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)

1991 Fiscal Year Annual Research Report

• Project/Area Number: 03211103
• Research Institution: Tokyo University of Science
• Principal Investigator: 笛木 和雄 東京理科大学, 理工学部, 教授 (80010750)
• Co-Investigator(Kenkyū-buntansha): 岸尾 光二 東京大学, 工学部, 助教授 (50143392) ; 川合 知二 大阪大学, 産業科学研究所, 助教授 (20092546) ; 福長 脩 東京工業大学, 工学部, 教授 (20199251) ; 石田 洋一 東京大学, 生産技術研究所, 教授 (60013108) ; 鯉沼 秀臣 東京工業大学, 工業材料研究所, 教授 (70011187)
• Keywords: 高温超伝導酸化物 / 酸素量 / 高温導電率 / キャリア濃度 / モビルテイ

Research Abstract

高温超伝導酸化物では、金惣成分組成が同一でも、酸素圧・温度によって酸素量が変化し、酸素量によって導電性、超伝導特性が変化する。昨年度の90K級123酸化物、Bi系に引き続いて、(Nd,Ba)_2(Nd,Ce)_2Cu_3O_y、(Pb_2Cu)Sr_2CaCu_2O_yなどの銅系酸化物についてT_0と酸素量が密接な関係のあることが明かにされたのみならず、非銅系のBaPb_<1‐x>Bi_xO_<3‐δ>,Ba_<1‐x>K_xBiO_<3‐δ>などの酸化物についても同じことが見出され、酸素量の問題は超伝導機構を解明する主要な鍵の一つであることが明らかになった。金属組成の変化は、酸素量の変化を誘い、その結果超伝導特性を変化させること及び、T_0は酸素過剰量がある最適値をとる時に最高になることも、Bi系について明らかにされた。これも酸素量が超伝導にとって極めて重要な因子であることの一証左となった。多価イオンを2種以上含む高温超伝導酸化物の場合、酸素ノンストイキオメトリの変化はこれら多価イオンの価数変化となる。多価イオンの価数を多価イオンの種類別に分析する方法の研究が進められ、Bi系(2201),(2223)相のいずれも、Biイオンの価数は常に3を越えるのに対し、Cuイオンの価数はほとんど2価が、それを若干上まわる程度で、(2223)相の場合、低酸素圧側では2価を僅かながら下まわる場合も生じ、Bi系ではホ-ルはよりBiイオンに多く存在し、すべてホ-ルはCu(II)‐O_2面上に存在するとの従来の考え方は大きな修正を必要とすることが明らかとなった。酸素量の変化が最もよく反映し、かつ超伝導特性とも密接に関係のある物性は高温超電率と考えられる。Bi系3相,Y系123,124相T^*相等について、酸素圧・温度の関数として高温導電率を測定し、酸素圧・温度の関数として測定した酸素量の結果と比較した所、両者の間に極めて密接な関係のあることが明らかになり、また両結果より、高温におけるキャリア濃度、モビルテイを温度の関数として求めた。

Research Products

• [Publications] Y.Idemoto: "High Temperature Conductivity of 2212 phase of Bi‐Sr‐Ca‐Cu‐O Superconducting Oxide" Physica C. 176. 325-330 (1991)
• [Publications] Y.Idemoto: "Diffusion Coefficients of Oxygen in Nd_2CuO_<4‐δ>" J.Solid State Chem.92. 489-495 (1991)
• [Publications] Y.Idemoto: "High Temperature Conductivity of 2223 phase of Bi‐Sr‐Ca‐Cu‐O Superconducting Oxide" Physica C. 179. 96-100 (1991)
• [Publications] 井手本 康: "高温超伝導酸化物の酸素ストイキオメトリ-" 表面技術. 42. 896-903 (1991)
• [Publications] Y.Idemoto: "Oxygen Nonstoichiometry of 2223 phase Bi‐Pb‐Sr‐Ca‐Cu‐O system Superconducting Oxide" Physica C. 181. 171-178 (1991)
• [Publications] K.Fueki: "Diffusion Coefficients of Oxygen in (La_<0.88>Sr_<0.12>)_2CuO_<4‐δ> and (Nd_<0.669>Ce_<0.136>Sr_<0.195>)_2Cu_<0.974>O_<4‐δ>" Ann.Chim.Fr.16. 423-435 (1991)
• [Publications] 笛木 和雄: "高温超伝導酸化物のキャラクタリゼ-ション," NSMF NEWS,. NO.27. 1-14 (1991)
• [Publications] Y.Idemoto: "Defect Thermodynamics of Nd_<2‐x>Ce_xCuO_<4‐δ>" Jpn.J.Appl.Phys.30. 2471-2476 (1991)
• [Publications] Y.Idemoto: "Substitution of Allovalent cations for(2201)and(2212)Phases and its Effect on T_C" Physica C. 185ー189. 679-680 (1991)
• [Publications] K.Fueki: "Defect Chemistry of BaPb_<1‐x>Bi_xO_3" Physica C. 190. 6-8 (1991)
• [Publications] Y.Idemoto: "Oxygen Nonstoichiometry and High Temperature Conductivity of 2201 phase Bi‐Sr‐Cu‐O system Superconducting Oxide" Physica c. 190. 502-510 (1992)
• [Publications] Y.Idemoto: "Standard Enthalpies of Formation of Member Oxides in the Y‐Ba‐Cu‐O System" Physica C,.
• [Publications] K.Kishio: "A Novel Method to Avoid Demagnetization Effect in Magnetization Studies of Bi_2Sr_2Cacu_2O_8 Single Crystals with the field Perpendicular to the CuO_2 Plane" Physica C. 185ー189. 2377-2378 (1991)
• [Publications] K.Kishio: "Ireversibility Field and Scaling Law of Flux Pinning in a(La,Sr)_2CuO_4 Single Crystal for Magnetic Field Perpendicular to the CuO_2 Plane" Physica C. 185ー189. 2523-2524 (1991)
• [Publications] H.Nakashima: "Intercalation of Bi_2Sr_2Ca_<n‐1>Cu_nO_y with Iodine and Other Halogens" Physica C. 185ー189. 677-678 (1991)
• [Publications] M.Fukuoka: "Superconductivity Of(La,Ca)_2CuO_4 Prepared in High Oxygen Pressure" Physica C. 190. 91-92 (1991)
• [Publications] K.Kishio: "Anisotropic Magnetization,Flux Pinning and Critical Current Density of La‐Sr‐Cu‐O Single Crystal" Supercond.Sci.Technol. 印刷中. 5. (1992)
• [Publications] T.Kimura: "Compositional Dependence of Transport Anisotropy in Large(La,Sr)_2CuO_4 Single Crystals and Second Peak in Magnetization Curves" Physica C 印刷中. 191. (1992)
• [Publications] Y.Ishida: "Structure and Properties of a Bi_2Sr_2Ca_2Cu_3O_x‐Ag Nanocomposite" Physica C. 190. 67-69 (1991)
• [Publications] H.Nagata: "Growth Mechanism of Epitaxial Oxide Films by Laser MBE" Mat.Res.Soc.Symp.Proc.202. 445-450 (1991)
• [Publications] H.Koinuma: "Ceramic Layer Epitaxy by Pulsed Laser Deposition in an Ultra‐High Vacuum System" Appl.Phys.Lett.58. 2027-2029 (1991)
• [Publications] H.Nagata: "Heteroepitaxial Growth of CeO_2(001)Films on Si(001)Substrate by Pulsed Laser Deposition in Ultrahigh Vacuum" Jpn.J.Appl.Phys.30. L1136-L1138 (1991)
• [Publications] N.Tomita: "The Superconducting Properties of(001)Twist Boundaries in a Bi‐Sr‐Ca‐Cu‐O Superconductor" Jpn.J.Appl.Phys.
• [Publications] Y.Matsumoto: "^<119>Sn‐Mossbauer Spectroscopic Study of the Single Phase of Bi(Pb)‐Sr‐Ca‐Cu(Sn)‐O" Physica C.
• [Publications] N.Miura: "Relation Between Oxygen Content and Superconductivity in Bi‐Sr‐Ca‐Cu‐O System" Physica C. 185ー189. 779-780 (1991)
• [Publications] M.Yoshimoto: "Laser MBE of Layered [(AE)^<2+>/(CuO_2)^<2->] _n(AE=Sr or Ba)Lattices" Physica C. 185ー189. 2085-2086 (1991)
• [Publications] H.Nagata: "Nanometer‐Scale Design and Growth of Ceramic Hetero‐Junctions and Superlattice" Ext.Abst.of the 23nd Conf.on Solid State Devices and Materials. 23. 543-545 (1991)
• [Publications] Y.Deshimaru: "Influence of Oxygen Content on the Superconductivity of Bi‐Based Oxides Homologous to 2212 Phase" Jpn.J.Appl.Phys.30. L1798-L1801 (1991)
• [Publications] 弟子丸 雄一: "Bi系酸化物超伝導体(2212相)の酸素収脱着挙動と超伝導特性" 日本セラミックス協会学術論文誌. 99. 774-779 (1991)
• [Publications] H.Koinuma: "Fabrication and Anomalous Conducting Behavior of Atomically Regulated(SrVO_<3‐x>)/(SrTiO_<3‐y>)Superlattices" Solid State Commun.80. 9-13 (1991)
• [Publications] T.Nishida: "^<119>Sn‐Mossbauer Study on the Normal Lattice Vibration of Superconducting Bi(Pb)_2Sr_2Cu_3Sn_<0.015>O_<10‐y>" Jpn.J.Appl.Phys.30. L735-L738 (1991)
• [Publications] T.Asakawa: "Preparation and Diffusion Behavior of Y‐Cu‐O/Ba‐Cu‐O Interface" Jpn.J.Appl.Phys.30(8). 1676-1678 (1991)
• [Publications] M.Yoshimoto: "^<151>Eu Mossbauer Spectroscopy and Structure of Electron‐Doped(Eu,La)_<2‐x>Ce_xCuO_<4‐y> Superconductor" Physica C. 181. 284-285 (1991)
• [Publications] Y.Watanabe: "Synthesis of Superconducting Oxides in the System of Gd‐La‐Ce‐Cu‐O" Physica C. 185ー189. 593-595 (1991)
• [Publications] H.Tagawa: "High Temperature X‐ray Diffraction of YBa_2Cu_3O_<7‐a>" Physica C.
• [Publications] Tooru Atake: "Heat Capacity and Related Thermodynamic Functionsilms of Ba_2YCu_3O_<7‐y>" Physica C.
• [Publications] M.Yoshimoto: "Novel Process for Ceramic Epitaxy Using Laser MBE" Mat.Res.Soc.Symp.Proc.201. 177-182 (1991)
• [Publications] H.Koinuma: "In Situ RHEED and XPS Stndies on Ceramic Layer Epitaxy in UHV System" Aip Conf.Proc.219. 326-335 (1991)
• [Publications] Tooru Atake: "Heat Capacity Anomalies due to Phase Transitions in La_<2‐x>Ba_xCuO_y and La_<2‐x>Sr_xCuO_y" Physica C. 185ー189. 1413-1414 (1991)
• [Publications] 鯉沼 秀臣: "ス-パ-ファインセラミックスの化学‐格子工学への展開‐" 化学. 46. 576-577 (1991)
• [Publications] Y.Kawada: "Fabrication and Photochemical Modification of High T_c Superconducting thin Films" J.Advanced Science. 3. 14-17 (1991)
• [Publications] Tooru Atake: "Heat Capacity Measurements and Thermodynamic Studies of the New Compound C_<60>" Physica C. 185ー189. 427-428 (1991)
• [Publications] T.Hashimoto: "Photo‐adsorption and Photochemical decomposition of Copper and alkaline‐earth β‐diket onates as Source Gases of High‐t_c Superconducting Thin Films" Appl.Organometallic Chem.5. 325-330 (1991)
• [Publications] T.Hashimoto: "Thermodynamic Estimation of Oxidation Ability of Various Gases Used for the Preparation of Superconduction Films at High Vacuum" Jpn.J.Appl.Phys.30. 1685-1686 (1991)
• [Publications] 鯉沼 秀臣: "高温超伝導薄膜研究の進展" 応用物理. 60. 433-442 (1991)
• [Publications] 鯉沼 秀臣: "セラミックス超格子の可能性" 表面. 29. 868-878 (1991)
• [Publications] 鯉沼 秀臣: "MBE法による超伝導薄膜の作製とキャラクタリゼ-ション" 表面技術. 42. 467-472 (1991)
• [Publications] K.Horiuchi: "Bi_2Sr_2CaCuO_2O_8/Bi_2Sr_2CuO_6 Superconducting Superlattices" Jpn.J.Appl.Phys.30. L1381-L1383 (1991)
• [Publications] S.Hontsu: "Crystal Orientation of YBa_2Cu_3O_7 Thin Films on LaSrGaO_4 Fabricated by Laser Ablation" Appl.Phys.Lett.59. 2886-2888 (1991)
• [Publications] T.Kawai: "High T_c Superconducting Artificial Lattice as a New Material" Physica C. 185ー189. 198-204 (1991)
• [Publications] M.Kawai: "Atomic Layer Control of SrCuO_x and Layer‐by‐layer Growth of Bi_2Sr_2Ca_<n‐1>Cu_nO_<2n+4>(n=1-4)" Jpn.J.Appl.Phys.31. (1992)
• [Publications] T.Matsumoto: "Tunneling Spectra of Au/Bi_2Sr_2CuO_6 Thin Films/Bi_2Sr_2Ca_1Cu_2O_8 Single Crystal Junctions" Physica C. 185ー189. 1907-1908 (1991)
• [Publications] K.Horiuchi: "Crystal Structure and Superconductivities of(La,Sr)_2CuO_4/Sm_2CuO_4 and YBa_2Cu_3O_7/(La,Sr)_2CuO_4" Physica C. 185ー189. 2049-2050 (1991)
• [Publications] N.Ohashi: "Carrier Behavior in the T^*‐Phase Compounds of(Ln_<1‐x‐y>,Ln'_<x,>Sr_y)_2CuO_<4‐δ>" Physica C. 177. 377-383 (1991)
• [Publications] N.Ohashi: "Metal‐Semiconductor Transition in Oxygen Defficient Layered Perovskite Compounds of Sr_4V_3O_<10‐δ>" J.Solid State Chem.
• [Publications] N.Ohashi: "Effect of Lanthanide Elements to the Properties of the T^*‐phase" Physica C(Proceeding of Chem HTSC '91).
• [Publications] N.Ohashi: "Effect of Lanthanide Substitution to the Properties of High t_c Oxide" Proceeding 2nd European Ceramic Int.Cong.
• [Publications] Tooru Atake: "Thermodynamic Properties of the New Compound C_<60>" Order/Disorder in Solids. 8. 16-20 (1991)
• [Publications] Tooru Atake: "Low‐Temperature Heat Capacities and Thermodynamic Functions of Tl_2Ba_2CaCu_2O_y" Thermochim.Acta. 183. 143-152 (1991)
• [Publications] N.Ichinose: "Partial Substitution of Cadmium in the Bi_2Sr_2Ca_1Cu_2O_y System" 粉体および粉末治金. 38(2). 291-294 (1991)
• [Publications] N.Ichinose: "Preparation of Superconducting Bi‐Pb‐Sr‐Ca‐Cu‐O Thick Films Prepared by Twin Roller Rapid Quenching Method" Physica C. 185ー189. 2391-2392 (1991)
• [Publications] N.Ichinose: "Partial Substitution of Cadmium in the Bi‐Sr‐Ca‐Cu‐O System" Proceeding of 1991 Japan IEMT Symposium. 241-244 (1991)
• [Publications] N.Ichinose: "Grain Orientation and Magnetic Evaluation of the Hot Forged Bi‐Sr‐Ca‐Cu‐O Oxide System" Proceeding of Waseda International Symposium on Superconducting Materials.
• [Publications] N.Ichinose: "Magnetic Evaluation of Grain Oriented Bi‐Sr‐Ca‐Cu‐O Superconductor" Proceeding of Waseda International Symposium on Superconducting Materials.
• [Publications] K.Takahashi: "Crystallization Process and Superconducting Properties of Bi‐Pb‐Sr‐Ca‐Cu‐O Thick Films Crystallized from an Amorphous State" Proceeding of Waseda International Symposium on Superconducting Materials.
• [Publications] S.Hirano: "Chemical Processing and Characterization of Bi‐Pb‐Sr‐Ca‐Cu‐O System Superconducting Films." Ceram.Trans.22. 701-706 (1991)
• [Publications] S.Hirano: "Processing of Bi‐(Pb)‐Sr‐Ca‐Cu‐O Oxide Superconductor Thin Films by Metal Alkoxide Route." Physica C.
• [Publications] H.R.Zhuang: "Preparation of Superconducting Bi‐Sr‐Ca‐Cu‐O Ceramics by the Sol‐Gel Method" J.Mater.Sci. 25. 4762-4766 (1990)
• [Publications] 金 基孫: "金属酢酸塩を出発物質とするゾル-ゲル法によるYBa_2Cu_3O_<7‐x>,超伝導体の合成" 材料. 40. 374-378 (1991)
• [Publications] S.Fujihara: "Superconductivity of La_<2‐x>Sr_xCuO_4 with high Sr Concentration by Sulfur Doping" Jpn.J.Appl.Phys.
• [Publications] Tooru Atake: "Heat Capacities of High‐T_c Oxide Superconductors Method" Thermochim.Acta. 174. 281-297 (1991)
• [Publications] Y.Iwai: "Superconductivity in Non‐Modulated(Bi,Pb)_2Sr_2Ca_<1‐x>Y_xCu_2O_y(x=0-1.0)" Physica C. 185. 641-642 (1991)
• [Publications] Y.Watanabe: "Synthesis of Superconducting Oxides in the System of Gd‐La‐Ce‐Cu‐O" Physica C. 185. 593-594 (1991)
• [Publications] Nobuyuki Koura: "Preparation of Various Shape Superconducting Ceramics by Using the Electrophoretic Deposition Method" MRS Int'I.Mtg.on Adv.Mats.6. 193-196 (1989)
• [Publications] 小浦 延幸: "各種形状の各種基板表面の超伝導化" 表面技術. 40. 72-73 (1989)
• [Publications] 小浦 延幸: "セラミックス表面の超伝導化" 表面技術. 40. 819-824 (1989)
• [Publications] 小浦 延幸: "泳動電着法を応用した各種形状の各種基材表面の超伝導化" 表面. 27. 719-725 (1989)
• [Publications] Nobuyuki Koura: "Preparation of Various Shap Superconducting Ceramics with Various Substrates by Electrophoretic Deposition Method" Mol.Cryst.Liq.Cryst.184. 243-247 (1990)
• [Publications] 小浦 延幸: "泳動電着法を応用した各種形状の各種基材上への酸化物超伝導体の作製" 表面技術. 42. 508-513 (1991)
• [Publications] Nobuyuki Koura: "Preparation of High‐t_c Superconductors by Electrophoretic Deposition Method‐Study on the Substrate and the Electrolyte" Physica C.
• [Publications] 南 直孝: "泳動電着法によるステンレス鋼板上へのYBCO超伝導体の作製" 表面技術.
• [Publications] Naotaka Minami: "Preparation of YBa_2Cu_3O_<7‐δ> Superconducting Coating on Austenitic Steel by Electrophoretic Deposition Method‐Study on Buffering Layers" Jpn.J.Appl.Phys.
• [Publications] Y.Iwai: "Preparation of YBa_2Cu_4O_8 by a Seeding Method at Ambient Pressure" Physica C. 181. 261-264 (1991)
• [Publications] Y.Sawai: "Stability of YBa_2Cu_3O_7,Y_2Ba_4Cu_7O_<15> and YBa_2Cu_4O_8 Superconductors under Variables of Oxygen Partial Pressure,Total Gas Pressure and Temperature;" Physica C. 176. 147-150 (1991)
• [Publications] Y.Iwai: "Influence of Oxygen Partial Pressure on the Solubility of Y_2O_3 in the High T_c Phase of Bi‐Pb‐Sr‐Ca(Y)‐Cu‐O" Jpn.J.Appl.Phys.30. L891-L893 (1991)
• [Publications] S.Ohara: "Synthesis of Bulk YBa_2Cu_4O_8 Superconductor by Addition of Ag_2O at an Ordinary Pressure of Oxygen" Appl.Phys.Lett.59. 603-605 (1991)
• [Publications] 岸尾 光二(分担執筆): "第4版実績化学講座 第9巻「電気・磁気」" 丸善, 13 (1991)
• [Publications] 岸尾 光二(分担執筆): "「21世紀に羽ばたくセラミックス(大観)」" 日本セラミックス協会, 6 (1991)
• [Publications] 高田 雅介,沼鯉 秀臣: "「レアメタル事典」"酸化物超伝導材料"" フジテクニシステム, 21 (1991)