JPH0733567B2 - Method for manufacturing thick film oxide superconductor - Google Patents
Method for manufacturing thick film oxide superconductorInfo
- Publication number
- JPH0733567B2 JPH0733567B2 JP62102237A JP10223787A JPH0733567B2 JP H0733567 B2 JPH0733567 B2 JP H0733567B2 JP 62102237 A JP62102237 A JP 62102237A JP 10223787 A JP10223787 A JP 10223787A JP H0733567 B2 JPH0733567 B2 JP H0733567B2
- Authority
- JP
- Japan
- Prior art keywords
- thick film
- oxide
- superconductor
- hours
- 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.)
- Expired - Lifetime
Links
- 239000002887 superconductor Substances 0.000 title claims description 29
- 238000000034 method Methods 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000000758 substrate Substances 0.000 claims description 33
- 238000007750 plasma spraying Methods 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000005507 spraying Methods 0.000 claims description 6
- 239000010408 film Substances 0.000 description 54
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 19
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- 239000010949 copper Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000001307 helium Substances 0.000 description 6
- 229910052734 helium Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 229910052788 barium Inorganic materials 0.000 description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 4
- 238000007751 thermal spraying Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 3
- 238000004544 sputter deposition Methods 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 229910016063 BaPb Inorganic materials 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 238000004458 analytical method 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- UFQXGXDIJMBKTC-UHFFFAOYSA-N oxostrontium Chemical compound [Sr]=O UFQXGXDIJMBKTC-UHFFFAOYSA-N 0.000 description 1
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N60/00—Superconducting devices
- H10N60/01—Manufacture or treatment
- H10N60/0268—Manufacture or treatment of devices comprising copper oxide
- H10N60/0296—Processes for depositing or forming copper oxide superconductor layers
- H10N60/0492—Processes for depositing or forming copper oxide superconductor layers by thermal spraying, e.g. plasma deposition
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Coating By Spraying Or Casting (AREA)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は任意の大きさ、形状の基板面上に、厚膜状態で
高速に形成できる厚膜酸化物超電導体の製造方法に関す
るものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a thick film oxide superconductor which can be formed on a substrate surface having an arbitrary size and shape in a thick film state at high speed.
従来の技術 従来の膜状酸化物超電導体の製造方法として、スパッタ
リングによる製造方法が知られている。これは、酸化物
超電導体焼結体、例えば、BaPb0.7Bi0.3O3（BPB）をタ
ーゲットとし、酸素を少し含むアルゴンガス中でスパッ
タリングにより、基板上に薄膜を形成するものである。2. Description of the Related Art As a conventional method for manufacturing a film-shaped oxide superconductor, a manufacturing method by sputtering is known. This is for forming a thin film on a substrate by sputtering an oxide superconductor sintered body, for example, BaPb 0.7 Bi 0.3 O 3 (BPB) as a target in argon gas containing a small amount of oxygen.
発明が解決しようとする問題点 しかし、従来例のこのような製造方法に基づくもので
は、膜形成速度が約１μm/時間と遅いこと、また真空中
で形成しなければならないことから、大型のものが得に
くいこと、またターゲット面と基板との距離がことなる
と、膜の厚み、均一性などが異なるようになることか
ら、生産性に種々の問題があった。Problems to be Solved by the Invention However, the conventional method based on such a manufacturing method has a large film formation rate because it has a low film forming rate of about 1 μm / hour and must be formed in a vacuum. Is difficult to obtain, and if the distance between the target surface and the substrate is different, the film thickness, uniformity, and the like will be different, resulting in various problems in productivity.
本発明はかかる点に鑑みなされたもので、任意の形状の
広い面積に、数μｍから数100μｍの厚膜を高速に形成
できる厚膜酸化物超電導体の製造方法を提供することを
目的としている。The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for manufacturing a thick-film oxide superconductor capable of forming a thick film of several μm to several 100 μm at a high speed in a wide area of an arbitrary shape. .
問題点を解決するための手段 本発明は上記問題点を解決するため、セラミック等の耐
熱性基板上に、プラズマ溶射法により、層状ペロブスカ
イト構造超電導体酸化物原料を溶射して厚膜を形成した
後、800〜1100℃で熱処理を行い、この熱処理によっ
て、前記厚膜を層状ペロブスカイト構造の超電導体酸化
物の状態にするという生産性に優れた厚膜酸化物超電導
体の製造方法を提供するものである。Means for Solving the Problems In order to solve the above problems, the present invention forms a thick film by thermally spraying a layered perovskite structure superconducting oxide raw material on a heat resistant substrate such as a ceramic by a plasma spraying method. After that, heat treatment is performed at 800 to 1100 ° C., and by this heat treatment, a method for producing a thick film oxide superconductor excellent in productivity of forming the thick film into a superconducting oxide state of a layered perovskite structure is provided. Is.
作用 本発明は、前記した製造方法により、任意の形状の大型
基板上に、高速に厚膜酸化物超電導体を形成することが
できる。Effect The present invention can form a thick film oxide superconductor on a large-sized substrate having an arbitrary shape at high speed by the above-described manufacturing method.
実施例 （実施例１） 酸化イットリウム（Y2O3）、酸化バリウム（BaO）と酸
化銅（CuO）をY0.4Ba0.6Cu1の比で含むようそれぞれ秤
量し、混合の後、900℃の空気中で５時間焼成した。こ
れをもう一度粉砕、混合した後、900℃の空気中で12時
間焼成し、再度粉砕し、プラズマ溶射用原料とした。Example (Example 1) Yttrium oxide (Y 2 O 3 ), barium oxide (BaO) and copper oxide (CuO) were weighed so as to be included in a ratio of Y 0.4 Ba 0.6 Cu 1 , and mixed at 900 ° C. Baking for 5 hours in air. This was pulverized and mixed once again, then fired in air at 900 ° C. for 12 hours and pulverized again to obtain a plasma spraying raw material.
次に、研磨、洗浄されたアルミナ基板に、前記焼成物粉
体を原料とし、プラズマ溶射法によって吹き付け、約50
μｍの厚膜をアルミナ基板上全面に形成した。その後、
950℃の空気中で10時間熱処理を行った。冷却後、得ら
れた厚膜の電気抵抗を液体窒素（77K）温度で測定した
結果、超電導性を示した。すなわちこのような方法で形
成した厚膜は、超電導体であった。得られた厚膜を、Ｘ
線解析で調べたところ、層状ペロブスカイト構造を示し
ていた。Next, the alumina substrate that has been polished and cleaned is sprayed by a plasma spraying method using the above-mentioned fired material powder as a raw material to about 50
A thick film of μm was formed on the entire surface of the alumina substrate. afterwards,
Heat treatment was performed in air at 950 ° C. for 10 hours. After cooling, the electric resistance of the obtained thick film was measured at liquid nitrogen (77K) temperature, and it showed superconductivity. That is, the thick film formed by such a method was a superconductor. The thick film obtained was
The line analysis revealed a layered perovskite structure.
第１図は本発明の厚膜酸化物超電導体をアルミナ基板上
に形成する場合の構造の一実施例を示したものである。
第１図において、１はアルミナセラミック基板、２はプ
ラズマ溶射により形成した厚膜酸化物超電導体層であ
る。FIG. 1 shows an embodiment of a structure in which the thick film oxide superconductor of the present invention is formed on an alumina substrate.
In FIG. 1, 1 is an alumina ceramic substrate and 2 is a thick film oxide superconductor layer formed by plasma spraying.
各層の厚みは、本実施例ではアルミナセラミック基板１
が635μｍ、厚膜酸化物超電導体の厚みは50μｍであ
る。The thickness of each layer is the alumina ceramic substrate 1 in this embodiment.
Is 635 μm, and the thickness of the thick-film oxide superconductor is 50 μm.
第２図は層状ペロブスカイト構造の基本構成単位である
ペロブスカイト構造を示したものであり、図において、
３はCu、４はＯ、５はＹまたはBaである。本実施例の層
状ペロブスカイト構造は、この構造がある周期をもっ
て、層状に積み重なったものである。FIG. 2 shows a perovskite structure which is a basic constitutional unit of a layered perovskite structure.
3 is Cu, 4 is O, 5 is Y or Ba. The layered perovskite structure of this embodiment is a layered structure having a certain period.
（実施例２） 酸化ランタン（La2O3）、酸化バリウム（BaO）と酸化銅
（CuO）を、La1.84Ba0.16Cu1の比で含むようそれぞれ秤
量し、混合の後、900℃の空気中で５時間焼成した。こ
れをもう一度粉砕、混合した後、900℃の空気中で12時
間焼成し、再度粉砕し、プラズマ溶射用原料とした。(Example 2) Lanthanum oxide (La 2 O 3 ), barium oxide (BaO) and copper oxide (CuO) were weighed so as to be included in a ratio of La 1.84 Ba 0.16 Cu 1 , and mixed, and then air at 900 ° C. Baking for 5 hours. This was pulverized and mixed once again, then fired in air at 900 ° C. for 12 hours and pulverized again to obtain a plasma spraying raw material.
次に、研磨、洗浄されたアルミナ基板に、前記焼成物粉
体を原料とし、プラズマ溶射法によって吹き付け、約50
μｍの厚膜をアルミナ基板上全面に形成した。その後、
800℃の空気中で10時間熱処理を行った。冷却後、得ら
れた厚膜の電気抵抗を液体ヘリウム温度で測定した結
果、超電導性を示した。すなわちこのような方法で形成
した厚膜は、超電導体であった。得られた厚膜を、Ｘ線
解析で調べたところ、層状ペロブスカイト構造を示して
いた。Next, the alumina substrate that has been polished and cleaned is sprayed by a plasma spraying method using the above-mentioned fired material powder as a raw material to about 50
A thick film of μm was formed on the entire surface of the alumina substrate. afterwards,
Heat treatment was performed in air at 800 ° C. for 10 hours. After cooling, the electric resistance of the obtained thick film was measured at the liquid helium temperature, and it showed superconductivity. That is, the thick film formed by such a method was a superconductor. When the obtained thick film was examined by X-ray analysis, it showed a layered perovskite structure.
（実施例３） 酸化ランタン（La2O3）、酸化カルシウム（Ca2O3）と酸
化銅（CuO）を、La1.84Ca0.16Cu1の比で含むようそれぞ
れ秤量し、混合の後、900℃の空気中で５時間焼成し
た。これをもう一度粉砕、混合した後、900℃の空気中
で12時間焼成し、再度粉砕し、プラズマ溶射用原料とし
た。(Example 3) Lanthanum oxide (La 2 O 3 ), calcium oxide (Ca 2 O 3 ) and copper oxide (CuO) were weighed so as to be included in the ratio of La 1.84 Ca 0.16 Cu 1 , and after mixing, 900 It was baked in air at 0 ° C. for 5 hours. This was pulverized and mixed once again, then fired in air at 900 ° C. for 12 hours and pulverized again to obtain a plasma spraying raw material.
次に、研磨、洗浄されたアルミナ基板に、前記焼成物粉
体を原料とし、プラズマ溶射法によって吹き付け、約50
μｍの厚膜をアルミナ基板上全面に形成した。その後、
900℃の空気中で10時間熱処理を行った。冷却後、得ら
れた厚膜の電気抵抗を液体ヘリウム（4K）温度で測定し
た結果、超電導性を示した。すなわちこのような方法で
形成した厚膜は、超電導体であった。得られた厚膜を、
Ｘ線解析で調べたところ、層状ペロブスカイト構造を示
していた。Next, the alumina substrate that has been polished and cleaned is sprayed by a plasma spraying method using the above-mentioned fired material powder as a raw material to about 50
A thick film of μm was formed on the entire surface of the alumina substrate. afterwards,
Heat treatment was performed in air at 900 ° C. for 10 hours. After cooling, the electric resistance of the obtained thick film was measured at liquid helium (4K) temperature, and it showed superconductivity. That is, the thick film formed by such a method was a superconductor. The thick film obtained is
When examined by X-ray analysis, it showed a layered perovskite structure.
（実施例４） 酸化ランタン（La2O3）、酸化ストロンチウム（SrO）と
酸化銅（CuO）を、La1.84Sr0.16Cu1の比で含むようそれ
ぞれ秤量し、混合の後、900℃の空気中で５時間焼成し
た。これをもう一度粉砕、混合した後、900℃の空気中
で12時間焼成し、再度粉砕し、プラズマ溶射用原料とし
た。(Example 4) Lanthanum oxide (La 2 O 3 ), strontium oxide (SrO) and copper oxide (CuO) were weighed so as to be included in a ratio of La 1.84 Sr 0.16 Cu 1 , and mixed, and then air at 900 ° C. Baking for 5 hours. This was pulverized and mixed once again, then fired in air at 900 ° C. for 12 hours and pulverized again to obtain a plasma spraying raw material.
次に、研磨、洗浄されたアルミナ基板に、前記焼成物粉
体を原料とし、プラズマ溶射法によって吹き付け、約50
μｍの厚膜をアルミナ基板上全面に形成した。その後、
1100℃の空気中で10時間熱処理を行った。冷却後、得ら
れた厚膜の電気抵抗を液体ヘリウム（4K）温度で測定し
た結果、超電導性を示した。すなわちこのような方法で
形成した厚膜は、超電導体であった。得られた厚膜を、
Ｘ線解析で調べたところ、層状ペロブスカイト構造を示
していた。Next, the alumina substrate that has been polished and cleaned is sprayed by a plasma spraying method using the above-mentioned fired material powder as a raw material to about 50
A thick film of μm was formed on the entire surface of the alumina substrate. afterwards,
Heat treatment was performed in air at 1100 ° C. for 10 hours. After cooling, the electric resistance of the obtained thick film was measured at liquid helium (4K) temperature, and it showed superconductivity. That is, the thick film formed by such a method was a superconductor. The thick film obtained is
When examined by X-ray analysis, it showed a layered perovskite structure.
（実施例５） 酸化イットリウム（Y2O3）、酸化スカンジウム（Sc
2O3）、酸化バリウム（BaO）と酸化銅（CuO）を、(YSc)
0.4Ba0.6Cu1の比で含むようそれぞれ秤量し、混合の
後、900℃の空気中で５時間焼成した。これをもう一度
粉砕、混合した後、900℃の空気中で12時間焼成し、再
度粉砕し、プラズマ溶射用原料とした。(Example 5) Yttrium oxide (Y 2 O 3 ) and scandium oxide (Sc
2 O 3 ), barium oxide (BaO) and copper oxide (CuO), (YSc)
Each of them was weighed so as to have a ratio of 0.4 Ba 0.6 Cu 1 , mixed, and then baked in air at 900 ° C. for 5 hours. This was pulverized and mixed once again, then fired in air at 900 ° C. for 12 hours and pulverized again to obtain a plasma spraying raw material.
次に、研磨、洗浄されたアルミナ基板に、前記焼成物粉
体を原料とし、プラズマ溶射法によって吹き付け、約50
μｍの厚膜をアルミナ基板上全面に形成した。その後、
950℃の空気中で10時間熱処理を行った。冷却後、得ら
れた厚膜の電気抵抗を液体ヘリウム（4K）温度で測定し
た結果、超電導性を示した。すなわちこのような方法で
形成した厚膜は、超電導体であった。得られた厚膜を、
Ｘ線解析で調べたところ、層状ペロブスカイト構造を示
していた。Next, the alumina substrate that has been polished and cleaned is sprayed by a plasma spraying method using the above-mentioned fired material powder as a raw material to about 50
A thick film of μm was formed on the entire surface of the alumina substrate. afterwards,
Heat treatment was performed in air at 950 ° C. for 10 hours. After cooling, the electric resistance of the obtained thick film was measured at liquid helium (4K) temperature, and it showed superconductivity. That is, the thick film formed by such a method was a superconductor. The thick film obtained is
When examined by X-ray analysis, it showed a layered perovskite structure.
（実施例６） 希土類酸化物（Yb、Tm、Er、Ho、Dy、Gdの酸化物）、酸
化バリウム（BaO）と酸化銅（CuO）を、酸化銅１に対
し、希土類酸化物と酸化物バリウムが、0.3および0.7に
なるよう上記希土類酸化物の種類と量の組合せを種々変
えて秤量し、混合の後、900℃の空気中で５時間焼成し
た。これをもう一度粉砕、混合した後、900℃の空気中
で12時間焼成し、再度粉砕し、プラズマ溶射用原料とし
た。(Example 6) Rare earth oxides (oxides of Yb, Tm, Er, Ho, Dy, and Gd), barium oxide (BaO) and copper oxide (CuO), with respect to 1 copper oxide, rare earth oxides and oxides. Various kinds and combinations of the above rare earth oxides were weighed so that barium was 0.3 and 0.7, and the mixture was mixed and then calcined in air at 900 ° C. for 5 hours. This was pulverized and mixed once again, then fired in air at 900 ° C. for 12 hours and pulverized again to obtain a plasma spraying raw material.
次に、研磨、洗浄されたアルミナ基板に、前記焼成物粉
体を原料とし、プラズマ溶射法によって吹き付け、約50
μｍの厚膜をアルミナ基板上全面に形成した。その後、
900℃の空気中で10時間熱処理を行った。冷却後、得ら
れた厚膜の電気抵抗を液体ヘリウム（4K）温度で測定し
た結果、超電導性を示した。すなわちこのような方法で
形成した厚膜は、超電導体であった。得られた厚膜を、
Ｘ線解析で調べたところ、層状ペロブスカイト構造を示
していた。Next, the alumina substrate that has been polished and cleaned is sprayed by a plasma spraying method using the above-mentioned fired material powder as a raw material to about 50
A thick film of μm was formed on the entire surface of the alumina substrate. afterwards,
Heat treatment was performed in air at 900 ° C. for 10 hours. After cooling, the electric resistance of the obtained thick film was measured at liquid helium (4K) temperature, and it showed superconductivity. That is, the thick film formed by such a method was a superconductor. The thick film obtained is
When examined by X-ray analysis, it showed a layered perovskite structure.
（実施例７） 酸化イットリウム（Y2O3）、酸化ストロンチウム（Sr
O）と酸化銅（CuO）を、Y0.4Sr0.6Cu1の比で含むようそ
れぞれ秤量し、混合の後、900℃の空気中で５時間焼成
した。これをもう一度粉砕、混合した後、900℃の空気
中で12時間焼成し、再度粉砕し、プラズマ溶射用原料と
した。Example 7 Yttrium oxide (Y 2 O 3 ) and strontium oxide (Sr
O) and copper oxide (CuO) were weighed so as to be included in the ratio of Y 0.4 Sr 0.6 Cu 1 and mixed, and then baked in air at 900 ° C. for 5 hours. This was pulverized and mixed once again, then fired in air at 900 ° C. for 12 hours and pulverized again to obtain a plasma spraying raw material.
次に、研磨、洗浄されたアルミナ基板に、前記焼成物粉
体を原料とし、プラズマ溶射法によって吹き付け、約50
μｍの厚膜をアルミナ基板上全面に形成した。その後、
950℃の空気中で10時間熱処理を行った。冷却後、得ら
れた厚膜の電気抵抗を液体ヘリウム（4K）温度で測定し
た結果、超電導性を示した。すなわちこのような方法で
形成した厚膜は、超電導体であった。得られた厚膜を、
Ｘ線解析で調べたところ、層状ペロブスカイト構造を示
していた。Next, the alumina substrate that has been polished and cleaned is sprayed by a plasma spraying method using the above-mentioned fired material powder as a raw material to about 50
A thick film of μm was formed on the entire surface of the alumina substrate. afterwards,
Heat treatment was performed in air at 950 ° C. for 10 hours. After cooling, the electric resistance of the obtained thick film was measured at liquid helium (4K) temperature, and it showed superconductivity. That is, the thick film formed by such a method was a superconductor. The thick film obtained is
When examined by X-ray analysis, it showed a layered perovskite structure.
以上述べた如く、本発明の方法によれば、任意の形状の
大型基板上に、厚膜酸化物超電導体を高速に形成するこ
とができる。As described above, according to the method of the present invention, a thick film oxide superconductor can be formed at high speed on a large-sized substrate having an arbitrary shape.
本実施例の製造方法によれば、層状ペロブスカイト構造
を有する酸化物超電導体については、いずれの材料につ
いても適用できるものである。第２図は、実施例１のも
のについて説明したものであるが、実施例２〜７のもの
は、Ｙ、Baの代りに、それぞれの実施例で用いられた、
Cu、Ｏ以外の元素が、置き代ったものである。According to the manufacturing method of the present embodiment, any material can be applied to the oxide superconductor having the layered perovskite structure. FIG. 2 illustrates the example 1, but the examples 2 to 7 were used in each example instead of Y and Ba.
Elements other than Cu and O are replaced.
また本実施例の方法では、プラズマ溶射された厚膜が超
電導体となる熱処理の温度は、いずれも800〜1100℃の
間であり、800℃より低くても、1100℃より高くても、
良好な結果は得られなかった。またプラズマ溶射のみで
熱処理を行わなかったものも良好な結果が得られなかっ
た。この場合には、溶射されただけでは、厚膜がきれい
な層状ペロブスカイト構造になっていないためと思われ
る。溶射後、適当な条件で熱処理することにより、きれ
いな層状ペロブスカイト構造となり、酸素欠陥が適当に
制御されて、超伝導性を示すようになるものと思われ
る。Further, in the method of the present example, the temperature of the heat treatment in which the plasma sprayed thick film becomes a superconductor is between 800 and 1100 ° C, both lower than 800 ° C and higher than 1100 ° C.
Good results have not been obtained. Also, good results could not be obtained in the case of only plasma spraying and not heat treatment. In this case, it is considered that the thick film does not have a clean layered perovskite structure only by thermal spraying. It is considered that after the thermal spraying, a heat treatment under appropriate conditions results in a clean layered perovskite structure, oxygen defects are appropriately controlled, and superconductivity is exhibited.
本実施例では、基板としてアルミナ基板を用いたが、10
00℃程度の温度の熱処理に耐えるもので、化学的にも安
定なものであれば、この材料に限る必要のないことは明
らかである。In this embodiment, an alumina substrate is used as the substrate,
Obviously, it is not necessary to limit to this material as long as it can withstand a heat treatment at a temperature of about 00 ° C. and is chemically stable.
また本実施例では、基板の厚み、および厚膜酸化物超電
導体の厚みとして特定の値を用いたが、基板の厚みは任
意であり、また厚膜の厚みは、10秒で数μｍから数10μ
ｍ程度の厚みが得られるので、この時間を適当に選ぶこ
とにより、数μｍ〜数100μｍの厚みを任意に選ぶこと
は極めて容易である。Further, in this example, although specific values were used as the thickness of the substrate and the thickness of the thick film oxide superconductor, the thickness of the substrate is arbitrary, and the thickness of the thick film is from several μm to several μm in 10 seconds. 10μ
Since a thickness of about m can be obtained, it is extremely easy to arbitrarily select the thickness of several μm to several 100 μm by appropriately selecting this time.
また本実施例で用いたプラズマ溶射装置は、溶射トー
チ、粉末送給装置、制御装置および電源から構成されて
いる。まずガスを溶射トーチ内のアーク発生部に導き、
数1000℃の高温に加熱する。これによりガスはプラズマ
状態となってノズルから噴出する。このプラズマジェッ
トの中へ、溶射用原料粉末を、送給用ガス流にのせて送
りこむと、この原料粉末は、溶融状態となって基板表面
に高速度で溶射され、皮膜状に析出する。上記各実施例
ではガスに不活性ガスを用い、アーク電流として900A流
し、３〜５分溶射を行って厚膜を形成した。厚膜は溶射
時間を変えることによって、容易に制御できる。またノ
ズルを動かすことによって、溶射場所を任意に移動でき
るので、基板の表面が曲面であっても、ノズルの陰にな
らない限り溶射が可能である。したがってノズルを動か
すことによって、基本的には任意の形状の基板上に厚膜
を形成することができる。また溶射速度は、スパッタリ
ング等に比べ、２桁から３桁程度早いので、大きな物に
も高速で形成することができる。The plasma spraying apparatus used in this example is composed of a spraying torch, a powder feeder, a controller and a power source. First, guide the gas to the arc generation part in the spray torch,
Heat to a high temperature of a few 1000 ° C As a result, the gas becomes a plasma state and is ejected from the nozzle. When the raw material powder for thermal spraying is fed into the plasma jet by being carried on the gas flow for feeding, the raw material powder is in a molten state and is sprayed at a high speed on the surface of the substrate to be deposited in the form of a film. In each of the above examples, an inert gas was used as a gas, and an arc current of 900 A was applied, and thermal spraying was performed for 3 to 5 minutes to form a thick film. Thick films can be easily controlled by changing the spray time. Further, since the spraying location can be arbitrarily moved by moving the nozzle, even if the surface of the substrate is a curved surface, the spraying is possible as long as it is not behind the nozzle. Therefore, by moving the nozzle, a thick film can be basically formed on a substrate having an arbitrary shape. Further, since the spraying speed is about two to three orders of magnitude higher than that of sputtering or the like, it is possible to form a large object at a high speed.
発明の効果 以上述べた如く、本発明は、基板上に、プラズマ溶射法
により、層状ペロブスカイト構造超電導体酸化物原料を
溶射して厚膜を形成した後、800〜1100℃で熱処理を行
い、この熱処理によって、厚膜を層状ペロブスカイト構
造の超電導体酸化物の状態にすることにより、任意の形
状の大型の基板上に、高速に厚膜酸化物超電導体を形成
できるようにしたものである。As described above, according to the present invention, by plasma spraying method, a layered perovskite structure superconductor oxide raw material is sprayed to form a thick film, and then heat treatment is performed at 800 to 1100 ° C. By heat-treating the thick film into a state of a superconductor oxide having a layered perovskite structure, a thick oxide superconductor can be formed at high speed on a large-sized substrate having an arbitrary shape.
第１図は本発明の構造の一実施例を示す構成図、第２図
は本発明に用いた酸化物超電導体の結晶構造である層状
ペロブスカイト構造の、基本構成要素であるペロブスカ
イト構造を示した説明図である。 １……アルミナセラミック基板、２……厚膜酸化物超電
導体、３……Cu、４……Ｏ、５……ＹまたはBa。FIG. 1 is a block diagram showing an embodiment of the structure of the present invention, and FIG. 2 shows a perovskite structure which is a basic constituent element of the layered perovskite structure which is the crystal structure of the oxide superconductor used in the present invention. FIG. 1 ... Alumina ceramic substrate, 2 ... Thick film oxide superconductor, 3 ... Cu, 4 ... O, 5 ... Y or Ba.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０１Ｌ 39/12 Ｃ 9276−4Ｍ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display location H01L 39/12 C 9276-4M
Claims (1)
層状ペロブスカイト構造超電導体酸化物原料を溶射して
厚膜を形成した後、800〜1100℃で熱処理を行い、この
熱処理によって、前記厚膜を層状ペロブスカイト構造の
超電導体酸化物の状態にすることを特徴とする厚膜酸化
物超電導体の製造方法。1. A plasma spraying method on a heat resistant substrate,
After forming a thick film by spraying a layered perovskite structure superconductor oxide raw material, heat treatment is performed at 800 to 1100 ° C., and by this heat treatment, the thick film is made into a state of a layered perovskite structure superconductor oxide. A method for producing a thick-film oxide superconductor characterized by the above-mentioned.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62102237A JPH0733567B2 (en) | 1987-04-24 | 1987-04-24 | Method for manufacturing thick film oxide superconductor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62102237A JPH0733567B2 (en) | 1987-04-24 | 1987-04-24 | Method for manufacturing thick film oxide superconductor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63270450A JPS63270450A (en) | 1988-11-08 |
| JPH0733567B2 true JPH0733567B2 (en) | 1995-04-12 |
Family
ID=14322029
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62102237A Expired - Lifetime JPH0733567B2 (en) | 1987-04-24 | 1987-04-24 | Method for manufacturing thick film oxide superconductor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0733567B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2573650B2 (en) * | 1987-04-10 | 1997-01-22 | 住友電気工業株式会社 | Superconductor manufacturing method |
| DE3853094T2 (en) * | 1987-04-28 | 1995-08-10 | Ibm | Fast, large-area coating made of superconductors with a high transition temperature. |
| JPS63289722A (en) * | 1987-05-20 | 1988-11-28 | Sumitomo Electric Ind Ltd | Superconductor manufacturing method |
| JP2604437B2 (en) * | 1987-10-15 | 1997-04-30 | 東燃株式会社 | High-temperature fuel cell interelectrode assembly and high-temperature fuel cell cathode current collector |
| JPH02192615A (en) * | 1989-01-20 | 1990-07-30 | Ngk Insulators Ltd | Metal coated superconductive ceramics compact and manufacture thereof |
| JPH0313556A (en) * | 1989-06-09 | 1991-01-22 | Ngk Insulators Ltd | Production of oxide superconductor |
| JP2584519B2 (en) * | 1989-12-29 | 1997-02-26 | 東洋インキ製造株式会社 | Method for producing perovskite-type composite oxide powder |
| WO2026080248A1 (en) * | 2024-10-11 | 2026-04-16 | Coorstek, Inc. | Polycrystalline rare earth aluminum perovskite materials and methods of making the same |
-
1987
- 1987-04-24 JP JP62102237A patent/JPH0733567B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63270450A (en) | 1988-11-08 |
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