JP2013122847A - Method for manufacturing oxide superconducting wiring material - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 title abstract 4
- 239000010409 thin film Substances 0.000 claims abstract description 42
- 239000010408 film Substances 0.000 claims abstract description 40
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000460 chlorine Substances 0.000 claims abstract description 21
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 21
- 239000011248 coating agent Substances 0.000 claims abstract description 16
- 238000000576 coating method Methods 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 8
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 8
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 5
- 239000011737 fluorine Substances 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims description 13
- 150000002902 organometallic compounds Chemical class 0.000 claims description 9
- 241000954177 Bangana ariza Species 0.000 claims description 4
- 238000000197 pyrolysis Methods 0.000 claims description 4
- 239000006193 liquid solution Substances 0.000 abstract 3
- 238000001035 drying Methods 0.000 abstract 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 15
- 239000010949 copper Substances 0.000 description 11
- 235000019270 ammonium chloride Nutrition 0.000 description 9
- 239000002887 superconductor Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 150000001805 chlorine compounds Chemical class 0.000 description 5
- -1 organic acid salt Chemical class 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- 229910052788 barium Inorganic materials 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910016036 BaF 2 Inorganic materials 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- 229910052689 Holmium Inorganic materials 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 2
- 238000009499 grossing Methods 0.000 description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical class OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E40/00—Technologies for an efficient electrical power generation, transmission or distribution
- Y02E40/60—Superconducting electric elements or equipment; Power systems integrating superconducting elements or equipment
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- Inorganic Compounds Of Heavy Metals (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
Description
本発明は、酸化物超電導線材の製造方法に関し、詳しくは、塗布熱分解法により、超電導特性が優れた酸化物超電導薄膜を作製して、酸化物超電導線材を製造する酸化物超電導線材の製造方法に関する。 The present invention relates to a method for manufacturing an oxide superconducting wire, and more specifically, an oxide superconducting wire manufacturing method by manufacturing an oxide superconducting thin film having excellent superconducting properties by a coating pyrolysis method. About.
近年、酸化物超電導薄膜を用いた超電導線材（酸化物超電導線材）の一層の普及のため、臨界電流値Ｉｃをより高めた酸化物超電導薄膜の製造に関する研究が盛んに行われている。 In recent years, in order to further spread superconducting wires (oxide superconducting wires) using oxide superconducting thin films, researches on the production of oxide superconducting thin films with higher critical current values Ic have been actively conducted.
このような酸化物超電導線材の製造方法の１つに、塗布熱分解法（Ｍｅｔａｌ Ｏｒｇａｎｉｃ Ｄｅｐｏｓｉｔｉｏｎ、略称：ＭＯＤ法）と言われる方法がある（特許文献１）。この方法は、Ｙ（イットリウム）、Ｇｄ（ガドリニウム）、Ｈｏ（ホルミウム）などのＲＥ（希土類元素）およびＢａ（バリウム）、Ｃｕ（銅）の各有機金属化合物を溶媒に溶解して製造された原料溶液（ＭＯＤ溶液）を配向基板に塗布して塗布膜を形成した後、例えば５００℃付近で仮焼熱処理して有機金属化合物を熱分解させ、さらに高温（例えば８００℃付近）で本焼熱処理することにより結晶化を行い、ＲＥＢａ２Ｃｕ３Ｏ７−Ｘ（ＲＥ１２３）で表される酸化物超電導体からなる酸化物超電導薄膜を製造するものであり、主に真空中で製造される気相法（蒸着法、スパッタ法、パルスレーザ蒸着法など）に比較して製造設備が簡単で済み、また大面積や複雑な形状への対応が容易であるなどの特徴を有している。 One method for producing such an oxide superconducting wire is a so-called coating pyrolysis method (Metal Organic Deposition, abbreviated as MOD method) (Patent Document 1). This method is a raw material produced by dissolving RE (rare earth elements) such as Y (yttrium), Gd (gadolinium), Ho (holmium), and organic metal compounds such as Ba (barium) and Cu (copper) in a solvent. After applying the solution (MOD solution) to the alignment substrate to form a coating film, the organometallic compound is thermally decomposed by, for example, calcining heat treatment at around 500 ° C., and then heat-treating at high temperature (eg, around 800 ° C.). Is produced, and an oxide superconducting thin film made of an oxide superconductor represented by REBa 2 Cu 3 O 7-X (RE123) is produced. Compared with (evaporation method, sputtering method, pulsed laser deposition method, etc.), the manufacturing facilities are simple, and it is easy to deal with large areas and complex shapes.
上記ＭＯＤ法には、原料としてフッ素を含む有機酸塩を用いるＴＦＡ−ＭＯＤ法（Ｍｅｔａｌ Ｏｒｇａｎｉｃ Ｄｅｐｏｓｉｔｉｏｎ ｕｓｉｎｇ ＴｒｉｆｌｕｏｒｏＡｃｅｔａｔｅｓ）とフッ素を含まない有機金属化合物を用いるフッ素フリーＭＯＤ法（以下、「ＦＦ−ＭＯＤ法」ともいう）とがある。 The MOD method includes a TFA-MOD method (Metal Organic Deposition using TrifluoroAcetates) using an organic acid salt containing fluorine as a raw material and a fluorine-free MOD method (hereinafter referred to as “FF-MOD method”) using an organometallic compound containing no fluorine. Also called).
一方、酸化物超電導薄膜は、例えば膜全体に亘りｃ軸配向しているなど、結晶配向性が揃っていなければ、超電導電流はスムースに流れず、Ｉｃは低くなる。このため、結晶化に際しては結晶を配向基板の配向性を受け継ぐエピタキシャル成長をさせる必要があり、基板から膜表面へ向けて結晶成長を進める必要がある。 On the other hand, if the oxide superconducting thin film does not have a uniform crystal orientation, for example, it is c-axis oriented over the entire film, the superconducting current does not flow smoothly and Ic decreases. For this reason, at the time of crystallization, it is necessary to perform epitaxial growth that inherits the orientation of the oriented substrate, and it is necessary to advance the crystal growth from the substrate toward the film surface.
ＴＦＡ−ＭＯＤ法を用いると、面内配向性に優れた酸化物超電導薄膜を得ることができる。しかし、この方法では、仮焼時にフッ化物であるＢａＦ２（フッ化バリウム）が生成され、このＢａＦ２が本焼時に分解して危険なフッ化水素ガスを発生する。このため、フッ化水素ガスを処理する装置、設備が必要となる。 When the TFA-MOD method is used, an oxide superconducting thin film excellent in in-plane orientation can be obtained. However, in this method, BaF 2 (barium fluoride), which is a fluoride, is generated during calcination, and this BaF 2 is decomposed during the main firing to generate dangerous hydrogen fluoride gas. For this reason, the apparatus and installation which process hydrogen fluoride gas are needed.
これに対して、ＦＦ−ＭＯＤ法は、フッ化水素ガスのような危険なガスを発生することがないため、環境にやさしく、また処理設備が不要であるという利点を有している。 On the other hand, the FF-MOD method has an advantage that it does not generate a dangerous gas such as hydrogen fluoride gas, and therefore is environmentally friendly and does not require processing equipment.
しかしながら、従来のＦＦ−ＭＯＤ法では、例えば厚さが５００ｎｍ(０．５μｍ）以上の厚膜を作製する場合、充分に良好なＩｃを有する酸化物超電導薄膜が得られないという問題があった。 However, the conventional FF-MOD method has a problem that, for example, when a thick film having a thickness of 500 nm (0.5 μm) or more is produced, an oxide superconducting thin film having sufficiently good Ic cannot be obtained.
そこで、本発明は、ＦＦ−ＭＯＤ法を用いた酸化物超電導薄膜線材の製造において、Ｉｃが充分に高い厚膜の酸化物超電導薄膜を安定して得ることが可能となる技術を提供することを課題とする。 Therefore, the present invention provides a technique capable of stably obtaining a thick oxide superconducting thin film having a sufficiently high Ic in the manufacture of an oxide superconducting thin film wire using the FF-MOD method. Let it be an issue.
本発明者は、ＦＦ−ＭＯＤ法を用いて厚膜の酸化物超電導薄膜を製造した場合、何故Ｉｃが高い酸化物超電導薄膜を安定して得ることができないかについて鋭意検討を行った。その結果、厚膜化した場合には、結晶化に際してｃ軸配向が阻害されて、表面部分が多結晶化し、その結果高いＩｃが得られないことが分かった。 The present inventor has intensively studied why an oxide superconducting thin film having a high Ic cannot be stably obtained when a thick oxide superconducting thin film is manufactured using the FF-MOD method. As a result, it was found that when the film was thickened, the c-axis orientation was inhibited during crystallization, and the surface portion was polycrystallized, and as a result, high Ic could not be obtained.
そして、このように、ＦＦ−ＭＯＤ法を用いて厚膜化された酸化物超電導薄膜において、結晶化に際してｃ軸配向が阻害された原因が、仮焼熱処理時、ＭＯＤ溶液中の有機金属化合物が熱分解されて、例えばＣｕ２Ｏ、ＣｕＯなどの酸化物が生成されたためであることが分かった。 Thus, in the oxide superconducting thin film thickened using the FF-MOD method, the cause of the inhibition of the c-axis orientation during crystallization is that the organometallic compound in the MOD solution is subjected to calcination heat treatment. It was found that this was due to thermal decomposition, and oxides such as Cu 2 O and CuO were produced.
即ち、これらの生成物の融点は、それぞれ、１２３５℃、１０２６℃であり、本焼熱処理温度約８００℃より高いため、本焼熱処理による酸化物超電導体の結晶化に際しても融けることがなく、酸化物超電導体結晶のｃ軸配向を阻害することが分かった。 That is, the melting points of these products are 1235 ° C. and 1026 ° C., respectively, and are higher than the heat treatment temperature of about 800 ° C., so that they are not melted during the crystallization of the oxide superconductor by the heat treatment. It was found that the c-axis orientation of the physical superconductor crystal is inhibited.
そこで、本発明者は、これらの生成物の発生を抑制することができれば、ｃ軸配向が阻害されず、Ｉｃが充分に高い酸化物超電導薄膜を安定して得ることができると考え、種々の実験を行った。そして、ＭＯＤ溶液中に塩素を添加した場合、ｃ軸配向が阻害されることなく酸化物超電導体の結晶化が行われることが分かった。 Therefore, the present inventor believes that if the generation of these products can be suppressed, the c-axis orientation is not inhibited, and an oxide superconducting thin film having a sufficiently high Ic can be stably obtained. The experiment was conducted. And when chlorine was added in the MOD solution, it turned out that crystallization of an oxide superconductor is performed, without inhibiting c-axis orientation.
即ち、塩素を添加したＭＯＤ溶液を用いた場合には、仮焼熱処理時、前記した各生成物に替えて、ＣｕＣｌ、ＣｕＣｌ２などの塩化物が生成される。そして、これらの塩化物の融点は、それぞれ４３０℃、４９８℃であり、本焼熱処理温度約８００℃よりも融点が低い。このため、これらの塩化物は、本焼熱処理による酸化物超電導体の結晶化に際しては融液となり、酸化物超電導体結晶のｃ軸配向を阻害しないことが分かった。 That is, when a MOD solution to which chlorine is added is used, chlorides such as CuCl and CuCl 2 are generated instead of the above-mentioned products during the calcining heat treatment. The melting points of these chlorides are 430 ° C. and 498 ° C., respectively, and the melting point is lower than the heat treatment temperature of about 800 ° C. For this reason, it was found that these chlorides became a melt upon crystallization of the oxide superconductor by the main annealing heat treatment and did not inhibit the c-axis orientation of the oxide superconductor crystal.
しかし、検討を進める中で、塩素の添加量が増加するに伴って、酸化物超電導体の多結晶化が抑制され、酸化物超電導薄膜の最表面が平滑化されるが、ある範囲を超えて添加量が多くなり過ぎると、棒状の塩素化合物が酸化物超電導薄膜の最表面に析出して、最表面の平滑化が阻害されることが分かった。また、最表面の多結晶化の抑制（平滑化）とＩｃの向上とは、必ずしも一致しないことが分かった。 However, as the amount of chlorine added increases as the study progresses, polycrystallization of the oxide superconductor is suppressed, and the outermost surface of the oxide superconductor thin film is smoothed. It was found that when the amount added was too large, rod-like chlorine compounds were deposited on the outermost surface of the oxide superconducting thin film, and the smoothing of the outermost surface was hindered. Further, it was found that the suppression (smoothing) of polycrystallization on the outermost surface and the improvement of Ic do not always coincide.
そこで、本発明者は、適切な塩素添加量について、さらに実験と検討を行い、その結果、ＭＯＤ溶液の全金属イオン質量に対して２ｐｐｍ以上２０００ｐｐｍ未満の塩素量が適切であることを見出した。 Therefore, the present inventor further conducted an experiment and examination on an appropriate chlorine addition amount, and as a result, found that a chlorine amount of 2 ppm or more and less than 2000 ppm was appropriate with respect to the total metal ion mass of the MOD solution.
そして、厚膜の酸化物超電導薄膜の形成に際しては、この塩素添加ＭＯＤ溶液の塗布と仮焼熱処理により仮焼膜を形成し、その後本焼熱処理を施すことにより、最表面における多結晶化が充分に抑制されて、厚膜であっても、充分に高いＩｃの酸化物超電導薄膜を安定して得ることが可能となることが分かった。 Then, when forming a thick oxide superconducting thin film, a calcined film is formed by applying this chlorine-added MOD solution and calcining heat treatment, followed by a main calcining heat treatment, so that polycrystallization on the outermost surface is sufficient. It was found that a sufficiently high Ic oxide superconducting thin film can be stably obtained even with a thick film.
請求項１に記載の発明は、上記の知見に基づく発明であり、
金属基板上に、フッ素を含まない有機金属化合物の溶液を用いて、塗布熱分解法により、酸化物超電導薄膜を作製して、酸化物超電導線材を製造する酸化物超電導線材の製造方法であって、
前記有機金属化合物溶液を、前記金属基板上に塗布、乾燥して塗膜を作製する塗膜作製工程と、
前記塗膜を加熱して、前記有機金属化合物を熱分解して、有機成分を除去することにより、仮焼膜を作製する仮焼熱処理工程と、
前記仮焼膜を加熱して、結晶化させることにより、酸化物超電導薄膜を作製する本焼熱処理工程と
を備えており、
前記有機金属化合物の溶液には、全金属イオン質量に対して２ｐｐｍ以上２０００ｐｐｍ未満の塩素が添加されている
ことを特徴とする酸化物超電導線材の製造方法である。
The invention according to claim 1 is an invention based on the above findings,
An oxide superconducting wire manufacturing method for manufacturing an oxide superconducting wire by producing an oxide superconducting thin film by a coating pyrolysis method using a solution of an organometallic compound not containing fluorine on a metal substrate. ,
The organic metal compound solution is applied onto the metal substrate and dried to prepare a coating film,
A calcining heat treatment step for producing a calcined film by heating the coating film, thermally decomposing the organometallic compound, and removing an organic component;
A heat treatment step of heating the calcined film to crystallize it to produce an oxide superconducting thin film,
In the organic metal compound solution, 2 ppm or more and less than 2000 ppm of chlorine is added to the total metal ion mass.
本請求項の発明において、希土類元素ＲＥとしては、イットリウム（Ｙ）、プラセオジウム（Ｐｒ）、ネオジウム（Ｎｄ）、サマリウム（Ｓｍ）、ユウロピウム（Ｅｕ）、ガドリウム（Ｇｄ）、ホルミウム（Ｈｏ）、イッテルビウム（Ｙｂ）などを挙げることができ、具体的には、これらのアセチルアセトン金属錯体などが用いられる。また、Ｂａ、Ｃｕの有機化合物としても、アセチルアセトン金属錯体などが用いられる。 In the present invention, the rare earth element RE includes yttrium (Y), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), holmium (Ho), ytterbium ( Yb) and the like, and specifically, these acetylacetone metal complexes are used. Moreover, an acetylacetone metal complex etc. are used also as an organic compound of Ba and Cu.
ＲＥ、Ｂａ、Ｃｕの各有機金属化合物を溶かす溶媒としては、メタノール、エタノール、プロパノール、ブタノールなどの各種アルコールが、溶解度が高く高濃度溶液を作製しやすいという観点から好ましく用いられる。 As the solvent for dissolving the RE, Ba, and Cu organometallic compounds, various alcohols such as methanol, ethanol, propanol, and butanol are preferably used from the viewpoint of high solubility and easy preparation of a high concentration solution.
塩素を添加するためにＭＯＤ溶液に添加される物質としては、トリクロロ酢酸などの有機化合物、塩酸、塩化アンモニウムなどがあるが、熱処理時に塩素をＭＯＤ膜に残留させるという観点から、塩化アンモニウムが好ましく用いられる。なお、塩素としての添加量は、ＭＯＤ溶液の全金属イオン質量に対して２ｐｐｍ以上２０００ｐｐｍ未満と微量であるため、本焼時に塩化水素ガスが発生する恐れはない。 Substances added to the MOD solution to add chlorine include organic compounds such as trichloroacetic acid, hydrochloric acid, and ammonium chloride. Ammonium chloride is preferably used from the viewpoint of leaving chlorine in the MOD film during heat treatment. It is done. In addition, since the addition amount as chlorine is a very small amount of 2 ppm or more and less than 2000 ppm with respect to the total metal ion mass of the MOD solution, there is no fear that hydrogen chloride gas is generated during the main firing.
請求項２に記載の発明は、
前記塗膜作製工程と前記仮焼熱処理工程により、厚さ０．５μｍ以上の仮焼膜を作製した後本焼熱処理を行うことを特徴とする請求項１に記載の酸化物超電導線材の製造方法である。
The invention described in claim 2
2. The method for producing an oxide superconducting wire according to claim 1, wherein a calcining film having a thickness of 0.5 μm or more is produced by the coating film producing step and the calcining heat treatment step, and then a main baking heat treatment is performed. It is.
塩素が適切な量添加されたＭＯＤ溶液を用いて厚さ０．５μｍ以上の仮焼膜を作製することにより、Ｉｃが充分に高い厚膜の酸化物超電導薄膜を安定して得ることができる。 By producing a calcined film having a thickness of 0.5 μm or more using a MOD solution to which an appropriate amount of chlorine is added, a thick oxide superconducting thin film having a sufficiently high Ic can be stably obtained.
請求項３に記載の発明は、
前記酸化物超電導薄膜が、ＲＥＢａ２Ｃｕ３Ｏ７−ｘの薄膜であることを特徴とする請求項１または請求項２に記載の酸化物超電導線材の製造方法である。
The invention according to claim 3
3. The method for producing an oxide superconducting wire according to claim 1, wherein the oxide superconducting thin film is a REBa 2 Cu 3 O 7-x thin film.
ＲＥＢａ２Ｃｕ３Ｏ７−ｘ（ＲＥ１２３）薄膜は、高いＩｃを有する酸化物超電導薄膜であるため、本発明における効果を顕著に発揮させることができる。 Since the REBa 2 Cu 3 O 7-x (RE123) thin film is an oxide superconducting thin film having a high Ic, the effect of the present invention can be remarkably exhibited.
本発明によれば、ＦＦ−ＭＯＤ法を用いた酸化物超電導薄膜線材の製造において、Ｉｃが充分に高い厚膜の酸化物超電導薄膜を安定して得ることが可能となる技術を提供することができる。 According to the present invention, it is possible to provide a technique capable of stably obtaining a thick oxide superconducting thin film having a sufficiently high Ic in the manufacture of an oxide superconducting thin film wire using the FF-MOD method. it can.
以下、本発明を実施例に基づいて具体的に説明する。 Hereinafter, the present invention will be specifically described based on examples.
以下の実施例においては、塩化アンモニウムを添加したＭＯＤ溶液を用いて仮焼膜を２回積層した２層構造の仮焼膜を作製した後、本焼熱処理して、Ｙ１２３（ＹＢａ２Ｃｕ３Ｏ７−ｘ）酸化物超電導薄膜を作製した。 In the following examples, a calcined film having a two-layer structure in which a calcined film is laminated twice using an MOD solution to which ammonium chloride is added is prepared, followed by a main-firing heat treatment to obtain Y123 (YBa 2 Cu 3 O 7-x ) An oxide superconducting thin film was prepared.
［１］酸化物超電導線材の作製
［Ａ．実施例１〜３］
１．仮焼膜の形成
（１）ＭＯＤ溶液の作製
イ．アセチルアセトン金属錯体溶液の調製
Ｙ、Ｂａ、Ｃｕの各アセチルアセトン金属錯体を、Ｙ：Ｂａ：Ｃｕのモル比が１：２：３となるように調製して、メタノールに溶解し、金属錯体溶液を調製した。
[1] Production of oxide superconducting wire [A. Examples 1 to 3]
1. Formation of calcined film (1) Preparation of MOD solution a. Preparation of acetylacetone metal complex solution Each acetylacetone metal complex of Y, Ba and Cu was prepared so that the molar ratio of Y: Ba: Cu was 1: 2: 3, and dissolved in methanol to prepare a metal complex solution. did.
ロ．塩素の添加
調製したアセチルアセトン金属錯体溶液に、１ｍｏｌ／Ｌの塩化アンモニウムを、ＭＯＤ溶液の全金属イオン質量に対して、２ｐｐｍ（実施例１）、２０ｐｐｍ（実施例２）、２００ｐｐｍ（実施例３）の塩素量となるように添加して、３種類のＭＯＤ溶液を作製した。
B. Addition of chlorine 1 mol / L of ammonium chloride was added to the prepared acetylacetone metal complex solution at 2 ppm (Example 1), 20 ppm (Example 2), and 200 ppm (Example 3) based on the total metal ion mass of the MOD solution. Three kinds of MOD solutions were prepared by adding so that the amount of chlorine became the same.
（２）仮焼熱処理
作製した３種類の薄塗ＭＯＤ溶液をそれぞれＣｅＯ２／ＹＳＺ／Ｙ２Ｏ３／Ｎｉ合金の配向基板上に塗布・乾燥後、大気雰囲気の下で、５００℃まで１〜１５℃／分の昇温速度で昇温後、１．５時間保持後炉冷し、厚さ３００ｎｍの仮焼膜を作製した。
(2) Calcining heat treatment Each of the prepared thin coating MOD solutions was applied to a CeO 2 / YSZ / Y 2 O 3 / Ni alloy alignment substrate, dried, and then heated to 500 ° C. in an air atmosphere. The temperature was raised at a rate of 15 ° C./min, held for 1.5 hours, and then cooled in the furnace to prepare a calcined film having a thickness of 300 nm.
上記のＭＯＤ溶液を用いて、仮焼膜を積層し、総膜厚が６００ｎｍの仮焼膜を作製した。 Using the above MOD solution, calcined films were stacked to prepare a calcined film having a total film thickness of 600 nm.
２．本焼熱処理
次に、作製した仮焼膜をアルゴン／酸素混合ガス（酸素濃度：１００ｐｐｍ、ＣＯ２濃度１ｐｐｍ以下）雰囲気の下、１０〜３３℃／分の昇温速度で８００℃まで昇温させ９０分間保持した。その後、酸素濃度１００％雰囲気の下で炉冷し、膜厚が５５０ｎｍ（厚膜）のＹ１２３酸化物超電導薄膜を形成した。
2. Next, the calcined film thus prepared is heated to 800 ° C. at a temperature rising rate of 10 to 33 ° C./min in an argon / oxygen mixed gas (oxygen concentration: 100 ppm, CO 2 concentration: 1 ppm or less) atmosphere. Hold for 90 minutes. Thereafter, the furnace was cooled in an atmosphere having an oxygen concentration of 100% to form a Y123 oxide superconducting thin film having a thickness of 550 nm (thick film).
３．酸化物超電導線材の作製
所定の方法を用いて酸化物超電導薄膜の表面にＡｇ安定化層を形成して、実施例１〜３のＹ１２３酸化物超電導線材を作製した。
3. Production of Oxide Superconducting Wire An Ag stabilizing layer was formed on the surface of the oxide superconducting thin film using a predetermined method, and Y123 oxide superconducting wires of Examples 1 to 3 were produced.
［Ｂ．比較例１〜３］
ＭＯＤ溶液の作製において、塩化アンモニウムの添加量を、ＭＯＤ溶液の全金属イオン質量に対して、それぞれ２ｐｐｂ（比較例１）、２０ｐｐｂ（比較例２）、２００ｐｐｂ（比較例３）の塩素量となるようにしたこと以外は、上記実施例と同様にして、比較例１〜３のＹ１２３酸化物超電導線材を作製した。
[B. Comparative Examples 1 to 3]
In the preparation of the MOD solution, the amount of ammonium chloride added is 2 ppb (Comparative Example 1), 20 ppb (Comparative Example 2), and 200 ppb (Comparative Example 3), respectively, with respect to the total metal ion mass of the MOD solution. Except for the above, Y123 oxide superconducting wires of Comparative Examples 1 to 3 were produced in the same manner as in the above Example.
［Ｃ．比較例４］
ＭＯＤ溶液の作製において、塩化アンモニウムの添加量を、ＭＯＤ溶液の全金属イオン質量に対して２０００ｐｐｍの塩素量となるようにし、仮焼膜を厚さ３００ｎｍの１層としたこと以外は、上記実施例と同様にして、比較例４のＹ１２３酸化物超電導線材を作製した。
[C. Comparative Example 4]
In the preparation of the MOD solution, the above procedure was performed except that the amount of ammonium chloride added was 2,000 ppm of chlorine with respect to the total metal ion mass of the MOD solution, and the calcined film was a single layer having a thickness of 300 nm. The Y123 oxide superconducting wire of Comparative Example 4 was produced in the same manner as the example.
［２］酸化物超電導線材の評価
（１）Ｙ１２３酸化物超電導薄膜の表面状態の観察
実施例１〜３、比較例１〜４の各Ｙ１２３酸化物超電導薄膜の表面をＳＥＭで観察した。観察結果を図１に示す。
[2] Evaluation of oxide superconducting wire (1) Observation of surface state of Y123 oxide superconducting thin film The surface of each Y123 oxide superconducting thin film of Examples 1-3 and Comparative Examples 1-4 was observed by SEM. The observation results are shown in FIG.
図１から、ＭＯＤ溶液に塩化アンモニウムを２〜２００ｐｐｍ添加した実施例１〜３の場合は、塩化アンモニウム添加量が増加するにつれ、平滑な膜の形成が進んでいくことが分かった。 From FIG. 1, it was found that in Examples 1 to 3 in which 2 to 200 ppm of ammonium chloride was added to the MOD solution, the formation of a smooth film progressed as the amount of ammonium chloride added increased.
これに対して、塩化アンモニウムの添加量が２ｐｐｂである比較例１、２０ｐｐｂである比較例２、並びに２００ｐｐｂである比較例３の場合は、塩素の添加効果が充分ではないため、平滑な膜が形成されておらず、一方、２０００ｐｐｍである比較例４では、塩素添加量が過剰なため、表面の凹凸が大きく棒状の塩素化合物が析出している。 On the other hand, in Comparative Example 1 in which the amount of ammonium chloride added is 2 ppb, Comparative Example 2 in which 20 ppb is added, and Comparative Example 3 in which 200 ppb is added, since the effect of adding chlorine is not sufficient, a smooth film is formed. On the other hand, in Comparative Example 4 where the concentration was 2000 ppm, the amount of added chlorine was excessive, so that the surface unevenness was large and a rod-shaped chlorine compound was deposited.
（２）Ｉｃの測定
実施例１〜３および比較例１〜４について、誘導法を用いて７７．３ＫにおけるＩｃを測定した。測定結果を表１に示す。
(2) Measurement of Ic For Examples 1 to 3 and Comparative Examples 1 to 4, Ic at 77.3 K was measured using an induction method. The measurement results are shown in Table 1.
表１より、実施例１〜３で作製されたＹ１２３酸化物超電導薄膜のＩｃは、塩素の添加量が適切でない比較例１〜２に比べてＩｃが高いことが分かる。加えて、塩素添加量とＩｃの傾向を考えると、塩素添加量２ｐｐｍを頂点とする山型になっている。 From Table 1, it can be seen that Ic of the Y123 oxide superconducting thin film produced in Examples 1 to 3 is higher than that of Comparative Examples 1 and 2 in which the addition amount of chlorine is not appropriate. In addition, considering the tendency of the chlorine addition amount and Ic, it has a mountain shape with the peak of the chlorine addition amount of 2 ppm.
以上の結果より、充分に高いＩｃを得るためには、塩素の添加量を２ｐｐｍ以上２０００ｐｐｍ未満にする必要があり、２ｐｐｍ程度が特に好ましいことが分かる。 From the above results, it can be seen that in order to obtain sufficiently high Ic, the amount of chlorine added must be 2 ppm or more and less than 2000 ppm, and about 2 ppm is particularly preferable.
以上のように、本発明によれば、厚膜化してもｃ軸配向が阻害されることがなく、厚膜化することにより、充分に高いＩｃを有する酸化物超電導薄膜が基板上に形成された酸化物超電導線材を提供することができる。 As described above, according to the present invention, the c-axis orientation is not hindered even when the film thickness is increased, and an oxide superconducting thin film having a sufficiently high Ic is formed on the substrate by increasing the film thickness. An oxide superconducting wire can be provided.
以上、本発明を実施の形態に基づき説明したが、本発明は上記の実施の形態に限定されるものではない。本発明と同一および均等の範囲内において、上記の実施の形態に対して種々の変更を加えることが可能である。 As mentioned above, although this invention was demonstrated based on embodiment, this invention is not limited to said embodiment. Various modifications can be made to the above-described embodiment within the same and equivalent scope as the present invention.
Claims (3)
前記有機金属化合物溶液を、前記金属基板上に塗布、乾燥して塗膜を作製する塗膜作製工程と、
前記塗膜を加熱して、前記有機金属化合物を熱分解して、有機成分を除去することにより、仮焼膜を作製する仮焼熱処理工程と、
前記仮焼膜を加熱して、結晶化させることにより、酸化物超電導薄膜を作製する本焼熱処理工程と
を備えており、
前記有機金属化合物の溶液には、全金属イオン質量に対して２ｐｐｍ以上２０００ｐｐｍ未満の塩素が添加されている
ことを特徴とする酸化物超電導線材の製造方法。 An oxide superconducting wire manufacturing method for manufacturing an oxide superconducting wire by producing an oxide superconducting thin film by a coating pyrolysis method using a solution of an organometallic compound not containing fluorine on a metal substrate. ,
The organic metal compound solution is applied onto the metal substrate and dried to prepare a coating film,
A calcining heat treatment step for producing a calcined film by heating the coating film, thermally decomposing the organometallic compound, and removing an organic component;
A heat treatment step of heating the calcined film to crystallize it to produce an oxide superconducting thin film,
2. The method for producing an oxide superconducting wire, wherein the organometallic compound solution contains 2 ppm or more and less than 2000 ppm of chlorine based on the total metal ion mass.
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| KR20240051943A (en) | 2021-09-06 | 2024-04-22 | 스미토모 덴키 고교 가부시키가이샤 | Raw material solution for producing oxide superconducting materials and method for producing oxide superconducting materials |
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| DE112017007199T5 (en) | 2017-03-09 | 2019-12-05 | Sumitomo Electric Industries, Ltd. | A superconducting oxide thin film material, a superconducting oxide thin film wire, and a method of producing an oxide superconductor thin film |
| US11763965B2 (en) | 2017-03-09 | 2023-09-19 | Sumitomo Electric Industries, Ltd. | Oxide superconducting thin film material, oxide superconducting thin film wire, and method for manufacturing oxide superconducting thin film |
| KR20240051943A (en) | 2021-09-06 | 2024-04-22 | 스미토모 덴키 고교 가부시키가이샤 | Raw material solution for producing oxide superconducting materials and method for producing oxide superconducting materials |
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