NonーStoichiometric Compounds,Surfaces,Grain Boundaries and Structural Defects" Kluwer Academic Publishers, (1989)
• [Publications] 山香英三 他: "高温超伝導入門" (株)オーム社, 176 (1989)
• [Publications] 鯉沼秀臣: "「化学」" 化学同人, 2 (1989)
• [Publications] Tomoji Kawai: "Science and Technology of Thin Film Superconductors" Plenum, 6 (1989)
• [Publications] 川合知二: "最先端レーザー加工技術" CMC, 13 (1989)