JPH0773758A - Structure of oxide superconductor with stabilized metallic layer - Google Patents

Structure of oxide superconductor with stabilized metallic layer

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Publication number
JPH0773758A
JPH0773758A JP5221467A JP22146793A JPH0773758A JP H0773758 A JPH0773758 A JP H0773758A JP 5221467 A JP5221467 A JP 5221467A JP 22146793 A JP22146793 A JP 22146793A JP H0773758 A JPH0773758 A JP H0773758A
Authority
JP
Japan
Prior art keywords
layer
oxide superconducting
stabilizing
intermediate layer
thickness
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.)
Granted
Application number
JP5221467A
Other languages
Japanese (ja)
Other versions
JP3568561B2 (en
Inventor
Kazunori Onabe
和憲 尾鍋
Yasuhiro Iijima
康裕 飯島
Nobuyuki Sadakata
伸行 定方
Takashi Saito
隆 斉藤
Tsukasa Kono
宰 河野
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujikura Ltd
Original Assignee
Fujikura Ltd
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Filing date
Publication date
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Priority to JP22146793A priority Critical patent/JP3568561B2/en
Publication of JPH0773758A publication Critical patent/JPH0773758A/en
Application granted granted Critical
Publication of JP3568561B2 publication Critical patent/JP3568561B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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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  • Crystals, And After-Treatments Of Crystals (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)

Abstract

PURPOSE:To provide a structure by which the rate of reduction in a critical current density in bending of a superconductive tape can be reduced and the critical current density can be increased. CONSTITUTION:An oxide superconductive layer 3 is formed on a tape base material 1 via an intermediate layer 2. A good conductive stabilized metallic layer 4, whose thickness is equal to the total thickness of the base member 1 and the intermediate layer 2, is formed on the oxide superconductive layer 3.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】この発明は、安定化金属層を備え
た酸化物超電導導体の製造方法に関するもので、この種
の酸化物超電導導体は、超電導マグネット、超電導発電
機、エネルギー貯蔵、電力輸送などへの応用開発が進め
られているものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an oxide superconducting conductor having a stabilizing metal layer, which is used as a superconducting magnet, a superconducting generator, energy storage, and electric power transport. The application development is being promoted.

【０００２】[0002]

【従来の技術】従来、レーザ蒸着法やＣＶＤ法などの成
膜法により、テープ状の基材上に酸化物超電導層を形成
して超電導導体を形成することがなされている。そし
て、この種の成膜法によって形成した薄膜状の酸化物超
電導層は、従来知られている酸化物超電導体の構成元素
の粉末を銅パイプに充填し、それに縮径加工を施し、更
に熱処理を施して得られる形式の超電導導体よりも高い
臨界電流密度（Ｊｃ）を示すことが知られている。ま
た、この種の超電導導体は、液体窒素温度（７７Ｋ）で
冷却して超電導状態とした上で磁場を作用させた場合
に、磁場による超電導特性の劣化割合も少ないとされて
いるので、この種のテープ状の酸化物超電導導体を用い
てコイル加工を施し、小型で軽量の超電導マグネットを
製造する試みがなされている。2. Description of the Related Art Conventionally, a superconducting conductor has been formed by forming an oxide superconducting layer on a tape-shaped substrate by a film forming method such as a laser vapor deposition method or a CVD method. Then, the thin film oxide superconducting layer formed by this kind of film forming method is filled with powder of the constituent elements of the conventionally known oxide superconductor in a copper pipe, subjected to diameter reduction processing, and further heat treated. It is known to have a higher critical current density (Jc) than that of the superconducting conductor of the type obtained by applying. In addition, this type of superconducting conductor is said to have a low rate of deterioration of superconducting properties due to a magnetic field when it is cooled at liquid nitrogen temperature (77 K) to be in a superconducting state and then subjected to a magnetic field. Attempts have been made to manufacture a compact and lightweight superconducting magnet by performing coil processing using the tape-shaped oxide superconducting conductor.

【０００３】ところが、金属テープなどの長尺の基材の
上に酸化物超電導層を直接成膜すると、金属テープが多
結晶体であり、金属テープの結晶構造が、酸化物超電導
層の結晶構造と大きく異なり、しかも、結晶の配向性も
揃っていない関係から、その上に成膜される酸化物超電
導層の結晶配向性も乱れたものになり、結晶配向性が乱
れた酸化物超電導層では、良好な超電導特性が得られな
い問題がある。また、金属テープと酸化物超電導層では
熱膨張係数が大きく異なるので、酸化物超電導層を形成
する際に施す熱処理時の加熱冷却処理の際に、熱膨張係
数の違いに起因する熱歪が蓄積され、場合によっては酸
化物超電導層にクラックを生じさせてしまい、臨界電流
密度が大幅に低下する問題がある。更に、前記熱処理の
際に、金属テープと酸化物超電導層との間に元素の拡散
現象を生じると、金属テープの構成元素の一部が酸化物
超電導層側に拡散するか、酸化物超電導層の構成元素の
一部が金属テープ側に拡散することになり、いずれにし
ても酸化物超電導層の組成が崩れて超電導特性が劣化す
る問題がある。However, when the oxide superconducting layer is directly formed on a long base material such as a metal tape, the metal tape is a polycrystal, and the crystal structure of the metal tape is the crystal structure of the oxide superconducting layer. However, since the crystal orientation is not uniform, the crystal orientation of the oxide superconducting layer formed on it is also disordered, and in the oxide superconducting layer with disordered crystal orientation, However, there is a problem that good superconducting characteristics cannot be obtained. In addition, since the thermal expansion coefficient of the metal tape and that of the oxide superconducting layer differ greatly, thermal strain due to the difference in thermal expansion coefficient accumulates during the heating / cooling process during the heat treatment performed when forming the oxide superconducting layer. As a result, cracks may occur in the oxide superconducting layer in some cases, and there is a problem that the critical current density is significantly reduced. Further, during the heat treatment, if an element diffusion phenomenon occurs between the metal tape and the oxide superconducting layer, some of the constituent elements of the metal tape diffuse to the oxide superconducting layer side or the oxide superconducting layer. Therefore, there is a problem that the composition of the oxide superconducting layer is destroyed and the superconducting characteristics are deteriorated, because a part of the constituent elements of (3) is diffused to the metal tape side.

【０００４】そこで従来、金属テープの上に結晶配向性
の優れた中間層、例えば、ＭｇＯやＳｒＴｉＯ3、イッ
トリウム安定化ジルコニア（ＹＳＺ）などのような酸化
物超電導体と結晶構造の類似した中間層を形成し、この
中間層上に酸化物超電導層を成膜することで、金属テー
プなどの長尺の基材上に結晶配向性の優れた酸化物超電
導層を形成することがなされている。このような中間層
を金属テープと酸化物超電導層の間に形成するならば、
熱膨張係数の差異に起因する熱歪の蓄積を緩和すること
ができ、酸化物超電導層と金属テープとの間の元素拡散
も抑制できるので、特性の優れた酸化物超電導層を備え
た酸化物超電導導体を得ることができる。Therefore, conventionally, an intermediate layer having a superior crystal orientation on a metal tape, for example, an intermediate layer having a crystal structure similar to that of an oxide superconductor such as MgO, SrTiO 3 , or yttrium-stabilized zirconia (YSZ). Is formed and an oxide superconducting layer is formed on this intermediate layer, whereby an oxide superconducting layer having excellent crystal orientation is formed on a long base material such as a metal tape. If such an intermediate layer is formed between the metal tape and the oxide superconducting layer,
Since the accumulation of thermal strain due to the difference in the coefficient of thermal expansion can be mitigated and the element diffusion between the oxide superconducting layer and the metal tape can be suppressed, the oxide having an oxide superconducting layer with excellent characteristics can be suppressed. A superconducting conductor can be obtained.

【０００５】そこで本発明者らは、ハステロイからなる
金属テープの上にイットリウム安定化ジルコニア（ＹＳ
Ｚ）の中間層を形成し、この中間層上に酸化物超電導体
の中でも安定性に優れたＹＢａＣｕＯ系の超電導体から
なる超電導層を形成することで超電導導体を製造し、こ
の超電導導体についてコイル加工を施してみた。まず、
幅１０ｍｍ、厚さ０.１ｍｍのハステロイからなる金属
テープを用い、この金属テープ上に厚さ０.５μｍのＹ
ＳＺの中間層をスパッタ装置によって形成し、この中間
層上にレーザ蒸着装置によって厚さ約１.０μｍのＹ1Ｂ
ａ2Ｃｕ3Ｏ7-xなる組成の酸化物超電導層を形成して超
電導導体を得た。この超電導導体の臨界電流密度（Ｊ
ｃ）は、特にコイル加工を施していない直線状態のまま
において、液体窒素温度（７７Ｋ）、磁場０テスラの条
件において１×１０4Ａ／ｃｍ2の値を示した。Therefore, the present inventors have developed a yttrium-stabilized zirconia (YS) on a metal tape made of Hastelloy.
Z), an intermediate layer is formed, and a superconducting layer made of a YBaCuO-based superconductor having excellent stability among oxide superconductors is formed on the intermediate layer to produce a superconducting conductor. I tried to process it. First,
A metal tape made of Hastelloy having a width of 10 mm and a thickness of 0.1 mm is used, and Y having a thickness of 0.5 μm is formed on the metal tape.
An intermediate layer of SZ is formed by a sputtering device, and Y 1 B having a thickness of about 1.0 μm is formed on the intermediate layer by a laser deposition device.
An oxide superconducting layer having a composition of a 2 Cu 3 O 7-x was formed to obtain a superconducting conductor. This superconducting conductor has a critical current density (J
c) shows a value of 1 × 10 4 A / cm 2 under the conditions of liquid nitrogen temperature (77 K) and a magnetic field of 0 Tesla, especially in the linear state where no coiling is applied.

【０００６】次にこの試料を複数用意し、これらについ
て種々の曲げ半径で曲げ加工を施し、得られた各コイル
について液体窒素温度（７７Ｋ）、磁場０テスラの条件
で臨界電流密度を測定した結果を図８に示す。なお、こ
の曲げ加工時においては、所定の径の巻胴に対し、基材
を内側に位置するように、かつ、酸化物超電導層を外側
に位置するように巻回して曲げ加工したものは酸化物超
電導層に対して引張歪を負荷するものとし、その逆に、
基材を外側に位置するように、かつ、酸化物超電導層を
内側に位置するように巻回して曲げ加工したものは酸化
物超電導層に対して圧縮歪を負荷するものとして評価し
た。Next, a plurality of these samples were prepared, subjected to bending with various bending radii, and the critical current density was measured for each obtained coil under the conditions of liquid nitrogen temperature (77 K) and magnetic field of 0 Tesla. Is shown in FIG. In addition, at the time of this bending process, a product obtained by winding and bending the base material on the inside and the oxide superconducting layer on the outside with respect to the winding cylinder of a predetermined diameter is oxidized. It is assumed that tensile strain is applied to the superconducting layer, and vice versa.
A product obtained by winding and bending the base material so as to be located outside and the oxide superconducting layer located inside was evaluated as being one that applies compressive strain to the oxide superconducting layer.

【０００７】ところで、種々の曲げ半径（ｒ）に伴って
酸化物超電導層に負荷される歪は、以下の計算式を採用
して算出することが一般的である。 歪（ε％）＝（ｔ／２ｒ）×１００ なお、この式において、εはテープ表面に加わる歪、ｔ
はテープ全体の厚み、ｒは曲げ半径の値を示す。By the way, the strain applied to the oxide superconducting layer with various bending radii (r) is generally calculated by using the following calculation formula. Strain (ε%) = (t / 2r) × 100 In this equation, ε is the strain applied to the tape surface, t
Indicates the thickness of the entire tape, and r indicates the value of the bending radius.

【０００８】更に、図８の縦軸は、コイル加工前の状態
における超電導テープの臨界電流密度をＪｃ（０）と
し、所定の歪を負荷した場合の臨界電流密度をＪｃとし
て、両者の比、Ｊｃ／Ｊｃ（０）の値を求めた結果を示
す。従って、歪が０の場合、即ち、超電導テープをコイ
ル加工していない直線状態では、データは１.００を示
している。Further, the vertical axis of FIG. 8 shows the critical current density of the superconducting tape before coiling as Jc (0), and the critical current density when a predetermined strain is applied as Jc, the ratio of the two, The result of having calculated the value of Jc / Jc (0) is shown. Therefore, when the strain is 0, that is, when the superconducting tape is not coiled, the data shows 1.00.

【０００９】図８に示す結果から明らかなように、コイ
ル加工を施した場合の臨界電流密度の変化状態を見る
と、歪が０.２％までは臨界電流密度の低下割合は小さ
いが、歪が０.２％を超えると大きく低下し始め、歪が
０.２５％を超えた場合、コイル加工していない試料の
８０％を割ってしまい、歪が０.３％の場合ではコイル
加工前の臨界電流密度の５０％以下に低下してしまう問
題を生じた。As is clear from the results shown in FIG. 8, the change state of the critical current density when coiling is performed shows that although the rate of decrease of the critical current density is small up to a strain of 0.2%, the strain When the strain exceeds 0.2%, it begins to decrease greatly, and when the strain exceeds 0.25%, it falls below 80% of the sample that has not been coiled. When the strain is 0.3%, it is before coiling. There was a problem that the critical current density was reduced to 50% or less.

【００１０】一方、本発明者らは、ハステロイテープな
どの金属テープの上にＹＳＺの中間層を形成し、この中
間層上に酸化物超電導体の中でも安定性に優れたＹＢａ
ＣｕＯ系の超電導体からなる超電導層を形成することで
超電導特性の優れたテープ状の超電導導体を製造する試
みを種々行なっている。On the other hand, the present inventors formed an intermediate layer of YSZ on a metal tape such as Hastelloy tape, and on this intermediate layer, YBa which is excellent in stability among oxide superconductors was formed.
Various attempts have been made to produce a tape-shaped superconducting conductor having excellent superconducting properties by forming a superconducting layer made of a CuO-based superconductor.

【００１１】このような試みの中から本発明者らは先
に、結晶配向性に優れた中間層を形成するために、ある
いは、超電導特性の優れた超電導導体を得るために、特
願平３ー１２６８３６号、特願平３ー１２６８３７号、
特願平３ー２０５５５１号、特願平４ー１３４４３号、
特願平４ー２９３４６４号などにおいて特許出願を行な
っている。これらの特許出願に記載された技術によれ
ば、ハステロイテープなどの金属テープの基材上にスパ
ッタ装置により中間層を形成する際に、スパッタリング
と同時に基材成膜面の斜め方向からイオンビームを照射
しながら中間層を成膜することにより、結晶配向性に優
れた中間層を形成することができるものである。この方
法によれば、中間層を形成する多数の結晶粒のそれぞれ
の結晶格子のａ軸あるいはｂ軸で形成する粒界傾角を３
０度以下に揃えることができ、結晶配向性に優れた中間
層を形成することができる。そして更に、この配向性に
優れた中間層上に酸化物超電導層を成膜するならば、酸
化物超電導層の結晶配向性も優れたものになり、これに
より、結晶配向性に優れた臨界電流密度の高い酸化物超
電導層を形成することができる。From the above-mentioned attempts, the inventors of the present invention have previously proposed, in order to form an intermediate layer having excellent crystal orientation, or to obtain a superconducting conductor having excellent superconducting properties, Japanese Patent Application No. -126836, Japanese Patent Application No. 3-126837,
Japanese Patent Application No. 3-205551, Japanese Patent Application No. 4-13443,
A patent application has been filed in Japanese Patent Application No. 4-293464. According to the techniques described in these patent applications, when forming an intermediate layer on a base material of a metal tape such as Hastelloy tape by a sputtering device, an ion beam is applied simultaneously with sputtering from an oblique direction of the base material film-forming surface. By forming the intermediate layer while irradiating, the intermediate layer excellent in crystal orientation can be formed. According to this method, the grain boundary tilt angle formed by the a-axis or the b-axis of each crystal lattice of a large number of crystal grains forming the intermediate layer is 3
It is possible to form the intermediate layer excellent in crystal orientation, since the intermediate layer can be aligned at 0 degrees or less. Furthermore, if an oxide superconducting layer is formed on the intermediate layer having excellent orientation, the crystal orientation of the oxide superconducting layer will also be excellent, and as a result, the critical current with excellent crystal orientation will be obtained. A dense oxide superconducting layer can be formed.

【００１２】次に本発明者らは、このような優れた超電
導特性を有するテープ状の超電導導体を用いて超電導コ
イルを製造するために、前記良好な結晶配向性を有する
超電導導体について曲げ加工を施す試験を行なった。ま
ず、幅１０ｍｍ、厚さ０.１ｍｍのハステロイからなる
金属テープを用い、この金属テープ上に、厚さ０.５μ
ｍのＹＳＺの中間層をスパッタ装置とイオンビーム照射
装置を用いて前述の特許出願に係る方法で形成した。具
体的には、ＹＳＺのターゲットを用いて金属テープ上に
スパッタリングを行なって中間層を形成する際に、基材
上面に対して５５度の角度からイオンビーム照射装置に
よりアルゴンと酸素の混合イオンを照射しながら成膜
し、次いで得られた中間層上にレーザ蒸着装置によって
厚さ約１.０μｍのＹ1Ｂａ2Ｃｕ3Ｏ7-xなる組成の酸化
物超電導層を形成して超電導導体を得た。Next, in order to manufacture a superconducting coil using the tape-shaped superconducting conductor having such excellent superconducting properties, the present inventors bend the superconducting conductor having good crystal orientation. An applied test was conducted. First, a metal tape made of Hastelloy having a width of 10 mm and a thickness of 0.1 mm is used, and a thickness of 0.5 μ is put on the metal tape.
The YSZ intermediate layer of m was formed by the method according to the above-mentioned patent application using a sputtering apparatus and an ion beam irradiation apparatus. Specifically, when performing sputtering on a metal tape using a YSZ target to form an intermediate layer, mixed ions of argon and oxygen are emitted from an angle of 55 degrees with respect to the upper surface of the substrate by an ion beam irradiation device. A film is formed while irradiating, and then an oxide superconducting layer having a composition of Y 1 Ba 2 Cu 3 O 7-x with a thickness of about 1.0 μm is formed on the obtained intermediate layer by a laser deposition apparatus to form a superconducting conductor. Obtained.

【００１３】この超電導導体の臨界電流密度（Ｊｃ）
は、特にコイル加工を施していない直線状態のままにお
いて、液体窒素温度（７７Ｋ）、磁場０テスラの条件に
おいて１×１０5Ａ／ｃｍ2の値を示し、特に優れた超電
導特性を有している。Critical current density (Jc) of this superconducting conductor
Shows a value of 1 × 10 5 A / cm 2 under the condition of liquid nitrogen temperature (77 K) and magnetic field of 0 Tesla, especially in a straight state without coiling, and has particularly excellent superconducting properties. There is.

【００１４】次に、前記のように結晶配向性を整えた中
間層を有する超電導導体を複数用意し、これらについて
種々の曲げ半径で曲げ加工を施し、得られた各超電導コ
イルについて液体窒素温度（７７Ｋ）、磁場０テスラの
条件で臨界電流密度を測定した結果を図９に示す。な
お、曲げ加工条件や歪の算出方法は、前記の例の場合と
同等である。Next, a plurality of superconducting conductors having an intermediate layer whose crystal orientation has been adjusted as described above are prepared, and these are bent at various bending radii, and the liquid nitrogen temperature ( FIG. 9 shows the result of measuring the critical current density under the conditions of 77 K) and a magnetic field of 0 Tesla. The bending conditions and the method of calculating strain are the same as in the case of the above example.

【００１５】図９に示す結果から明らかなように、コイ
ル加工を施した場合の臨界電流密度の変化状態を見る
と、歪が大きくなる毎に少しずつ臨界電流密度が低下し
始め、歪が０.３％を超えた場合、コイル加工していな
い試料の９０％を下回り、更に歪が０.４５％を超えた
場合、コイル加工していない試料の８０％を割って７６
％程度になってしまう問題を生じた。As is clear from the results shown in FIG. 9, when the state of change in the critical current density when the coil is processed is observed, the critical current density begins to gradually decrease as the strain increases, and the strain becomes zero. When it exceeds 0.3%, it is lower than 90% of the uncoiled sample, and when the strain exceeds 0.45%, it is divided by 80% of the uncoiled sample to obtain 76.
There was a problem that it became about%.

【００１６】以上のことから、中間層の結晶を配向させ
ていない酸化物超電導導体は勿論、中間層を結晶配向さ
せた酸化物超電導導体においても、いずれにしても曲げ
加工を施す超電導特性の劣化を生じることが明かになっ
た。From the above, in any case, not only in the oxide superconducting conductor in which the crystal of the intermediate layer is not oriented, but also in the oxide superconducting conductor in which the crystal of the intermediate layer is oriented, the superconducting characteristic is deteriorated by bending. It has become clear that

【００１７】本発明は前記事情に鑑みてなされたもので
あり、超電導テープを曲げ加工した場合の臨界電流密度
の低下割合を少なくすることができ、臨界電流密度を高
くできる構造を提供することを目的とする。The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a structure in which the rate of decrease in critical current density when bending a superconducting tape can be reduced and the critical current density can be increased. To aim.

【００１８】[0018]

【課題を解決するための手段】請求項１記載の発明は前
記課題を解決するために、テープ状の基材上に中間層を
介して酸化物超電導層を形成し、この酸化物超電導層上
に良導電性の安定化金属層を形成するとともに、前記基
材と中間層を合わせた部分の厚さと、前記安定化金属層
の厚さを同等の厚さに形成してなるものである。In order to solve the above-mentioned problems, the invention according to claim 1 forms an oxide superconducting layer on a tape-shaped substrate with an intermediate layer interposed therebetween, and the oxide superconducting layer is formed on the oxide superconducting layer. In addition to forming a stabilizing metal layer having good conductivity, the thickness of the portion where the base material and the intermediate layer are combined and the stabilizing metal layer have the same thickness.

【００１９】請求項２記載の発明は前記課題を解決する
ために、テープ状の基材上に中間層を介して酸化物超電
導層を形成し、この酸化物超電導層上に、Ａｇ、Ｐｔな
どの貴金属またはその合金製の良導電性の下地安定化薄
膜と、ＣｕまたはＡｌなどの良導電製の安定化層からな
る安定化金属層を形成するとともに、前記基材と中間層
を合わせた部分の厚さと、前記安定化金属層を合わせた
部分の厚さを同等にしてなるものである。In order to solve the above-mentioned problems, the invention according to claim 2 forms an oxide superconducting layer on a tape-shaped substrate via an intermediate layer, and Ag, Pt, etc. are formed on the oxide superconducting layer. Forming a stabilizing metal layer composed of a noble metal or its alloy of good conductivity and a stabilizing layer of good conductivity such as Cu or Al, and combining the base material and the intermediate layer. And the thickness of the portion where the stabilizing metal layer is combined are made equal to each other.

【００２０】[0020]

【作用】本発明においては、基材上に中間層を介して酸
化物超電導層を形成し、その上に基材と中間層を合わせ
た厚さと同等の厚さの安定化金属層を設けているので、
全体をコイル加工などのように曲げ加工する際に酸化物
超電導層に歪がかかりにくい構成であり、酸化物超電導
層に曲げ加工を施しても超電導特性の劣化を生じにく
い。In the present invention, the oxide superconducting layer is formed on the base material via the intermediate layer, and the stabilizing metal layer having the same thickness as the total thickness of the base material and the intermediate layer is provided on the oxide superconducting layer. Because
The structure is such that the oxide superconducting layer is less likely to be strained when the whole is bent, such as by coiling, and the superconducting characteristics are less likely to deteriorate even if the oxide superconducting layer is bent.

【００２１】また、下地安定化薄膜と安定化層を酸化物
超電導層上に形成した構造の酸化物超電導導体において
も、基材と中間層を合わせた部分の厚さと、下地安定化
薄膜と安定化層を合わせた安定化金属層部分の厚さを同
等にすることで前記と同等の効果を得ることができる。
更に、基材上に中間層を介して酸化物超電導層を設け、
かつ、前記の如くＡｇなどの貴金属やその合金の下地安
定化薄膜と良導電性金属材料製の安定化層を酸化物超電
導層上に形成した構造を採用すると、酸化物超電導層の
熱処理時において、酸化物超電導層の構成元素と基材の
構成元素が相互拡散することを中間層が抑制するととも
に、酸化通超電導層の構成元素と安定化層の構成元素が
相互拡散することを安定化薄膜が抑制するので、熱処理
によって酸化物超電導層の超電導特性が劣化することが
ない。Further, also in the oxide superconducting conductor having a structure in which the underlayer stabilizing thin film and the stabilizing layer are formed on the oxide superconducting layer, the thickness of the portion where the base material and the intermediate layer are combined and the underlayer stabilizing thin film and the stabilizing layer are stable. By making the thickness of the stabilizing metal layer portion including the functionalized layers equal, the same effect as described above can be obtained.
Furthermore, an oxide superconducting layer is provided on the base material via an intermediate layer,
In addition, as described above, when a structure in which an underlayer stabilizing thin film of a noble metal such as Ag or an alloy thereof and a stabilizing layer made of a highly conductive metal material are formed on an oxide superconducting layer, heat treatment of the oxide superconducting layer is possible. , The intermediate layer suppresses the mutual diffusion of the constituent elements of the oxide superconducting layer and the base material, and stabilizes the mutual diffusion of the constituent elements of the oxidative superconducting layer and the stabilizing layer. Therefore, the superconducting property of the oxide superconducting layer is not deteriorated by the heat treatment.

【００２２】[0022]

【実施例】以下、図面を参照して本発明の実施例につい
て説明する。図１は本発明の第１実施例を示すものであ
って、この例の酸化物超電導導体Ａは、テープ状の基材
１の上面に中間層２が形成され、この中間層２上に酸化
物超電導層３が形成され、この酸化物超電導層３上に安
定化金属層４が形成されてなる。そして、前記の構造に
おいて、基材１と中間層２から基材部５が構成され、こ
の基材部５の厚さと、安定化金属層４の厚さが同等にさ
れている。Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 shows a first embodiment of the present invention. In the oxide superconducting conductor A of this example, an intermediate layer 2 is formed on the upper surface of a tape-shaped base material 1, and the intermediate layer 2 is oxidized. The object superconducting layer 3 is formed, and the stabilizing metal layer 4 is formed on the oxide superconducting layer 3. In the above structure, the base material portion 5 is composed of the base material 1 and the intermediate layer 2, and the thickness of the base material portion 5 and the thickness of the stabilizing metal layer 4 are made equal.

【００２３】前記基材１は、ステンレス鋼、銅、また
は、ハステロイ（ハステロイＣ-２７６等）などのニッ
ケル合金などに代表される各種金属材料から、あるい
は、各種のガラスまたはセラミックスなどから構成され
るもののいずれを用いても良い。前記の中間層２を形成
する材料は、後に中間層２の上に形成される酸化物超電
導層の結晶に近い結晶構造（例えば、立方晶系の結晶構
造）を有し、酸化物超電導層の熱膨張率に近い熱膨張率
を有するものが好ましい。よって、中間層２を構成する
材料は、ＹＳＺ（イットリウム安定化ジルコニア）、Ｓ
ｒＴｉＯ3、ＭｇＯなどのセラミックス系の材料が好ま
しい。The base material 1 is made of various metal materials such as stainless steel, copper, nickel alloys such as Hastelloy (Hastelloy C-276), or glass or ceramics. Any of these may be used. The material forming the intermediate layer 2 has a crystal structure (for example, a cubic crystal structure) close to that of the oxide superconducting layer formed on the intermediate layer 2 later, and the material of the oxide superconducting layer is Those having a coefficient of thermal expansion close to the coefficient of thermal expansion are preferable. Therefore, the material forming the intermediate layer 2 is YSZ (yttrium-stabilized zirconia), S
Ceramic-based materials such as rTiO 3 and MgO are preferable.

【００２４】前記の酸化物超電導層３は、Ｙ1Ｂa2Ｃｕ3
Ｏ7-x、Ｙ2Ｂa4Ｃｕ8Ｏx、Ｙ3Ｂa3Ｃｕ6Ｏxなる組成、
あるいは（Ｂｉ,Ｐｂ）2Ｃａ2Ｓｒ2Ｃｕ3Ｏx、（Ｂｉ,
Ｐｂ）2Ｃａ2Ｓｒ3Ｃｕ4Ｏxなる組成、あるいは、Ｔｌ2
Ｂａ2Ｃａ2Ｃｕ3Ｏx、Ｔｌ1Ｂａ2Ｃａ2Ｃｕ3Ｏx、Ｔｌ1
Ｂａ2Ｃａ3Ｃｕ4Ｏxなる組成などに代表される臨界温度
の高い酸化物超電導体のいずれからなるものを用いても
良い。前記安定化金属層４は、Ａｇ、Ｐｔ、Ａｕなどの
貴金属あるいはそれらの合金、または、ＣｕやＡｌなど
の良導電性金属材料からなる。The oxide superconducting layer 3 is made of Y 1 Ba 2 Cu 3
O 7-x, Y 2 Ba 4 Cu 8 O x, Y 3 Ba 3 Cu 6 Ox a composition,
Alternatively, (Bi, Pb) 2 Ca 2 Sr 2 Cu 3 O x , (Bi,
Pb) 2 Ca 2 Sr 3 Cu 4 O x or Tl 2
Ba 2 Ca 2 Cu 3 O x , Tl 1 Ba 2 Ca 2 Cu 3 O x , Tl 1
Any oxide superconductor having a high critical temperature represented by a composition such as Ba 2 Ca 3 Cu 4 O x may be used. The stabilizing metal layer 4 is made of a noble metal such as Ag, Pt, or Au or an alloy thereof, or a highly conductive metal material such as Cu or Al.

【００２５】前記構造の酸化物超電導導体Ａにあって
は、例えば基材部５の厚さが０.０５〜０.１ｍｍ程度で
あり、酸化物超電導層３の厚さが１〜２μｍ程度であ
り、安定化金属層４の厚さが０.０５〜０.１ｍｍ程度に
形成されている。このように同等の厚さの基材部５と安
定化金属層４で酸化物超電導層３が挟まれて酸化物超電
導導体Ａが構成されている場合、この酸化物超電導導体
Ａを多少曲げ加工しても酸化物超電導層３の臨界電流特
性の劣化を生じない。よって、臨界電流密度の高い超電
導コイルを得ることができる。この理由は、前記構造の
酸化物超電導導体Ａを曲げ加工すると、基材部５の上に
設けられた酸化物超電導層３に対しては基材部５から見
ると引張歪が負荷されるが、安定化金属層４から見ると
その下側に酸化物超電導層３が設けられていて安定化金
属層４から酸化通超電導層３に対して圧縮歪が負荷され
るので、両者の負荷がバランスする結果、酸化物超電導
層３に対する実際の応力負荷が軽減されることに起因し
ているものと思われる。In the oxide superconducting conductor A having the above structure, for example, the thickness of the base material portion 5 is about 0.05 to 0.1 mm, and the thickness of the oxide superconducting layer 3 is about 1 to 2 μm. The thickness of the stabilizing metal layer 4 is about 0.05 to 0.1 mm. Thus, when the oxide superconducting conductor A is formed by sandwiching the oxide superconducting layer 3 between the base material portion 5 and the stabilizing metal layer 4 having the same thickness, the oxide superconducting conductor A is slightly bent. Even if it does, the deterioration of the critical current characteristics of the oxide superconducting layer 3 does not occur. Therefore, a superconducting coil having a high critical current density can be obtained. The reason is that when the oxide superconducting conductor A having the above structure is bent, tensile strain is applied to the oxide superconducting layer 3 provided on the base member 5 when viewed from the base member 5. When viewed from the stabilizing metal layer 4, the oxide superconducting layer 3 is provided below the stabilizing metal layer 4, and the compressive strain is applied from the stabilizing metal layer 4 to the oxidation-conducting superconducting layer 3. Therefore, both loads are balanced. As a result, it seems that the actual stress load on the oxide superconducting layer 3 is reduced.

【００２６】図２は本発明の第２実施例を示すものであ
り、この実施例の酸化物超電導導体Ｂにおいて先の実施
例の構成要素と同一の構成要素には同一の符号を付して
それらの部分の説明は省略する。この第２実施例におい
て先の第１実施例と異なっているのは、安定化金属層
４’が、下地安定化薄膜４ａと安定化層４ｂとから構成
されている点である。前記下地安定化薄膜４ａは、Ａ
ｇ、Ａｕ、Ｐｔなどの貴金属またはそれらの合金からな
り、安定化層４ｂは、ＣｕやＡｌなどのように貴金属よ
りも安価な良電導性金属材料から構成されている。FIG. 2 shows a second embodiment of the present invention. In the oxide superconducting conductor B of this embodiment, the same components as those of the previous embodiment are designated by the same reference numerals. A description of those parts will be omitted. The second embodiment differs from the first embodiment in that the stabilizing metal layer 4'is composed of a base stabilizing thin film 4a and a stabilizing layer 4b. The base stabilizing thin film 4a is
The stabilizing layer 4b is made of a noble metal such as g, Au or Pt or an alloy thereof, and the stabilizing layer 4b is made of a highly conductive metal material such as Cu or Al which is cheaper than the noble metal.

【００２７】次にこの第２実施例の酸化部超電導導体Ｂ
を製造する方法について説明する。この例の酸化物超電
導導体Ｂを製造するには、まず、図３に示すようなテー
プ状の基材１を用意する。前記基材１を用意したなら
ば、図３に示すように、この基材１上に拡散バリアとし
ての中間層２を成膜法により形成する。この中間層２を
形成する具体的方法は、スパッタ法、真空蒸着法、レー
ザ蒸着法、化学気相成長法（ＣＶＤ）などのいずれの成
膜法を用いても良い。基材１として長尺のものを用いる
場合は、使用する成膜装置の真空チャンバの内部にテー
プの送出装置と巻取装置を設け、送出装置から送り出し
た基材を真空チャンバの内部で連続的に所定の速度で移
動させながら巻取装置で巻き取り、移動中の基材に連続
成膜処理を行なえば良い。なお、ここで行なう成膜処理
においては長尺の基材１を用いることを想定しているの
で、均質な膜を連続的に長時間成膜することが可能なレ
ーザ蒸着法を用いることが好ましい。Next, the superconducting conductor B of the oxidized portion of the second embodiment
A method of manufacturing the will be described. To manufacture the oxide superconducting conductor B of this example, first, a tape-shaped substrate 1 as shown in FIG. 3 is prepared. After the base material 1 is prepared, as shown in FIG. 3, the intermediate layer 2 as a diffusion barrier is formed on the base material 1 by a film forming method. As a specific method for forming the intermediate layer 2, any film forming method such as a sputtering method, a vacuum vapor deposition method, a laser vapor deposition method, and a chemical vapor deposition method (CVD) may be used. When a long substrate 1 is used, a tape feeding device and a winding device are provided inside the vacuum chamber of the film forming apparatus used, and the substrate fed from the feeding device is continuously fed inside the vacuum chamber. The film may be taken up by a take-up device while being moved at a predetermined speed, and a continuous film formation process may be performed on the moving substrate. Since it is assumed that a long base material 1 is used in the film forming process performed here, it is preferable to use a laser vapor deposition method capable of forming a uniform film continuously for a long time. .

【００２８】基材１上に中間層２を形成したならば、次
に中間層２上に酸化物超電導層３を図４に示すように形
成する。この酸化物超電導層３の成膜においても前記と
同様の種々の成膜法を用いることができるが、均質な膜
を連続的に長時間成膜することが可能なレーザ蒸着法を
用いることが好ましい。このレーザ蒸着を行なうには、
ターゲットとして例えばＹ1Ｂａ2Ｃｕ3Ｏ7-xなる組成の
酸化物あるいは酸化物超電導体ターゲットを使用し、基
材を５００〜８００℃程度の所望の温度に加熱し、真空
チャンバの内部を酸素を含む減圧雰囲気とし、基材１を
１時間に数１０ｃｍ程度の速度で移動させながら成膜処
理を行えば良い。この処理によって数時間〜数１０時間
の処理で１〜数μｍ程度の厚さの酸化物超電導層３を長
さ数１０ｃｍ〜数ｍにわたり形成することができる。After the intermediate layer 2 is formed on the base material 1, the oxide superconducting layer 3 is then formed on the intermediate layer 2 as shown in FIG. In forming the oxide superconducting layer 3, various film forming methods similar to the above can be used, but a laser deposition method capable of forming a homogeneous film continuously for a long time is used. preferable. To perform this laser deposition,
For example, an oxide or oxide superconductor target having a composition of Y 1 Ba 2 Cu 3 O 7-x is used as a target, the substrate is heated to a desired temperature of about 500 to 800 ° C., and the inside of the vacuum chamber is oxygenated. The film forming process may be performed while the substrate 1 is moved at a speed of about several tens of cm per hour in a reduced pressure atmosphere containing. By this treatment, the oxide superconducting layer 3 having a thickness of about 1 to several μm can be formed over a length of several 10 cm to several m in a treatment of several hours to several tens hours.

【００２９】次に前記の酸化物超電導層３の上に下地安
定化薄膜４ａを形成して図５に示す素導体１５を形成す
る。前記下地安定化薄膜４ａは、銀、金、白金などの貴
金属あるいはそれらの合金からなり、厚さ数μｍ〜数１
０μｍ程度のものである。ここで用いる下地安定化薄膜
４ａの構成材料として、酸素の拡散係数が高い銀あるい
は白金などを用いることが特に好ましい。この下地安定
化薄膜４ａは、後述する酸素雰囲気中で行なう熱処理時
において、雰囲気中の酸素を酸化物超電導層３側に導く
必要があるので必要以上に厚く形成する必要はない。ま
た、この下地安定化薄膜４ａは酸化物超電導層３を保護
し、後述する最終熱処理時に酸化物超電導層３の元素が
外部に拡散しないように保護する役割をはたすので、薄
く形成し過ぎることも好ましくない。よって数μｍ〜２
０μｍ程度の厚さにすることが好ましい。Next, a base stabilizing thin film 4a is formed on the oxide superconducting layer 3 to form the element conductor 15 shown in FIG. The base stabilizing thin film 4a is made of a noble metal such as silver, gold, platinum, or an alloy thereof, and has a thickness of several μm to several 1
It is about 0 μm. It is particularly preferable to use silver or platinum, which has a high oxygen diffusion coefficient, as the constituent material of the underlayer stabilizing thin film 4a used here. This underlayer stabilizing thin film 4a does not need to be formed thicker than necessary because it is necessary to guide oxygen in the atmosphere to the oxide superconducting layer 3 side during heat treatment performed in an oxygen atmosphere described later. In addition, since the base stabilizing thin film 4a protects the oxide superconducting layer 3 and protects the elements of the oxide superconducting layer 3 from diffusing to the outside during the final heat treatment described later, it may be formed too thin. Not preferable. Therefore, several μm to 2
The thickness is preferably about 0 μm.

【００３０】下地安定化薄膜４ａを形成する方法は、前
述の各種成膜法のいずれを用いても良い。この下地安定
化薄膜４ａの厚さは、前述のように数μｍ〜２０μｍ程
度であるので、前述のいずれの成膜法を用いても前記の
範囲の厚さで支障なく十分な厚さの下地安定化薄膜４ａ
を長尺の酸化物超電導層３上に形成できる。よってこの
下地安定化薄膜４ａの形成のために長い時間を要するこ
とはない。As the method for forming the underlayer stabilizing thin film 4a, any of the various film forming methods described above may be used. Since the thickness of the underlayer stabilizing thin film 4a is about several μm to 20 μm as described above, the thickness of the above range can be used without any problem even if any of the film forming methods described above is used. Stabilizing thin film 4a
Can be formed on the elongated oxide superconducting layer 3. Therefore, it does not take a long time to form the base stabilizing thin film 4a.

【００３１】素導体１５を形成したならば、これを酸素
ガスを含む雰囲気中において５００〜６００℃の温度で
数時間加熱する熱処理を施す。この熱処理により雰囲気
中の酸素を下地安定化薄膜４ａを介して酸化物超電導層
３に供給し、酸素不足を補う処理を施す。この熱処理に
より、酸化超電導層３の酸素不足を補なって結晶構造を
整え、超電導特性の向上を図ると同時に、酸化物超電導
層３とＡｇなどからなる下地安定化薄膜４ａとの界面抵
抗値を低減する。After the element conductor 15 is formed, it is heat-treated by heating it at a temperature of 500 to 600 ° C. for several hours in an atmosphere containing oxygen gas. By this heat treatment, oxygen in the atmosphere is supplied to the oxide superconducting layer 3 through the underlayer stabilizing thin film 4a, and a treatment for compensating for oxygen deficiency is performed. By this heat treatment, oxygen deficiency of the oxidized superconducting layer 3 is supplemented to adjust the crystal structure to improve the superconducting property, and at the same time, the interfacial resistance value between the oxide superconducting layer 3 and the underlayer stabilizing thin film 4a made of Ag or the like is increased. Reduce.

【００３２】次に、前記下地安定化薄膜４ａの上にメッ
キ法により良導電性の金属材料からなる厚さ数１０〜数
１００μｍ程度の安定化層４ｂを形成して酸化物超電導
導体Ｂを得る。前記のメッキ法によれば、長尺の基材１
上の下地安定化薄膜４ａの上にも厚い層を容易に被覆で
きるので、超電導特性の安定化のための層として十分な
厚さを有する安定化層４ｂを容易に形成できる。Next, a stabilizing layer 4b made of a metal material having good conductivity and having a thickness of several tens to several hundreds of μm is formed on the underlayer stabilizing thin film 4a by a plating method to obtain an oxide superconducting conductor B. . According to the above plating method, the long base material 1
Since a thick layer can be easily coated on the upper base stabilizing thin film 4a, the stabilizing layer 4b having a sufficient thickness as a layer for stabilizing the superconducting characteristics can be easily formed.

【００３３】安定化層４ｂを形成したならば、全体をＮ
2あるいはＡｒガスなどの不活性ガス雰囲気中において
５００〜６００℃の温度において数時間加熱する最終熱
処理を施す。この最終熱処理は、下地安定化薄膜４ａと
安定化層４ｂとの界面の抵抗値を下げるために行なう。
また、不活性ガス雰囲気中で行なうのは、安定化層４ｂ
を構成する金属元素の酸化を防止するためである。な
お、この最終熱処理を行なう場合に、安定化層４ｂの構
成元素が酸化物超電導層３側に拡散するおそれがある
が、それらの間に下地安定化薄膜４ａを設けているの
で、酸化物超電導層３に対する不用元素の拡散を抑制で
きる。よって最終熱処理により酸化物超電導層３の特性
が劣化することはない。以上の方法を実施することで十
分な厚さを有する良導電性の安定化層４ｂを備えた超電
導特性に優れた酸化物超電導導体Ｂを得ることができ
る。Once the stabilizing layer 4b has been formed, the whole is N
2 or a final heat treatment of heating at a temperature of 500 to 600 ° C. for several hours in an atmosphere of an inert gas such as Ar gas. This final heat treatment is performed to reduce the resistance value at the interface between the underlayer stabilizing thin film 4a and the stabilizing layer 4b.
In addition, what is performed in the inert gas atmosphere is the stabilization layer 4b.
This is for preventing the oxidation of the metal element constituting the. When this final heat treatment is performed, the constituent elements of the stabilizing layer 4b may diffuse to the oxide superconducting layer 3 side, but since the underlayer stabilizing thin film 4a is provided between them, the oxide superconducting It is possible to suppress the diffusion of the unnecessary element into the layer 3. Therefore, the final heat treatment does not deteriorate the characteristics of the oxide superconducting layer 3. By carrying out the method described above, it is possible to obtain the oxide superconducting conductor B having excellent superconducting characteristics, which is provided with the stabilizing layer 4b having good conductivity and having a sufficient thickness.

【００３４】前記構造の酸化物超電導導体Ｂは、基材１
上に中間層２を介して酸化物超電導層３を形成し、その
上に貴金属などからなる下地安定化薄膜４ａを介してメ
ッキ法により良導電性金属材料の安定化層４ｂを形成
し、熱処理を施して製造するものであるので、メッキ法
により厚い安定化層４ｂを容易に短時間で形成できる。
よって、十分な厚さの安定化層４ｂを具備する長尺の超
電導導体Ｂを容易に製造できるので、超電導特性の安定
性に優れた長尺の超電導導体Ｂを従来の成膜法による場
合に比べて短時間で容易に製造することができる。The oxide superconducting conductor B having the above structure is the base material 1
An oxide superconducting layer 3 is formed on the intermediate layer 2, and a stabilizing layer 4b of a good conductive metal material is formed on the oxide superconducting layer 3 via a base stabilizing thin film 4a made of a noble metal or the like by a heat treatment. The thick stabilizing layer 4b can be easily formed in a short time by the plating method.
Therefore, the long superconducting conductor B including the stabilizing layer 4b having a sufficient thickness can be easily manufactured. Therefore, when the long superconducting conductor B excellent in stability of superconducting properties is formed by the conventional film forming method. In comparison, it can be easily manufactured in a short time.

【００３５】また、酸化物超電導層３を中間層２上に形
成し、その後に貴金属またはその合金からなる下地安定
化被膜４ａを形成した後に酸素雰囲気中で１次熱処理
し、酸素拡散係数が高く、薄い下地安定化被膜４ａを介
して酸化物超電導層３に雰囲気中の酸素を供給するの
で、この熱処理により酸化物超電導層３に十分な酸素を
補給して酸素不足を補うことができ、超電導特性を向上
させる効果を得ることができる。更に、安定化層４ｂと
酸化物超電導層３との間に貴金属またはその合金からな
る下地安定化被膜４ａを形成するので、熱処理時に安定
化層４ｂの元素と酸化物超電導層３の元素が相互拡散す
ることを下地安定化被膜４ａで防止することができ、熱
処理を施しても超電導特性が劣化しない酸化物超電導導
体Ｂを得ることができる。Further, the oxide superconducting layer 3 is formed on the intermediate layer 2, and then the undercoat stabilizing coating 4a made of a noble metal or its alloy is formed, and then primary heat treatment is carried out in an oxygen atmosphere to obtain a high oxygen diffusion coefficient. Since oxygen in the atmosphere is supplied to the oxide superconducting layer 3 through the thin undercoat stabilizing film 4a, sufficient oxygen can be replenished to the oxide superconducting layer 3 by this heat treatment to supplement the oxygen deficiency. The effect of improving the characteristics can be obtained. Furthermore, since the undercoat stabilizing coating 4a made of a noble metal or its alloy is formed between the stabilizing layer 4b and the oxide superconducting layer 3, the elements of the stabilizing layer 4b and the elements of the oxide superconducting layer 3 are mutually separated during heat treatment. It is possible to prevent the diffusion by the base stabilizing coating 4a, and it is possible to obtain the oxide superconducting conductor B in which the superconducting properties are not deteriorated even if the heat treatment is performed.

【００３６】更にまた、酸化物超電導層３上に下地安定
化被膜４ａを形成した後に１次熱処理を施し、下地安定
化被膜４ａ上に安定化層４ｂを形成した後に最終熱処理
するので、１次熱処理により酸化物超電導層３と下地安
定化被膜４ａの界面の接触電気抵抗を低減できるととも
に、最終熱処理により下地安定化被膜４ａと安定化層４
ｂの界面の接触電気抵抗を低減できるので、酸化物超電
導層３と下地安定化被膜４ａと安定化層４ｂがそれらの
界面の低い接触電気抵抗を介して連続されることにな
る。よって酸化物超電導層３に通電中に酸化物超電導層
３の一部領域に常電導の芽の部分を生じてもこの部分に
流れる電流を下地安定化被膜４ａを介して安定化層４ｂ
に円滑に流すことができ、これにより酸化物超電導層３
の安定性を高めることができる。よって、安定化層付き
の臨界電流特性の優れた酸化物超電導導体Ｂを製造でき
る。Furthermore, since the primary stabilizing coating 4a is formed on the oxide superconducting layer 3, the primary heat treatment is performed, and the stabilizing layer 4b is formed on the underlying stabilizing coating 4a, and the final thermal treatment is performed. The heat treatment can reduce the contact electric resistance at the interface between the oxide superconducting layer 3 and the undercoat stabilizing film 4a, and the final heat treatment can reduce the contact electrical resistance.
Since the contact electric resistance at the interface of b can be reduced, the oxide superconducting layer 3, the undercoat stabilizing coating 4a, and the stabilizing layer 4b are continuous through the low contact electric resistance at their interface. Therefore, even if a portion of normal-conductivity buds is generated in a partial region of the oxide superconducting layer 3 while the oxide superconducting layer 3 is energized, the current flowing in this portion is passed through the underlayer stabilizing coating 4a to the stabilizing layer 4b.
Flow smoothly into the oxide superconducting layer 3
The stability of can be increased. Therefore, the oxide superconducting conductor B having the stabilizing layer and excellent in critical current characteristics can be manufactured.

【００３７】[0037]

【実施例】【Example】

（実施例１）ハステロイＣ-２７６からなる金属テープ
基材（幅５ｍｍ、厚さ０.１ｍｍ、長さ１０００ｍｍ）
を用い、この金属テープ基材上に、拡散バリアとしての
厚さ０.５μｍのＹＳＺの中間層をＲＦスパッタ法によ
り形成した。中間層を形成するには、２×１０-3Ｔｏｒ
ｒに減圧した真空チャンバの内部で金属テープ基材を
０.２ｍ／時間の割合で移動させて室温にて３０ｃｃＭ
のＡｒガスを導入し、２５０ＷのＲＦパワーで成膜する
方法を行なった。次に、エキシマレーザをターゲットに
照射するレーザ蒸着法を用いて中間層上にＹ1Ｂａ2Ｃｕ
3Ｏ7-xなる組成の酸化部超電導層を形成した。この際の
ターゲット組成とレーザ蒸着条件は、以下の表１の通り
である。 （以下、余白）(Example 1) Metal tape base material made of Hastelloy C-276 (width 5 mm, thickness 0.1 mm, length 1000 mm)
An intermediate layer of YSZ having a thickness of 0.5 μm as a diffusion barrier was formed on this metal tape substrate by RF sputtering. To form the intermediate layer, 2 × 10 −3 Tor
The metal tape base material is moved at a rate of 0.2 m / hour inside the vacuum chamber depressurized to r, and 30 ccM at room temperature.
Then, Ar gas was introduced, and a film was formed with an RF power of 250 W. Then, Y 1 Ba 2 Cu is formed on the intermediate layer by using a laser deposition method in which a target is irradiated with an excimer laser.
An oxide superconducting layer having a composition of 3 O 7-x was formed. The target composition and laser deposition conditions at this time are as shown in Table 1 below. (Hereafter, margin)

【００３８】[0038]

【表１】 [Table 1]

【００３９】真空チャンバの内部で中間層付きの金属テ
ープ基材を０.２ｍ／時間の割合で移動させて表１の条
件でレーザ蒸着を行ない、厚さ１.０μｍの酸化物超電
導層を形成した。次に、スパッタリングにより前記の酸
化物超電導層上に厚さ約０.１ｍｍの銀の安定化金属層
を形成した。次いで全体を酸素雰囲気中において５００
℃で２時間加熱し、安定化金属層と酸化物超電導層の界
面抵抗を低減するとともに、酸化物超電導層に安定化金
属層を介して酸素を供給するための熱処理を施した。A metal tape substrate with an intermediate layer was moved inside the vacuum chamber at a rate of 0.2 m / hour, and laser deposition was performed under the conditions shown in Table 1 to form an oxide superconducting layer having a thickness of 1.0 μm. did. Next, a stabilized metal layer of silver having a thickness of about 0.1 mm was formed on the above oxide superconducting layer by sputtering. Then the whole is 500 in an oxygen atmosphere.
The mixture was heated at 0 ° C. for 2 hours to reduce the interfacial resistance between the stabilizing metal layer and the oxide superconducting layer, and at the same time, to perform heat treatment for supplying oxygen to the oxide superconducting layer through the stabilizing metal layer.

【００４０】得られた酸化物超電導導体から長さ５０ｃ
ｍの部分を切り出し、これに引張歪を加えた場合の臨界
電流値の変化を測定した。この測定方法は、先に説明し
た場合と同様に、所定の径の巻胴に対し、基材を内側に
位置するように、かつ、酸化物超電導層を外側に位置す
るように巻回してコイル加工して酸化物超電導層に対し
て引張歪を負荷するものとした。また、この場合の歪の
計算方法は、先に説明したε＝（ｔ／２ｒ）×１００の
関係式に基づいて算出した。その結果を図７に示す。図
７に示す結果から、本発明構造を採用することで０.８
％まで引張歪を負荷しても臨界電流値が劣化しなかっ
た。なおまた、この結果は、負荷する歪を圧縮歪とした
場合も同等であった。From the obtained oxide superconducting conductor, length 50c
The portion of m was cut out, and the change in the critical current value when tensile strain was applied to this was measured. This measuring method is similar to the case described above, in which the coil is wound by winding the base material inside and the oxide superconducting layer outside with respect to the winding cylinder of a predetermined diameter. It was processed to apply tensile strain to the oxide superconducting layer. The strain calculation method in this case was calculated based on the relational expression of ε = (t / 2r) × 100 described above. The result is shown in FIG. 7. From the results shown in FIG. 7, it is possible to obtain 0.8 by adopting the structure of the present invention.
The critical current value did not deteriorate even when tensile strain was applied up to%. Furthermore, this result was the same when the strain applied was compression strain.

【００４１】（実施例２）ハステロイＣ-２７６からな
る金属テープ基材（幅５ｍｍ、厚さ０.１ｍｍ、長さ２
０００ｍｍ）を用い、この金属テープ基材上に、拡散バ
リアとしてのＹＳＺの中間層と酸化物超電導層を実施例
１と同等の方法で形成した。(Example 2) Metal tape substrate made of Hastelloy C-276 (width 5 mm, thickness 0.1 mm, length 2)
000 mm), an intermediate layer of YSZ as a diffusion barrier and an oxide superconducting layer were formed on this metal tape substrate by the same method as in Example 1.

【００４２】次に、スパッタリングにより酸化物超電導
層上に厚さ１０μｍの銀の下地安定化薄膜を２時間かけ
て形成した。この際に、スパッタ装置の真空チャンバの
内部を１×１０-5Ｔｏｒｒに減圧し、銀のターゲットを
用いた。次いで全体を５００℃で２時間加熱する１次熱
処理を施し、下地安定化薄膜と酸化物超電導層の界面抵
抗を低減する１次熱処理を施した。Next, a 10 μm thick underlayer stabilizing thin film of silver was formed on the oxide superconducting layer by sputtering for 2 hours. At this time, the inside of the vacuum chamber of the sputtering apparatus was depressurized to 1 × 10 −5 Torr and a silver target was used. Then, the whole was subjected to a primary heat treatment of heating at 500 ° C. for 2 hours, and a primary heat treatment of reducing the interface resistance between the underlayer stabilizing thin film and the oxide superconducting layer.

【００４３】続いて全体をメッキ液に浸漬した後に引き
上げるメッキ処理を施して下地安定化薄膜上に厚さ１０
０μｍの銅の安定化層を形成した。この際に、メッキ液
としてシアン系の組成のものを用い、電流密度１０Ａ／
ｄｍ2として１時間の処理を行なった。最後に、Ｎ2ガス
雰囲気において５００℃で２時間加熱する最終熱処理を
施した。Subsequently, the whole is immersed in a plating solution and then subjected to a plating treatment of withdrawing it to a thickness of 10 on the underlayer stabilizing thin film.
A 0 μm copper stabilizing layer was formed. At this time, a plating solution having a cyan composition was used, and the current density was 10 A /
The treatment was carried out for 1 hour as dm 2 . Finally, a final heat treatment of heating at 500 ° C. for 2 hours in a N 2 gas atmosphere was performed.

【００４４】得られた酸化物超電導テープを液体窒素で
冷却してその臨界電流密度（Ｊｃ）を測定したところ、
Ｊｃ＝１×１０4Ａ／ｃｍ2（７７Ｋ、０Ｔ）の優れた特
性を得ることができた。次に、前記と同等の手段により
この酸化物超電導導体に引張歪を負荷する試験を行なっ
たところ、実施例１と同様に優れた特性を得ることがで
きた。これにより、Ｙ1Ｂａ2Ｃｕ3Ｏ7-xなる組成の酸化
物超電導層上に銀の下地安定化被膜と銅の安定化層を形
成した超電導テープは、優れた歪特性を発揮することを
確認できた。The obtained oxide superconducting tape was cooled with liquid nitrogen and its critical current density (Jc) was measured.
Excellent characteristics of Jc = 1 × 10 4 A / cm 2 (77K, 0T) could be obtained. Next, a test was conducted by applying a tensile strain to this oxide superconducting conductor by the same means as above, and as a result, excellent characteristics could be obtained as in Example 1. As a result, a superconducting tape in which a silver undercoat stabilizing film and a copper stabilizing layer are formed on an oxide superconducting layer having a composition of Y 1 Ba 2 Cu 3 O 7-x exhibits excellent strain characteristics. It could be confirmed.

【００４５】[0045]

【発明の効果】以上説明したように本発明によれば、基
材上に中間層を介して酸化物超電導層を設け、その上に
基材と中間層の合計厚さに相当する厚さの安定化金属層
を設けているので、曲げ加工した場合に酸化物超電導層
に負荷される応力の影響を小さくすることができ、臨界
電流特性の優れた酸化物超電導導体を提供できる効果が
ある。よって、臨界電流特性の優れた酸化物超電導コイ
ルを提供できる効果がある。As described above, according to the present invention, an oxide superconducting layer is provided on a base material via an intermediate layer, and an oxide superconducting layer having a thickness corresponding to the total thickness of the base material and the intermediate layer is provided thereon. Since the stabilizing metal layer is provided, it is possible to reduce the influence of the stress applied to the oxide superconducting layer when it is bent, and it is possible to provide an oxide superconducting conductor having excellent critical current characteristics. Therefore, there is an effect that an oxide superconducting coil having excellent critical current characteristics can be provided.

【００４６】また、下地安定化薄膜と安定化層を酸化物
超電導層上に形成した構造の酸化物超電導導体において
は、基材と中間層を合わせた部分の厚さと、下地安定化
薄膜と安定化層を合わせた安定化金属層部分の厚さを同
等にしているので、曲げ加工した場合に酸化物超電導層
に負荷される応力の影響を小さくすることができ、臨界
電流特性の優れた酸化物超電導導体を提供できる効果が
ある。よって、臨界電流特性の優れた酸化物超電導コイ
ルを提供できる効果がある。更に、基材上に中間層を介
して酸化物超電導層を設け、かつ、Ａｇなどの貴金属や
その合金の下地安定化薄膜と良導電性金属材料製の安定
化層を酸化物超電導層上に形成した構造を採用すると、
酸化物超電導層の熱処理時において、酸化物超電導層の
構成元素と基材の構成元素が相互拡散することを中間層
が抑制するとともに、酸化通超電導層の構成元素と安定
化層の構成元素が相互拡散することを安定化薄膜が抑制
するので、熱処理を施したものであっても超電導特性が
劣化していない酸化物超電導導体を得ることができる。In the oxide superconducting conductor having a structure in which the underlayer stabilizing thin film and the stabilizing layer are formed on the oxide superconducting layer, the thickness of the portion including the base material and the intermediate layer, the underlayer stabilizing thin film and the stabilizing layer are stable. Since the thickness of the stabilized metal layer part including the oxide layers is made equal, the effect of the stress applied to the oxide superconducting layer when bending is reduced and the oxidation with excellent critical current characteristics can be achieved. There is an effect that a superconducting conductor can be provided. Therefore, there is an effect that an oxide superconducting coil having excellent critical current characteristics can be provided. Furthermore, an oxide superconducting layer is provided on the base material via an intermediate layer, and a base stabilizing thin film of a noble metal such as Ag or its alloy and a stabilizing layer made of a good conductive metal material are provided on the oxide superconducting layer. Adopting the formed structure,
During the heat treatment of the oxide superconducting layer, the intermediate layer suppresses the mutual diffusion of the constituent elements of the oxide superconducting layer and the constituent elements of the base material, and the constituent elements of the oxidation conducting superconducting layer and the constituent elements of the stabilizing layer are Since the stabilizing thin film suppresses mutual diffusion, it is possible to obtain an oxide superconducting conductor whose superconducting properties are not deteriorated even when heat-treated.

【図面の簡単な説明】[Brief description of drawings]

【図１】図１は本発明の第１実施例の断面図である。FIG. 1 is a sectional view of a first embodiment of the present invention.

【図２】図２は本発明の第２実施例の断面図である。FIG. 2 is a sectional view of a second embodiment of the present invention.

【図３】図３は基材上に中間層を形成した状態を示す断
面図である。FIG. 3 is a cross-sectional view showing a state in which an intermediate layer is formed on a base material.

【図４】図４は図３に示す中間層上に酸化物超電導層を
形成した状態を示す断面図である。4 is a cross-sectional view showing a state in which an oxide superconducting layer is formed on the intermediate layer shown in FIG.

【図５】図５は図４に示す酸化物超電導層上に下地安定
化被膜を形成した状態を示す断面図である。5 is a cross-sectional view showing a state in which a base stabilizing coating is formed on the oxide superconducting layer shown in FIG.

【図６】図６は得られた酸化物超電導テープを示す断面
図である。FIG. 6 is a cross-sectional view showing the obtained oxide superconducting tape.

【図７】図７は本発明に係る酸化物超電導導体の歪と臨
界電流密度の関係を示すグラフである。FIG. 7 is a graph showing the relationship between the strain and the critical current density of the oxide superconducting conductor according to the present invention.

【図８】図８は特に結晶配向させていない中間層を用い
た場合の酸化物超電導導体の歪と臨界電流密度の関係を
示すグラフである。FIG. 8 is a graph showing the relationship between the strain of an oxide superconducting conductor and the critical current density when an intermediate layer in which no crystal orientation is used is used.

【図９】図９は結晶配向させた中間層を用いた場合の酸
化物超電導導体の歪と臨界電流密度の関係を示すグラフ
である。FIG. 9 is a graph showing the relationship between the strain of an oxide superconducting conductor and the critical current density when a crystal-oriented intermediate layer is used.

【符号の説明】[Explanation of symbols]

Ａ、Ｂ…酸化物超電導導体、１…基材、
２…中間層、 ３…酸化物超電導層、４、
４’…安定化金属層、 ４ａ…下地安定化薄膜、４ｂ
…安定化層、５…基材部、A, B ... Oxide superconducting conductor, 1 ... Base material,
2 ... Intermediate layer, 3 ... Oxide superconducting layer, 4,
4 '... stabilizing metal layer, 4a ... base stabilizing thin film, 4b
... Stabilizing layer, 5 ... Base material part,

───────────────────────────────────────────────────── フロントページの続き (72)発明者 斉藤 隆 東京都江東区木場１丁目５番１号 株式会 社フジクラ内 (72)発明者 河野 宰 東京都江東区木場１丁目５番１号 株式会 社フジクラ内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Takashi Saito 1-5-1 Kiba, Koto-ku, Tokyo Fujikura Ltd. Inside Fujikura

Claims (2)

【特許請求の範囲】[Claims] 【請求項１】 テープ状の基材上に中間層を介して酸化
物超電導層が形成され、この酸化物超電導層上に良導電
性の安定化金属層が形成されるとともに、前記基材と中
間層を合わせた部分の厚さと、前記安定化金属層の厚さ
が、同等にされてなることを特徴とする安定化金属層を
備えた酸化物超電導導体の構造。1. An oxide superconducting layer is formed on a tape-shaped substrate via an intermediate layer, and a stabilized metal layer having good conductivity is formed on the oxide superconducting layer. A structure of an oxide superconducting conductor having a stabilizing metal layer, wherein a thickness of a portion including the intermediate layers and a thickness of the stabilizing metal layer are made equal to each other. 【請求項２】 テープ状の基材上に中間層を介して酸化
物超電導層が形成され、この酸化物超電導層上に、Ａ
ｇ、Ｐｔなどの貴金属またはその合金製の良導電性の下
地安定化薄膜と、ＣｕあるいはＡｌなどの良導電性金属
材料製の安定化層とからなる安定化金属層が形成される
とともに、前記基材と中間層を合わせた部分の厚さと、
前記安定化金属層の厚さが、同等にされてなることを特
徴とする安定化金属層を備えた酸化物超電導導体の構
造。2. An oxide superconducting layer is formed on a tape-shaped substrate via an intermediate layer, and A is formed on the oxide superconducting layer.
A stabilizing metal layer composed of a noble metal such as g and Pt or an alloy thereof having good conductivity and a stabilizing layer made of a good conductive metal material such as Cu or Al is formed, and The thickness of the part where the base material and the intermediate layer are combined,
The structure of an oxide superconducting conductor having a stabilizing metal layer, wherein the stabilizing metal layer has an equal thickness.
JP22146793A 1993-09-06 1993-09-06 Structure of oxide superconductor with stabilizing metal layer Expired - Lifetime JP3568561B2 (en)

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