新高温超伝導酸化物の化学設計とプロセッシング.第1班(新物質.新組成.相図班)

1989 Fiscal Year Annual Research Report

• Project/Area Number: 01645002
• Research Institution: Kyoto University
• Principal Investigator: 坂東 尚周 京都大学, 化学研究所, 教授 (70027027)
• Co-Investigator(Kenkyū-buntansha): 山本 治 三重大学, 工学部, 教授 (70023116) ; 三浦 嘉也 岡山大学, 工学部, 教授 (80032952) ; 小松 啓 東北大学, 金属材料研究所, 教授 (00108565) ; 小菅 皓二 京都大学, 理学部, 教授 (00025371) ; 金丸 文一 大阪大学, 産業化学研究所, 教授 (40029848)
• Keywords: 高温酸化物超伝導体 / エピタキシャル薄膜 / 単結晶 / 価数分析 / 微細構造 / 結晶構造 / 状態図 / 光学スペクトル

Research Abstract

研究成果を(1)新物質の探索、(2)状態図の作成、(3)微細構造解析と状態分布、(4)単結晶合成とその物性、の課題に分けて述べる。(1)は(a)La_<2ーx>Nd_xCuO_<4+y>、(b)La_2NiO_<4+y>、(c)BaTIO_4について検討し、(a)では高酸素圧下で合成して酸素量を変化させた結果、酸素量が多いとTcが上昇し、超伝導の体積割合は増加する。(b)および(c)では超伝導を示さない。Tc=7KのBiーSrーCuーO系にPbを置換し、少し還元するとTc=14Kの超伝導体が得られた。(2)Bi系の初晶面を検討し、またBi_2O_3ーSrOーCuO系、PbOーCaOーSrO系、Bi_2O_3ーPbOーCuO系の固相領域での状態図を正確に決定し、いくつかの新しい化合物を確認した。(3)高分解能電子顕微鏡によってYBCOの酸素量が不足した場合に正方晶と斜方晶が常に共存していることを見出し、またBi,PbーSrーCuーO系の変調構造を調べ、変調構造のない超伝導相が存在することを見出した。YBCOにFeをドープした場合、熱処理条件によってFeの分布が変化し、それが微細構造に影響し、Tcを変化させる。X線吸収スペクトルによれば、Tl系ではCuが2.2価、Tlは1価であり、TlからCuーO面へホールが供給されている。Bi系のBiとCuの価数の分析法として酸化ー還元滴定法を確立した。(4)徐冷法によってYBCO単結晶の育成を試み、単結晶のCrO_3の熱分解酸素による酸化処理に成功した。反応性蒸着法によるYBCO薄膜はRHEEDの観察によれば層状成長している。またこの単結晶薄膜を用いて角度分解光電子スペクトル、さらに高感度の磁気抵抗効果の測定を行い、電子状態に関する貴重な見知を得た。単結晶の反射スペクトルを測定し、光学常数を求めた。交互スパッタによるBi系超伝導薄膜を作製し、その微細構造を検討した。以上、本研究によって、各研究課題について多くの基礎的で重要なデータや知見が得られた。

Research Products

• [Publications] Y.Sakisaka: "AngleーResolved Photoemission Investigation of the Electronic Band Properties of YBa_2Cu_3O_<7ーx>(001)" Phys.Rev.B. 39. 9080-9090 (1989)
• [Publications] Y.Sakisaka: "AngleーResolved Photomissin from Epitaxial YBa_2Cu_3O_<7ーx>(001)Films" Phys.Rev.B. 39. 2304-2307 (1989)
• [Publications] Z.Hiroi: "Oxygen Ordering Model Describing the TwoーPhase Microstructures in YBa_2Cu_3O_<6+c>" Solid State Commu. 69. 223-228 (1989)
• [Publications] Z.Hiroi: "TwoーPhase Microstructures in YBa_2Cu_3O_y Observed by Transmission Electron Microscopy" Physica C. 158. 269-275 (1989)
• [Publications] K.Kamigaki: "Xーray Study on a 100Åーthick YBa_2Cu_3O_<7ーδ> Epitaxial Film:The Relationship between the Orthorhombic Symmetry and Superconductivity" Physica C. 159. 505-512 (1989)
• [Publications] T.Terasima: "In Situ Reflection High Energy Electron Diffraction Observation during Growth of YBa_2Cu_3O_<7ーx> Thin Films by Activated Reactive Evaporation" Jpn.J.Appl.Phys. 28. L987-L990 (1989)
• [Publications] 寺嶋孝仁: "InーSitu RHEEDによるYBa_2Cu_3O_<7ーx>の結晶成長観察" 粉体および粉末冶金. 36. 592-596 (1989)
• [Publications] 間崎啓匡: "単結晶YBa_2Cu_3O_<7ーx>の帯磁率(I)" 粉体および粉末冶金. 36. 597-600 (1989)
• [Publications] 山本和貫: "単結晶YBa_2Cu_3O_<7ーx>複素帯磁率(II)" 粉体および粉末冶金. 36. 601-604 (1989)
• [Publications] 池田靖訓: "840°Cにおける固相域でのBiO_<1.5>ーSrOーCuO系状態図" 粉体および粉末冶金. 36. 564-570 (1989)
• [Publications] Y.Bando: "Low Temperature Growth and Properties of YBCO SingleーCrystal Films" Thin Solid Films. 181. 147-155 (1989)
• [Publications] Y.Bando: "Crystal Growth and Some Properties of YBa_2Cu_3O_<7ーx> SingleーCrystal Thin Film" Proc.Tsukuba Seminar on High T_cSuperconductivity,May 31ーJune 2,1989,Tsukuba,Japan. 133-142 (1989)
• [Publications] T.Sekine: "LowーFrequency Raman Spectra in the Single Crystal YBa_2Cu_3O_<7ーδ> and the Film GdBa_2Cu_3O_<7ーδ>" Proc.Tsukuba Seminar on High T_C Superconductivity,May 31ーJune 2,1989,Tsukuba,Japan. 121-126 (1989)
• [Publications] K.Yamamoto: "ThirdーHarmonic Susceptibility in SingleーCrystal YBa_2Cu_3O_<7ーx> Thin Films" Jpn.J.Appl.Phys. 28. L1568-L1570 (1989)
• [Publications] Y.Matsuda: "Magnetoresistance of cーAxisーOriented Epitaxial YBa_2Cu_3O_<7ーx> Films above T_c" Phys.Rev.B. 40. 5176-5179 (1989)
• [Publications] T.Terasima: "Initial Stage of Epitaxial Growth of YBa_2Cu_3O_<7ーx> Thin Films" Physica C. (1990)
• [Publications] H.Mazaki: "AC Susceptibility in Single Crystal YBa_2Cu_3O_<7ーx> I" Physica C. (1990)
• [Publications] K.Yamamoto: "Ac Susceptibility in Single Crystal YBa_2Cu_3O_<7ーx> II" Physica C. (1990)
• [Publications] Y.Ochiai: "Low Temperature Transport in GdBa_2Cu_3O_y(y<6.5)" Physica C. (1990)
• [Publications] Y.Ikeda: "Bi,PbーSrーCuーO System Including a ModulationーFree Superconductor" Physica C. 165. 189-198 (1989)
• [Publications] Y.Iye: "Dissipation in the Mixed State of Conventional and High Temperature Superconductor" Physica C.
• [Publications] 坂東尚周: "反応性蒸着による酸化物のエピタキシャル成長ー人工格子と酸化物超伝導体を中心としてー" 表面. 27. 103-111 (1989)
• [Publications] 坂東尚周: "高温超伝導体薄膜の作製.評価技術の現状“薄膜化の必要性と諸問題"" 表面科学. 10. 224-231 (1989)
• [Publications] 坂東尚周: "超伝導薄膜形成プロセス" Semiconductor World. 9. 76-79 (1989)
• [Publications] 寺嶋孝仁: "高温超伝導薄膜" 応用物理. (1990)
• [Publications] H.Adachi: "Cluster Model Investigation of the Electronic State and Chemical Bond in Cuprous and Cupric Oxide" Physica C. 157. 169-179 (1989)
• [Publications] H.Maeda: "EXAFS and Neutron Diffraction Studies of Local and Average Structures for YBa_2Cu_<2.8>Zn_<0.2>O_<7ーδ>" Physica C. 157. 483-490 (1989)
• [Publications] F.Izumi: "Neutron and Electron Diffraction Study of the ElectronーDoped Superconductor Nd_<1.845>Ce_<0.155>CuO_<4ーy>" Physica C. 158. 433-439 (1989)
• [Publications] F.Izumi: "Metal Ordering and Oxygen Displacement in(Nd,Sr,Ce)_2CuO_<4ーy>" Physica C. 158. 440-448 (1989)
• [Publications] F.Izumi: "Oxygen Dificiency and Atomic displacements in Superconducting(Ba_<1ーx>Nd_x)_2(Nd_<1ーy>Ce_y)_2Cu_3O_<8+z>" Physica C. 160. 235-242 (1989)
• [Publications] 泉富士夫: "超伝導酸化物の結晶化学" 化学工業. 41. 216-221 (1990)
• [Publications] 鍋島茂之: "Bi系超伝導材料の初晶面と凝固パス" 日本金属学会誌.
• [Publications] 森山斉昭: "RFースパッタ法によって作製したYーBaーCuーO系薄膜の結晶化" 粉体および粉末冶金. 36. 123-127 (1989)
• [Publications] 鄂剛: "YーBaーCuーO系酸化物の高圧合成およびフッ素添加" 粉体および粉末冶金. 37. 172-175 (1990)
• [Publications] S.Kikkawa: "Compatible Materials with YBa_2Cu_3O_y" Mat.Res.Bull.
• [Publications] N.Moriyama: "Crystallization of Amorphous YーBaーCuーO Film Prepared by RFーSputtering" Mol.Cryst.Liq.Cryst.
• [Publications] G.Lai: "Phase Transition in BlーType Mo_<1ーx>NB_xN Sputtered Films under Ammonica Annealing" J.Solid State Chem. 82. 1-7 (1989)
• [Publications] H.Shimooka: "Microstructure and Superconducting Properties in YBCO Ceramics" Proc.Int.Symp.on.Ceramics,Areta. 214-215 (1989)
• [Publications] M.Kuwabara: "Grain Size Dependence of the Critical Current Density in YBa_2Cu_3O_x Superconductors" Appl.Phys.Lett. 55. 2781-2783 (1989)
• [Publications] M.Kuwabara: "Preparation of HighーDensity YBa_2Cu_3O_x Ceramics with Improved Superconducting Properties by HotーPressing under Controlled Atmosphere" Appl.Phys.Lett.
• [Publications] M.Kuwabara: "Correlation between Mechanical Properties and the Critical Current Density in YBa_2Cu_3O_x" Appl.Phys.Lett.
• [Publications] H.Yasuoka: "Cu Chemistry of YBa_2Cu_3O_<6+c> Investigated by Nuclear Quadrupole Resonance" Phase Transitons. 15. 183-199 (1989)
• [Publications] T.Imai: "NQR and NMR Studies of YBa_2Cu_3Ox(6.0≦x≦6.91)" Int.J.of Modern.B. 3. 93-95 (1989)
• [Publications] H.Mazaki: "Possible Existence of a Superconducting Phase in Highly OxygenーDeficient" Jpn.J.Apple Phys.28. L368-L370 (1989)
• [Publications] K.Yoshimura: "Cupper NMR and NQR in La_<2ーx>Sr_xCuo_4ーNo Evidence for Coexistence of Magnetic Ordering and Superconductivity down to 1.3K" J.Phy.Soc.Japan. 58. 3057-3060 (1989)
• [Publications] T.Imai: "Cu Spin Dynamics in HighーT_c and Related Oxides Investigated by Nuclear SpinーLattice Relaxion" J.Phys.Soc.Japan. (1990)
• [Publications] S.Katsuyama: "Ion Configuration and Superconducting Properties of YBa_2(Cu_<1ーx>Fe_x)_3O_y Prepared by various Thermal Treatments" Physica C. (1990)
• [Publications] H.Komatsu: "Discrimination between Topographic and Optical Anisotropic Features in High T_c Superconducting Crystals" J.Mat.Sci.Lett. 8. 505-506 (1989)
• [Publications] Y.Suzuki: "Synthesis and Decomposition of the HighーT_c Phase of a PbーDoped BiーSrーCaーCuーO Superconductor" Jpn.J.Appl.Phys.28. L1382-L1384 (1989)
• [Publications] S.Hayashi: "Growth and Characterization of RBa_2Cu_3O_<7ーδ>(R=Er or Gd)Single Crystals" Proc.3rd Topical Meeting on Crystal Growth Mechanism,Tokyo(1990). 107-110 (1990)
• [Publications] T.Inoue: "A Method for Improving Superconductivity in Plate Crystals of DyBa_2Cu_3O_y" Proc.9th Int.Conf.on Crystal Growth,Sendai(1989). (1990)
• [Publications] 末野重穂: "酸化物高温超伝導体の分類と結晶学的特徴" 日本結晶学会誌. 31. 119-122 (1989)
• [Publications] J.Tanaka: "Optical Spectra of Single Crystals of High T_c Superconductors" Synth.Metals. 29. F597-F602 (1989)
• [Publications] J.Tanaka: "Opical Spectra and Erectronic Structure of High T_c Oxide Superconductors" Physica C. 162ー164. 1117-1118 (1989)
• [Publications] J.Tanaka: "Electronic Structure of the CuO_2ーPlane of Cuprate Superconductors" Physica C. 161. 451-458 (1989)
• [Publications] 田仲二郎: "高温超伝導体の物性:光物性" 応用物理. 58. 719-726 (1989)
• [Publications] E.P.Okamura: "Structure and Stability of High T_c Superconductors" Proc.Special Symp.on Advanced Mater.,Tokyo. 77-82 (1989)
• [Publications] K.Nakamura: "Synthesis of Artificially Layered BiーSrーCaーCu Oxide Films and Their Thermal Stability" Jpn.J.Appl.Phys.28. L437-L440 (1989)
• [Publications] K.Nakamura: "Formation of Theramally Stable Multilayered BSCCO Films with 2223,2234 and 2245 Structures" Jpn.J.Appl.Phys.29. L77-L80 (1990)
• [Publications] K.Aota: "Growth of the 2223 Phase in Leaded BiーSrーCaーCu Oxide under Reduced Oxygen Partial Pressure" Jpn.J.Appl.Phys.28. L2196-L2199 (1989)
• [Publications] H.Hattori: "Effects of OxigenーPotentialーControlled Annealing on the Superconducting Properties of(BiPb)_2Sr_2Ca_2Cu_3O_y Thin Films" Jpn.J.Appl.Phys.29. L36-L39 (1990)
• [Publications] H.Hayakawa: "Growth of the 2223 Phase in BiーSrーCaーCu Oxide Films under a Controlled Pb Potentail" Jpn.J.Appl.Phys.28. L967-L969 (1990)
• [Publications] T.Nakamura: "Oxigen Introduction beyond the Stoichiometry of Y(Ba_<1ーx>LX_x)_2Cu_3O_7 Superconductors by Valence Regulation of BaーSite" MRS Int.Mtg.on Adv.Mats. 6. 463-466 (1989)
• [Publications] M.Yoshimura: "Preparation of BiーSrーCaーCu Superconductors from Rapidly Quenched Amorphous Films" MRS Int.Mtg.on Adv.Mats.6. 1011-1016 (1989)
• [Publications] H.Nagano: "Evidence of SrーDificiency in Bi_2Sr_<2ーα>Ca_1Cu_2O_8 and Preparation Stoichiometric Semiconducting Bi_2Sr_2Ca_1Cu_2O_8" Jpn.J.Appl.Phys.28. L364-L367 (1989)
• [Publications] M.Itoh: "Synthesis of BaTio_<2.5> with OxygenーDeficient Perovskite Structure" J.Solid State Chem. 82. 172-175 (1989)
• [Publications] M.Yoshimura: "Preparation of highーT_c(110K)BiーSrーCaーCuーO Superconductors from Amorphous Films by Rapid Quenching after Rapid Melting" J.Mater.Sci.Lett.8. 687-688 (1989)
• [Publications] T.Atake: "Specific Heat of TlーBaーCaーCuーO Superconductors" Physica C. 162ー164. 488-489 (1989)
• [Publications] R.Aoki: "CoーExistance of 3 Classes of Phase Transition up to 90K Including Superconductivity in La_<2ーx>CuO_<4ーy> System" Physica C. 162ー164. 921-922 (1989)
• [Publications] 成台鉉: "Ba_2YCu_3O_<7ーx>の合成に対するBa塩の影響" 日本セラミックス協会. 97. 1039-1043 (1989)
• [Publications] 中村哲朗: "室温超伝導体は存在するかー高温超伝導体をBCS機構で設計するー" 材料科学. 26. 240-250 (1989)
• [Publications] M.Oku: "Determination of the Oxidation States of Bithmuth and Copper in Superconductor BiーCaーSrーCuーO by OxidationーReduction Titration" Fresenius Z.Anal.Chem. 335. 382-385 (1989)
• [Publications] H.Kitaguchi: "Magnetic Suspension of a Bi,PbーSrーCaーCuーO Superconductor due to the Meissner Effect" Physica C. 157. 267-271 (1989)
• [Publications] 大橋憲太郎: "BiーSrーCaーCuーO系超伝導体の高Tc相生成に及ぼす“inert pair"元素酸化物の添加物効果" 粉体および粉末冶金. 36. 474-477 (1989)
• [Publications] 高田潤: "Bi,PbーSrーCaーCuーO系高Tc相の生成と電気特性" 粉体および粉末冶金. 36. 527-532 (1989)
• [Publications] 高田潤: "PboーROーR′O(R,R′=Ca,Sr,Cu)系状態図について" 粉末および粉末冶金. 36. 533-541 (1989)
• [Publications] 高田潤: "BiーPb系高Tc相の生成に及ぼす仮焼温度の影響" 粉末および粉末冶金. 37. 54-59 (1990)
• [Publications] 高田潤: "BiーPb系酸化物高温超伝導体のHIP処理" 粉末および粉末冶金. 37. 83-88 (1990)
• [Publications] 高田潤: "BiーPbーSrーCaーCuーO系Pb rich試料における高Tc相の生成" 粉体および粉末冶金. 37. 108-113 (1990)
• [Publications] H.Kitaguchi: "Equilibrium Phase Diagram for the System PbOーCaOーCuO" J.Mat.Res. 5. (1990)
• [Publications] Y.Takeda: "Structure and Properties of YBaSrCu_3O_y(y=6.2ー7.3)" Physica C. 157. 358-364 (1989)
• [Publications] Y.Takeda: "Annealing Effects on the PbーDoped 2223 Phase under Various Temperatures and Oxygen Pressures" Physica C. 159. 789-793 (1989)
• [Publications] 武田保雄: "La_<2ーx>Sr_xNiO_4(O【less than or equal】x【less than or equal】1.6)の構造と電気伝導" 粉体および粉末冶金. 36. 99-102 (1989)
• [Publications] Y.Takeda: "Crystal Chemistry and Physical Properties of La_<2ーx>Sr_xNio_4(0【less than or equal】x【less than or equal】1.6)" Mat.Res.Bull.25. (1990)
• [Publications] 坂東尚周: "先端材料応用事典" 産業調査会事典出版センター, 1239 (1990)
• [Publications] 坂東尚周: "超微粒子開発応用ハンドブック" サイエンスフォーラム, 406 (1989)
• [Publications] 小菅皓二: "美しい地球化学の森" 三田出版会, 130 (1989)
• [Publications] 小菅皓二: "超伝導体の化学と物理" 三共出版, 175 (1990)
• [Publications] K.Nakamura: "Studies of High Temperature Superconductors" Nova Science Publishers Inc., 402 (1989)