CN113614858A - 氧化物超导线材 - Google Patents
氧化物超导线材 Download PDFInfo
- Publication number
- CN113614858A CN113614858A CN202080021295.4A CN202080021295A CN113614858A CN 113614858 A CN113614858 A CN 113614858A CN 202080021295 A CN202080021295 A CN 202080021295A CN 113614858 A CN113614858 A CN 113614858A
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- China
- Prior art keywords
- layer
- oxide superconducting
- superconducting wire
- plating
- substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 238000007747 plating Methods 0.000 claims abstract description 57
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 230000006641 stabilisation Effects 0.000 claims description 20
- 238000011105 stabilization Methods 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 7
- 230000000087 stabilizing effect Effects 0.000 abstract description 8
- 239000010410 layer Substances 0.000 description 132
- 239000010949 copper Substances 0.000 description 51
- 238000000034 method Methods 0.000 description 20
- 239000011241 protective layer Substances 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
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- 239000000654 additive Substances 0.000 description 5
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000007735 ion beam assisted deposition Methods 0.000 description 4
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- 229910000990 Ni alloy Inorganic materials 0.000 description 3
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 3
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- 239000011247 coating layer Substances 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- JYTUFVYWTIKZGR-UHFFFAOYSA-N holmium oxide Inorganic materials [O][Ho]O[Ho][O] JYTUFVYWTIKZGR-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
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- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
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- -1 Ag alloy Chemical class 0.000 description 2
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- 229910002609 Gd2Zr2O7 Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910002328 LaMnO3 Inorganic materials 0.000 description 2
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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- 239000008139 complexing agent Substances 0.000 description 2
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
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- 238000001659 ion-beam spectroscopy Methods 0.000 description 2
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- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- 229910002929 BaSnO3 Inorganic materials 0.000 description 1
- 241000954177 Bangana ariza Species 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910002480 Cu-O Inorganic materials 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
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- 229910052689 Holmium Inorganic materials 0.000 description 1
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- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000007545 Vickers hardness test Methods 0.000 description 1
- 229910001080 W alloy Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 229910008253 Zr2O3 Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 229910021523 barium zirconate Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 1
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(III) oxide Inorganic materials O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 238000010894 electron beam technology Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 1
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B12/00—Superconductive or hyperconductive conductors, cables, or transmission lines
- H01B12/02—Superconductive or hyperconductive conductors, cables, or transmission lines characterised by their form
- H01B12/06—Films or wires on bases or cores
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/615—Microstructure of the layers, e.g. mixed structure
- C25D5/617—Crystalline layers
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- C—CHEMISTRY; METALLURGY
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C23C14/021—Cleaning or etching treatments
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C—CHEMISTRY; METALLURGY
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C14/083—Oxides of refractory metals or yttrium
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- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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- C23C14/3485—Sputtering using pulsed power to the target
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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- C23C14/46—Sputtering by ion beam produced by an external ion source
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C14/5806—Thermal treatment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
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Abstract
本发明提供一种氧化物超导线材，其具备：在基板上具有氧化物超导层的超导层叠体、及作为覆盖于超导层叠体的外周的Cu镀层的稳定化层，Cu镀层的维氏硬度为80～190HV的范围。
Description
技术领域
本发明涉及一种氧化物超导线材。
本申请基于2019年3月28日在日本提出申请的日本特愿第2019-064778号主张优先权，并将其内容援用于此。
背景技术
RE123类氧化物超导体(REBa2Cu3Oy，RE为稀土元素)在超过液氮温度(77K)的温度(约90K)下显示出超导性。这样的超导体与其他高温超导体相比在磁场中的临界电流密度更高，因此被期待应用于线圈、电缆等。例如专利文献1中记载了一种在基板上形成氧化物超导层与Ag稳定化层之后通过电镀而形成有Cu稳定化层的氧化物超导线材。
现有技术文献
专利文献
专利文献1：日本特开第2007-80780号公报
发明内容
本发明要解决的技术问题
氧化物超导线材需具备作为机械特性的拉伸强度。对于氧化物超导线材的基板，通常使用镍合金基板，对于稳定化层，通常使用铜(Cu)，但是与基板相比Cu的硬度更低。因此，由于稳定化层越厚则稳定化层在氧化物超导线材的截面面积中所占的比例越大，氧化物超导线材整体的拉伸强度会降低。
本发明鉴于上述情况而完成，本发明提供一种拉伸强度优异的氧化物超导线材。
解决技术问题的技术手段
本发明的第一方案为一种氧化物超导线材，其具备：在基板上具有氧化物超导层的超导层叠体、及作为覆盖于所述超导层叠体的外周的Cu镀层的稳定化层，所述Cu镀层的维氏硬度为80～190HV的范围。
本发明的第二方案中，上述第一方案的氧化物超导线材中的所述Cu镀层的平均晶粒尺寸可以为0.52～1.00μm的范围。
本发明的第三方案中，上述第一方案或第二方案的氧化物超导线材中的所述Cu镀层的每100μm长度中的平均晶界数量可以为100个以上。
发明效果
由于构成稳定化层的Cu镀层的维氏硬度大，因此本发明的上述方案能够提供拉伸强度优异的氧化物超导线材。
附图说明
图1为实施方式的氧化物超导线材的截面图。
具体实施方式
以下，基于优选的实施方式，参照附图对本发明进行说明。
如图1所示，实施方式的氧化物超导线材10具备超导层叠体15、及覆盖于超导层叠体15的外周的稳定化层16。超导层叠体15在基板11上方具有氧化物超导层13即可。超导层叠体15例如也可以为具有基板11、中间层12、氧化物超导层13以及保护层14的结构。
基板11例如为在厚度方向的两侧分别具有第一主面11a以及第二主面11b的带状金属基板。作为构成金属基板的金属的具体实例，可列举出以哈氏合金(Hastelloy，注册商标)为代表的镍合金、不锈钢、向镍合金中导入了织构的取向Ni-W合金等。在使用统一金属晶体的排列并取向的取向基板作为基板11的情况下，可以不形成中间层12，而在基板11上直接形成氧化物超导层13。将基板11上形成氧化物超导层13的一侧称为第一主面11a，将与第一主面11a相反的一侧的面、即背面称为第二主面11b。基板11的厚度根据目的适当调整即可，例如为10～1000μm的范围。
中间层12可以为多层结构，例如可以自基板11侧至氧化物超导层13侧依次具有防扩散层、基础层(bed layer)、取向层、覆盖层(cap layer)等。这些层并不仅限于一定以每层各为一层的方式设置，有时会省略部分层，或者有时会将同一种层重复层叠两层以上。中间层12可以为金属氧化物。通过将氧化物超导层13成膜于取向性优异的中间层12上，易于获得取向性优异的氧化物超导层13。
氧化物超导层13例如由氧化物超导体构成。作为氧化物超导体，例如可列举出以通式REBa2Cu3Oy(RE123)等表示的RE-Ba-Cu-O类氧化物超导体。作为稀土元素RE，可列举出Y、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu中的一种或两种以上。在RE123的通式中，y为7-x(氧缺位量)。此外，RE:Ba:Cu的比率不仅限于1:2:3，也可以为非整比。氧化物超导层13的厚度例如为0.5～5μm左右。
氧化物超导层13中也可以导入有基于不同种类的材料的人工钉扎等作为人工的晶体缺陷。作为用于向氧化物超导层13中导入人工钉扎的不同种类的材料，例如可列举出BaSnO3(BSO)、BaZrO3(BZO)、BaHfO3(BHO)、BaTiO3(BTO)、SnO2、TiO2、ZrO2、LaMnO3、ZnO等中的至少一种以上。
保护层14具有使过电流分流、或者抑制氧化物超导层13与设置于保护层14上方的层之间发生的化学反应等的功能。作为构成保护层14的材料，可列举出银(Ag)、铜(Cu)、金(Au)或者包含上述金属中的一种以上的合金(例如Ag合金、Cu合金、Au合金)。保护层14的厚度优选为例如1～30μm左右，在减薄保护层14的情况下，也可以为10μm以下、5μm以下、2μm以下等。保护层14也可以形成于超导层叠体15的侧面15s或者基板11的第二主面11b。超导层叠体15的不同的面上所形成的保护层14的厚度可以大致相同也可以不同。保护层14也可以由两种以上的金属或者两层以上的金属层构成。保护层14能够通过蒸镀法、溅射法等形成。
稳定化层16可以以遍布超导层叠体15的包括第一主面15a、第二主面15b及侧面15s的整个外周的方式而形成。超导层叠体15的第一主面15a例如为保护层14的表面，但并不仅限于此。超导层叠体15的第二主面15b例如为基板11的第二主面11b，但并不仅限于此，例如在保护层14也形成于基板11的第二主面11b上的情况下也可以为保护层14上的面。超导层叠体15的侧面15s为厚度方向两侧的两个面。
稳定化层16具有使过电流分流、或者对氧化物超导层13以及保护层14进行机械性增强等的功能。稳定化层16为由铜(Cu)等金属构成的镀层。稳定化层16的厚度没有特别的限定，但优选为例如1～300μm左右，例如可以为200μm以下、100μm以下、50μm以下、20μm等。超导层叠体15的第一主面15a、第二主面15b、侧面15s上所形成的稳定化层16的厚度可以大致相同。
在构成稳定化层16的Cu镀层中，Cu镀层的维氏(Vickers)硬度优选为80～190HV的范围。由于Cu镀层的维氏硬度大，可提高氧化物超导线材10的拉伸强度。维氏硬度能够按照例如JIS Z 2244(维氏硬度试验-试验方法)进行测定。氧化物超导线材10的拉伸强度受到各层在垂直于氧化物超导线材10的长度方向的截面面积中所占比例的影响。因此，若Cu镀层的维氏硬度大，则即使在增厚稳定化层16的情况下，也能够提高氧化物超导线材10的拉伸强度。基板11的维氏硬度与稳定化层16的维氏硬度之间的关系没有特别的限定，可以前者比后者大，也可以前者比后者小，也可以前者与后者大致相等。
在构成稳定化层16的Cu镀层中，Cu镀层的平均晶粒尺寸优选为0.52～1.00μm的范围。通过使Cu镀层的平均晶粒尺寸相对较小，能够使金属组织变得致密，增大维氏硬度。
此外，在构成稳定化层16的Cu镀层中，Cu镀层的每100μm长度中的平均晶界数量优选为100个以上。由于Cu镀层的每单位长度中的平均晶界数量多，可使金属组织变得致密，增大维氏硬度。作为单位长度，例如可列举出氧化物超导线材10的长度方向上的100μm的长度。Cu镀层的每100μm长度中的平均晶界数量的上限没有特别的限定，例如可列举出100个、120个、150个、180个、200个等。
Cu镀层的平均晶粒尺寸以及Cu镀层的每单位长度中的平均晶界数量例如能够使用采用了扫描型电子显微镜(SEM：Scanning Electron Microscope)的Cu镀层的截面照片进行测定。
构成稳定化层16的铜镀层例如能够通过电镀形成。在通过电镀形成铜镀层的情况下，可以事先通过蒸镀法、溅射法等形成银(Ag)、铜(Cu)、锡(Sn)等的金属层作为衬底层。作为Cu镀层的电镀中所使用的镀浴，可列举出硫酸铜镀浴、氰化铜镀浴、焦磷酸铜镀浴等。作为硫酸铜镀液，通常可使用含有硫酸铜五水合物、硫酸、添加剂、氯离子的水溶液等。
Cu镀层的至少一部分也可以通过无电解电镀形成。在该情况下，可使用甲醛浴、乙醛酸浴、次亚磷酸盐浴、钴盐浴等。常规的甲醛浴可使用含有二价铜盐、还原剂(甲醛等)及络合剂(罗谢尔盐等)、pH调节剂(氢氧化钠)、添加剂(氰化物)的镀液。
作为调整Cu镀层的平均晶粒尺寸或Cu镀层的每单位长度中的平均晶界数量的方法，可列举出对Cu的电镀条件中的至少一个以上的条件进行变更的方法。作为具体的电镀条件，例如可列举出镀液的浓度、镀浴的种类、电流密度、过电压的程度、温度、有无添加剂、有无电镀后的热处理等。例如，电流密度越大，则Cu镀层的平均晶粒尺寸会变得越小。此外，通过进行电镀后的热处理，Cu镀层的平均晶粒尺寸变大。作为镀浴的添加剂没有特别的限定，可列举出络合剂、pH调节剂、流平剂等。
本实施方式的氧化物超导线材10中，构成稳定化层16的Cu镀层的晶粒尺寸小、或者每单位长度中的平均晶界数量多，因此能够增大稳定化层16的维氏硬度。由此，即使增厚稳定化层16，也能够抑制氧化物超导线材10的拉伸强度降低、或提高氧化物超导线材10的拉伸强度。
以上，基于优选的实施方式对本发明进行了说明，但本发明并不限定于上述的实施方式，可以在不脱离本发明主旨的范围内进行各种变更。作为变更，可列举出各实施方式中的构成要素的追加、替换、省略以及其他变更。
关于中间层12以及氧化物超导层13的成膜法，只要能够根据金属氧化物的组成适当成膜，则没有特别的限定。作为成膜法，例如可列举出溅射法、蒸镀法等干式成膜法；溶胶凝胶法等湿式成膜法。作为蒸镀法，可列举出电子束蒸镀法、离子束辅助沉积(IBAD：Ion-Beam-Assisted Deposition)法、脉冲激光沉积(PLD：Pulsed Laser Deposition)法、化学气相沉积(CVD：Chemical Vapor Deposition)法等。
中间层12中的防扩散层具有抑制基板11的部分成分发生扩散并作为杂质混入氧化物超导层13侧的功能。防扩散层例如可由Si3N4、Al2O3、GZO(Gd2Zr2O7)等构成。防扩散层的厚度例如可列举出10～400nm。
中间层12中的基础层具有减少基板11与氧化物超导层13的界面上的反应、提高形成于其上方的层的取向性等的功能。作为基础层的材质，例如可列举出Y2O3、Er2O3、CeO2、Dy2O3、Eu2O3、Ho2O3、La2O3等。基础层的厚度例如可列举出10～100nm。
中间层12中的取向层由双轴取向的物质形成，以控制其之上的覆盖层的晶体取向性。作为取向层的材质，例如可列举出Gd2Zr2O7、MgO、ZrO2-Y2O3(YSZ)、SrTiO3、CeO2、Y2O3、Al2O3、Gd2O3、Zr2O3、Ho2O3、Nd2O3等金属氧化物。取向层优选通过IBAD法形成。
中间层12中的覆盖层成膜于取向层的表面，且晶粒沿面内方向取向。作为覆盖层的材质，例如可列举出CeO2、Y2O3、Al2O3、Gd2O3、ZrO2、YSZ、Ho2O3、Nd2O3、LaMnO3等。覆盖层的厚度例如可列举出50～5000nm。
为了确保对氧化物超导线材周围的电绝缘，可以在氧化物超导线材的外周缠绕聚酰亚胺等的绝缘胶带，或在氧化物超导线材的外周形成树脂层。另外，绝缘胶带或树脂层等绝缘包覆层并非是必须的，可以根据氧化物超导线材的用途适当设置绝缘包覆层，或者也可以制成无绝缘包覆层的构成。
为了使用氧化物超导线材制作超导线圈，例如在将氧化物超导线材沿着缠线框的外周面缠绕必要的层数而构成线圈形状的多层卷绕线圈之后，以覆盖缠绕的氧化物超导线材的方式将氧化物超导线材含浸于环氧树脂等树脂中，由此能够固定氧化物超导线材。
实施例
以下，使用具体的实施例对氧化物超导线材10的制造方法进行说明。另外，本发明并不限定于如下实施例。
首先，按照如下步骤，准备规定宽度的超导层叠体15。
(1)对哈氏合金(注册商标)C-276的带状基板11进行研磨。
(2)使用丙酮对基板11进行脱脂·清洗。
(3)通过离子束溅射法使Al2O3防扩散层成膜。
(4)通过离子束溅射法使Y2O3基础层成膜。
(5)通过IBAD法使MgO取向层成膜。
(6)通过PLD法使CeO2覆盖层成膜。
(7)通过PLD法使GdBa2Cu3O7-x氧化物超导层13成膜。
(8)通过自氧化物超导层13的表面方向实施的溅射法使Ag保护层14成膜。
(9)对超导层叠体15进行氧退火处理。
(10)通过4mm宽的纵切(slit)加工对超导层叠体15进行细线化处理。
接着，通过自第一主面15a的方向及第二主面15b的方向实施的溅射法，使Cu衬底层成膜于超导层叠体15。
接着，通过硫酸铜电镀形成厚度为20μm的稳定化层16。
实施例中，镀液的组成为硫酸铜五水合物、硫酸、盐酸、添加剂，并在1～13A/dm2的范围内变更每个样本的电流密度。
接着，对获得的氧化物超导线材10测定拉伸强度。并测定构成稳定化层16的Cu镀层的维氏硬度以及平均晶粒尺寸。
对于Cu镀层的平均晶粒尺寸，对每一个样本拍摄45张截面SEM照片(23μm×23μm的视野范围)，在每一张照片中沿氧化物超导线材10的长度方向画出三条线段，按照JIS H0501(锻造铜及铜合金平均晶粒度评估的方法)的切断法，计数被线段完全切断的晶粒数，将作为其切断长度的平均值而求出的以μm为单位的晶粒度直接用作Cu镀层的平均晶粒尺寸。对于沿氧化物超导线材10的长度方向画出的三条线段，在厚度为20μm的稳定化层16的自其表面约3.2μm、约10.0μm、约16.8μm深的位置(相对于稳定化层16厚度分别为约16％、约50％、约84％的位置)画出。
Cu镀层的每100μm长度中的平均晶界数量(个)作为下述数值而算出，即，将长度100μm除以上述平均晶粒尺寸(μm)而得到的数值。
将以上的测定结果示于表1。
[表1]
通常，氧化物超导线材所需的拉伸强度为600MPa以上。因此，作为评价结果，将拉伸强度为600MPa以上的样本判定为优良品(优良)，将拉伸强度小于600MPa的样本判定为不良品(不良)。结果显示构成稳定化层的Cu镀层的维氏硬度越大，则氧化物超导线材的拉伸强度的值越高。
编号7的样本为了提高维氏硬度而在形成Cu镀层时增大了电流密度。但由于成为所谓的“电镀烧损”的状态而未能进行晶粒的观察、拉伸强度的测定，因外观不良而判定为不良品(不良)。因此，编号7的样本仅测定了维氏硬度。
附图标记说明
10：氧化物超导线材；11：基板；11a：基板的第一主面；11b：基板的第二主面；12：中间层；13：氧化物超导层；14：保护层；15：超导层叠体；15a：超导层叠体的第一主面；15b：超导层叠体的第二主面；15s：超导层叠体的侧面；16：稳定化层。
Claims (3)
1.一种氧化物超导线材，其特征在于，具备:
在基板上具有氧化物超导层的超导层叠体、及
作为覆盖于所述超导层叠体的外周的Cu镀层的稳定化层，
所述Cu镀层的维氏硬度为80～190HV的范围。
2.根据权利要求1所述的氧化物超导线材，其特征在于，
所述Cu镀层的平均晶粒尺寸为0.52～1.00μm的范围。
3.根据权利要求1或2所述的氧化物超导线材，其特征在于，
所述Cu镀层的每100μm长度中的平均晶界数量为100个以上。
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