JP5096974B2 - RE-Ba-Cu-O-based superconducting tape wire manufacturing method and plasma processing apparatus used therefor - Google Patents

RE-Ba-Cu-O-based superconducting tape wire manufacturing method and plasma processing apparatus used therefor Download PDF

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JP5096974B2
JP5096974B2 JP2008078432A JP2008078432A JP5096974B2 JP 5096974 B2 JP5096974 B2 JP 5096974B2 JP 2008078432 A JP2008078432 A JP 2008078432A JP 2008078432 A JP2008078432 A JP 2008078432A JP 5096974 B2 JP5096974 B2 JP 5096974B2
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隆司 長谷
雅夫 水野
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酸化物超電導テープ線材であって、ＹＢａ２Ｃｕ３Ｏｙ系に代表されるＲＥＢａ２Ｃｕ３Ｏｙ系超電導テープ線材は、超電導磁石、超電導モータなどの各種超電導応用機器への利用を図る研究が盛んになっている。本発明は、ＲＥ−Ｂａ−Ｃｕ−Ｏ系超電導テープ線材の製造方法、及びそれに用いるプラズマ処理装置に関するものである。 REBa 2 Cu 3 O y- based superconducting tape wire, which is an oxide superconducting tape wire represented by YBa 2 Cu 3 O y, has been studied for use in various superconducting applications such as superconducting magnets and superconducting motors. It is flourishing. The present invention relates to a method for producing a RE-Ba-Cu-O-based superconducting tape wire and a plasma processing apparatus used therefor.

テープ状の希土類系酸化物超電導体、すなわち、ＹＢａ２Ｃｕ３Ｏｙ系に代表されるＲＥＢａ２Ｃｕ３Ｏｙ（以下、ＲＥ１２３と記す。ＲＥは、Ｙ、Ｎｄ、Ｓｍ、Ｇｄ、Ｅｕ、Ｙｂ、Ｐｒ及びＨｏのうち少なくとも１種の元素、６．４≦ｙ≦７．０）系超電導体の製造にあたり、ＭＯＤ法（金属有機酸塩堆積法：Ｍｅｔａｌ Ｏｒｇａｎｉｃ Ｄｅｐｏｓｉｔｉｏｎ Ｐｒｏｃｅｓｓ）が知られている。 Tape-shaped rare earth-based oxide superconductor, i.e., REBa 2 Cu 3 O y (hereinafter typified by YBa 2 Cu 3 O y system, .RE referred to as RE123 is, Y, Nd, Sm, Gd , Eu, Yb MOD (Metal Organic Deposition Process: Metal Organic Deposition Process) is known for producing at least one element of Pr, Ho and 6.4 ≦ y ≦ 7.0.

このＭＯＤ法は、金属有機酸塩が均一に溶解した原料溶液を基板上に塗布した後、これを加熱して熱分解させることにより、基板上に成膜を行う方法である。このＭＯＤ法は、非真空プロセスであるため、真空中でガスを導入して行う他のプロセスに比べて、低コストで高速成膜が可能という特長があり、長尺のＲＥ−Ｂａ−Ｃｕ−Ｏ系超電導テープ線材の製造に適するものである。   This MOD method is a method in which a raw material solution in which a metal organic acid salt is uniformly dissolved is applied on a substrate, and then heated and thermally decomposed to form a film on the substrate. Since this MOD method is a non-vacuum process, it has a feature that high-speed film formation is possible at a lower cost than other processes performed by introducing gas in a vacuum, and a long RE-Ba-Cu- It is suitable for the production of O-based superconducting tape wires.

ここで、ＲＥ１２３系超電導体膜は、その超電導特性が超電導相結晶の結晶方位に強く依存することから、基板表面に垂直な方向に結晶のｃ軸を配向させるだけでなく、基板面に平行な方向にも、超電導相結晶のａ軸やｂ軸を揃えて二軸配向させる必要がある。そのために、基板材料として、超電導相結晶の結晶格子定数に近い格子定数を有する材料を選択し、その基板材料も二軸配向させる必要がある。   Here, since the superconducting properties of the RE123-based superconductor film strongly depend on the crystal orientation of the superconducting phase crystal, not only the c-axis of the crystal is oriented in a direction perpendicular to the substrate surface but also parallel to the substrate surface. Also in the direction, it is necessary to align the a-axis and b-axis of the superconducting phase crystal so that they are biaxially oriented. Therefore, it is necessary to select a material having a lattice constant close to the crystal lattice constant of the superconducting phase crystal as the substrate material, and to make the substrate material also biaxially oriented.

そして、ＭＯＤ法においては、出発原料である金属有機酸塩を熱分解させると、通常はＢａの炭酸塩が生成する。一度このＢａの炭酸塩が生じると、ＲＥ１２３系超電導膜を生成させるには、このＢａ炭酸塩を分解させなければいけないため、８００℃以上の高温で熱処理を行う必要がある。ところが、８００℃以上の高温で熱処理を行うと、基板の結晶性の影響が弱くなった条件で成長するため、得られるＲＥ１２３系超電導膜の結晶の面内配向性に乱れが生じる可能性が高くなることとなる。   In the MOD method, when a metal organic acid salt as a starting material is pyrolyzed, Ba carbonate is usually generated. Once this Ba carbonate is generated, in order to produce an RE123-based superconducting film, this Ba carbonate must be decomposed, and thus heat treatment must be performed at a high temperature of 800 ° C. or higher. However, if heat treatment is performed at a high temperature of 800 ° C. or higher, the crystal growth of the RE123-based superconducting film is likely to be disturbed because it grows under the condition that the influence of the crystallinity of the substrate is weakened. Will be.

そこで、前記Ｂａ炭酸塩を経由せずに、８００℃以下の温度での熱処理によりＲＥ１２３系超電導膜を生成するために、フッ素を含む有機酸塩（例えば、トリフルオロ酢酸塩）を出発原料として、水蒸気雰囲気中で熱処理を行い、フッ化物を経由してＲＥ１２３系超電導膜を生成させるプロセスの開発が近年精力的に行われている。   Therefore, in order to produce a RE123-based superconducting film by heat treatment at a temperature of 800 ° C. or less without passing through the Ba carbonate, an organic acid salt containing fluorine (for example, trifluoroacetate) is used as a starting material. In recent years, development of a process for generating a RE123-based superconducting film via fluoride by performing a heat treatment in a steam atmosphere has been vigorously performed.

ところが、ＭＯＤ法においてフッ素を含む有機酸塩を水蒸気雰囲気中で処理する場合には、フッ化水素が発生する。フッ化水素は有毒であるため、その排気のために処理設備が必要となる。さらに、塗布膜に供給する水蒸気ガスのフロー状態によって、ＲＥ１２３系超電導膜の生成が強く影響されるため、水蒸気ガスフローの状態を細かく制御する必要がある。一方、フッ素を含む有機酸塩を含まない場合は、発生するフッ化水素の排気処理設備は必要ないし、水蒸気ガスのフローによって、ＲＥ１２３系超電導膜の生成が影響されることもない。   However, when an organic acid salt containing fluorine is treated in a steam atmosphere in the MOD method, hydrogen fluoride is generated. Since hydrogen fluoride is toxic, a treatment facility is required for exhausting the hydrogen fluoride. Furthermore, since the generation of the RE123-based superconducting film is strongly influenced by the flow state of the water vapor gas supplied to the coating film, it is necessary to finely control the state of the water vapor gas flow. On the other hand, when an organic acid salt containing fluorine is not included, an exhaust treatment facility for the generated hydrogen fluoride is not required, and the generation of the RE123-based superconducting film is not affected by the flow of water vapor gas.

また、ＭＯＤ法においてフッ素を含む金属有機酸塩を出発原料とする場合、金属有機酸塩の分解速度に影響する仮焼処理中の昇温速度が速いと、金属有機酸塩の熱分解が不充分であり、仮焼後に得られる、ＲＥ１２３系超電導体の前駆体膜の膜中に、溶媒やフッ化物の有機鎖が残存する傾向がある。そのため、ＲＥ１２３系超電導膜の生成のための、その後の熱処理（本焼）の昇温中に、残存している溶媒やフッ化物の有機鎖が急激に分解して、膜中にクラックやボイドが多数発生する。これらのクラックやボイドのため、ＲＥ１２３系超電導膜の超電導特性が著しく低下することとなる。   In addition, when a metal organic acid salt containing fluorine is used as a starting material in the MOD method, if the rate of temperature rise during the calcination treatment that affects the decomposition rate of the metal organic acid salt is high, the metal organic acid salt is not thermally decomposed. It is sufficient, and the organic chain of the solvent or fluoride tends to remain in the film of the RE123-based superconductor precursor film obtained after calcination. Therefore, the remaining solvent and fluoride organic chains are rapidly decomposed during the temperature rise of the subsequent heat treatment (main firing) for the production of the RE123-based superconducting film, and cracks and voids are formed in the film. Many occur. Due to these cracks and voids, the superconducting properties of the RE123-based superconducting film are significantly deteriorated.

そこで、従来、仮焼処理中の昇温速度を制御するようにした、テープ状酸化物超電導体の製造方法が提案されている（特開２００３−３００７２６号公報）。   Therefore, conventionally, a method for producing a tape-shaped oxide superconductor has been proposed in which the temperature rising rate during the calcination treatment is controlled (Japanese Patent Laid-Open No. 2003-300726).

しかしながら、この従来の製造方法では、残存している溶媒やフッ化物の有機鎖の急激な分解が抑制され、ＲＥ１２３系超電導膜の厚膜化は達成されるものの、ＲＥ１２３系超電導膜の厚みが２μｍ程度になると、クラックが発生するという問題があった。   However, in this conventional manufacturing method, although the rapid decomposition of the remaining solvent and fluoride organic chains is suppressed and the RE123-based superconducting film is thickened, the thickness of the RE123-based superconducting film is 2 μm. When it was about, there was a problem that cracks occurred.

また、特開２００７−１６５１５３号公報には、厚膜テープ状ＲＥ系（１２３）超電導体の製造方法が提案されている。この製造方法は、前駆体を形成する熱処理（仮焼）と、超電導体生成の熱処理（本焼）との間に、超電導体生成の熱処理温度よりも低い温度で中間熱処理を施すことにより、厚膜条件でも溶媒やフッ化物の有機鎖を低減し、クラックの発生を防止して、高い臨界電流を有する厚みが２μｍを超える厚膜（約２．５〜４μｍ）のテープ状ＲＥ系（１２３）超電導体を製造するようにしたものである。   Japanese Unexamined Patent Application Publication No. 2007-165153 proposes a method for manufacturing a thick film tape-shaped RE (123) superconductor. In this manufacturing method, an intermediate heat treatment is performed at a temperature lower than the heat treatment temperature for superconductor generation between the heat treatment for forming the precursor (calcination) and the heat treatment for the production of the superconductor (main firing). Reducing the organic chain of solvent and fluoride even under film conditions, preventing the generation of cracks, and having a high critical current thickness of over 2 μm (about 2.5-4 μm) tape-like RE system (123) A superconductor is manufactured.

しかしながら、この従来の製造方法では、前記中間熱処理の温度に上昇させるまでに２００分程度の時間を要し、到達した中間熱処理温度で６０〜１２０分の保持時間を必要としており、前記中間熱処理に相当の長い時間を要し、生産性が低いという問題があった。
特開２００３−３００７２６号公報 特開２００７−１６５１５３号公報 However, in this conventional manufacturing method, it takes about 200 minutes to raise the temperature of the intermediate heat treatment, and a holding time of 60 to 120 minutes is required at the reached intermediate heat treatment temperature. There was a problem that it took a considerable amount of time and productivity was low.
Japanese Patent Laid-Open No. 2003-300726 JP 2007-165153 A

そこで、本発明の課題は、フッ素を含む金属有機酸塩を出発原料として、ＲＥ−Ｂａ−Ｃｕ−Ｏ系超電導テープ線材を製造するに際し、ＲＥＢａ２Ｃｕ３Ｏｙ系（ＲＥ１２３系）超電導体の前駆体膜の形成に要する加熱処理時間を従来に比べて大幅に短縮することができるとともに、厚みが２μｍを超える厚膜で、かつ、高い臨界電流を有するＲＥ−Ｂａ−Ｃｕ−Ｏ系超電導テープ線材を得ることができる、ＲＥ−Ｂａ−Ｃｕ−Ｏ系超電導テープ線材の製造方法、及びそれに用いるプラズマ処理装置を提供することにある。 Thus, the object of the present invention is to manufacture a RE-Ba-Cu-O-based superconducting tape wire using a metal organic acid salt containing fluorine as a starting material, and to produce a REBa 2 Cu 3 O y- based (RE123-based) superconductor. RE-Ba-Cu-O-based superconducting tape that can significantly reduce the heat treatment time required for forming the precursor film and has a high critical current with a thickness exceeding 2 μm. An object of the present invention is to provide an RE-Ba-Cu-O-based superconducting tape wire manufacturing method capable of obtaining a wire, and a plasma processing apparatus used therefor.

前記の課題を解決するため、本願発明は、次の技術的手段を講じている。   In order to solve the above-described problems, the present invention takes the following technical means.

請求項１の発明は、テープ状基板上に、ＲＥＢａ２Ｃｕ３Ｏｙ（ＲＥは、Ｙ、Ｎｄ、Ｓｍ、Ｇｄ、Ｅｕ、Ｙｂ、Ｐｒ及びＨｏのうち少なくとも１種の元素、６．４≦ｙ≦７．０）系超電導体を構成する各金属元素を所定の組成比で含む金属有機酸塩を混合してなる原料溶液を塗布し、該原料溶液を乾燥して、原料塗布テープ状基板を作製する第１工程と、グロー放電プラズマ中を前記原料塗布テープ状基板を通過させることにより、前記超電導体の前駆体膜が形成された前駆体膜形成テープ状基板を得る第２工程と、得られた前記前駆体膜形成テープ状基板に前記超電導体を生成させる熱処理を施す第３工程とを備え、前記金属有機酸塩がフッ素を含むものであり、前記グロー放電プラズマのプラズマ生成ガスが水素を含むものであることを特徴とするＲＥ−Ｂａ−Ｃｕ−Ｏ系超電導テープ線材の製造方法である。 According to the first aspect of the present invention, REBa 2 Cu 3 O y (RE is at least one element of Y, Nd, Sm, Gd, Eu, Yb, Pr and Ho, 6.4 ≦ y ≦ 7.0) A raw material solution obtained by mixing a metal organic acid salt containing each metal element constituting a superconductor in a predetermined composition ratio is applied, and the raw material solution is dried to form a raw material-coated tape-like substrate And a second step of obtaining a precursor film-formed tape-like substrate on which the precursor film of the superconductor is formed by passing the raw material-coated tape-like substrate through the glow discharge plasma. A third step of performing a heat treatment for generating the superconductor on the precursor film-formed tape-shaped substrate obtained , wherein the metal organic acid salt contains fluorine, and a plasma generation gas of the glow discharge plasma is It must contain hydrogen Which is a RE-Ba-Cu-O based superconducting manufacturing method of a tape wire, wherein.

請求項２の発明は、請求項１記載のＲＥ−Ｂａ−Ｃｕ−Ｏ系超電導テープ線材の製造方法において、前記第２工程において、円筒状外周面を有する回転電極に高周波電力又は直流電力を供給して前記グロー放電プラズマを発生させることを特徴とするものである。 A second aspect of the present invention, the supply method of manufacturing a RE-Ba-Cu-O based superconducting tape according to claim 1, wherein in the second step, the high-frequency power or DC power to the rotating electrode having a cylindrical outer peripheral surface Then, the glow discharge plasma is generated.

請求項３の発明は、請求項１又は２記載のＲＥ−Ｂａ−Ｃｕ−Ｏ系超電導テープ線材の製造方法において、前記第２工程において、前記原料塗布テープ状基板を加熱しながら、前記グロー放電プラズマ中を通過させることを特徴とするものである。 The invention according to claim 3 is the method for producing a RE-Ba-Cu-O-based superconducting tape wire according to claim 1 or 2 , wherein in the second step, the glow discharge is performed while heating the raw material coated tape substrate. It is characterized by passing through plasma.

請求項４の発明は、請求項１、２又は３記載のＲＥ−Ｂａ−Ｃｕ−Ｏ系超電導テープ線材の製造方法の製造方法における前記第２工程に用いられるプラズマ処理装置であって、グロー放電プラズマを発生させるための電極と、長尺の前記原料塗布テープ状基板を前記グロー放電プラズマ中を通過させ、該プラズマ中を通過させて得られた前記前駆体膜形成テープ状基板を引き取る搬送手段と、プラズマ生成ガスを導入するガス導入管を有するとともに、前記電極及び前記搬送手段を内部に収容する反応容器とを備えたことを特徴とするプラズマ処理装置である。 Invention of Claim 4 is a plasma processing apparatus used for the said 2nd process in the manufacturing method of the manufacturing method of RE-Ba-Cu-O type | system | group superconducting tape wire of Claim 1, 2 or 3 , Comprising: Glow discharge Electrodes for generating plasma, and conveying means for passing the elongated raw material-coated tape-like substrate through the glow discharge plasma and picking up the precursor film-forming tape-like substrate obtained by passing through the plasma And a reaction vessel having a gas introduction pipe for introducing a plasma generation gas and containing the electrode and the transfer means inside.

請求項５の発明は、請求項４記載のプラズマ処理装置において、前記電極は、回転駆動され、円筒状外周面を有するドラム状の回転電極であることを特徴とするものである。 According to a fifth aspect of the present invention, in the plasma processing apparatus of the fourth aspect , the electrode is a drum-shaped rotating electrode that is driven to rotate and has a cylindrical outer peripheral surface.

請求項６の発明は、請求項４又は５記載のプラズマ処理装置において、前記反応容器内に、前記グロー放電プラズマへ搬送されている前記原料塗布テープ状基板を加熱する基板加熱手段を備えていることを特徴とするものである。 A sixth aspect of the present invention is the plasma processing apparatus according to the fourth or fifth aspect , further comprising a substrate heating means for heating the raw material-coated tape-shaped substrate transported to the glow discharge plasma in the reaction vessel. It is characterized by this.

本発明のＲＥ−Ｂａ−Ｃｕ−Ｏ系超電導テープ線材の製造方法は、原料塗布テープ状基板を、グロー放電プラズマ中を通過させることにより、ＲＥ１２３系超電導体の前駆体膜が形成された前駆体膜形成テープ状基板（前駆体膜形成テープ線材）を得るようにした工程を備えている。これにより、ＲＥ１２３系超電導体の前駆体膜の形成に要する加熱処理時間を従来に比べて大幅に短縮することができ、さらに、良質な前駆体膜を得ることができるので、厚みが２μｍを超える厚膜で、かつ、高い臨界電流を有するＲＥ１２３系超電導テープ線材を得ることができる。   The RE-Ba-Cu-O-based superconducting tape wire manufacturing method of the present invention is a precursor in which a precursor film of RE123-based superconductor is formed by passing a raw material-coated tape-shaped substrate through glow discharge plasma. A step of obtaining a film-forming tape-like substrate (precursor film-forming tape wire); As a result, the heat treatment time required for the formation of the RE123-based superconductor precursor film can be significantly shortened as compared with the conventional one, and a high-quality precursor film can be obtained, so that the thickness exceeds 2 μm. A RE123-based superconducting tape wire having a thick film and a high critical current can be obtained.

また、本発明のプラズマ処理装置は、長尺の前駆体膜形成テープ状基板を生産性良く作製することができる。   Moreover, the plasma processing apparatus of the present invention can produce a long precursor film-formed tape-shaped substrate with high productivity.

以下、本発明について、実施例を含めてより詳しく説明する。   Hereinafter, the present invention will be described in more detail including examples.

本発明の製造方法では、原料塗布テープ状基板を加熱処理して、テープ状基板表面にＲＥ１２３系超電導体の前駆体膜をするに際し、電気炉などの加熱炉を用いる従来方法とは違って、グロー放電プラズマを用いるようにしている（第２工程）。   In the production method of the present invention, when a raw material-coated tape-like substrate is heat-treated to form a RE123-based superconductor precursor film on the surface of the tape-like substrate, unlike a conventional method using a heating furnace such as an electric furnace, Glow discharge plasma is used (second step).

このようなグロー放電プラズマ中には、プラズマ生成ガス元素のイオンやラジカルなどの活性種が高い密度で存在する。本発明者らは、このようなグロー放電プラズマにさらされた塗布膜では、熱エネルギーのみによる熱分解とは異なり、金属有機酸塩の化学結合がほぼ同時に切断され、分解が５分未満の短時間の間に進行し、かつ、いわゆる仮焼前駆体として、分子レベルでより均一分散された良質な前駆体膜が得られることを見出したものである。   In such glow discharge plasma, active species such as ions and radicals of plasma generating gas elements are present at a high density. In the coating film exposed to such glow discharge plasma, unlike the thermal decomposition using only thermal energy, the chemical bond of the metal organic acid salt is cut almost simultaneously, and the decomposition is a short period of less than 5 minutes. It has been found that a high-quality precursor film that progresses over time and is more uniformly dispersed at the molecular level can be obtained as a so-called calcined precursor.

本発明の方法では、塗布膜中にフッ素を含む金属有機酸塩が含まれるものの、第２工程において、プラズマ生成ガスとして水素を含有させたガスを用いることにより、塗布膜中に存在するフッ素は水素と反応してフッ化水素として除去できる。この場合、グロー放電プラズマ中の水素分圧を０．５Ｔｏｒｒ（０．５×１３３．３Ｐａ）以上にすれば、塗布膜中のフッ素を十分に除去する効果が期待できる。また、１．０Ｔｏｒｒ（１．０×１３３．３Ｐａ）以上の酸素を含有させることにより、塗布膜中に存在する炭素を酸素と反応させて炭酸ガスとして効果的に排除することができる。 In the method of the present invention, although a metal organic acid salt containing fluorine is contained in the coating film, in the second step, by using a gas containing hydrogen as a plasma generating gas, fluorine existing in the coating film is It can be removed as hydrogen fluoride by reacting with hydrogen. In this case, if the hydrogen partial pressure in the glow discharge plasma is set to 0.5 Torr (0.5 × 133.3 Pa) or more, an effect of sufficiently removing fluorine in the coating film can be expected. Further, by containing oxygen of 1.0 Torr (1.0 × 133.3 Pa) or more, carbon existing in the coating film can be reacted with oxygen and effectively eliminated as carbon dioxide gas.

参考として、塗布膜中にフッ素を含む金属有機酸塩を含まない場合、加熱炉による通常の熱分解ではＢａ炭酸塩が生成するが、グロー放電プラズマを用いることにより、Ｂａ炭酸塩が生成せず、さらに、Ｙ、Ｂａ、Ｃｕの各金属有機酸塩がミクロに均一分散された良質な前駆体膜が得られる。 For reference, when the coating film does not contain a metal organic acid salt containing fluorine, Ba carbonate is generated by normal pyrolysis in a heating furnace, but Ba carbonate is not generated by using glow discharge plasma. In addition, a high-quality precursor film in which the metal organic acid salts of Y, Ba, and Cu are uniformly dispersed microscopically can be obtained.

これにより、熱処理の温度が８００℃未満（例えば、７８０℃）の温度でも、二軸配向したＲＥ１２３系超電導体膜の生成が可能である。フッ素を含む金属有機酸塩を処理する場合に発生するフッ化水素は有毒であるため、その排気のために処理設備が必要となるが、塗布膜中にフッ素を含む有機酸塩を含まない場合は、そのような設備は必要ない。また、１．０Ｔｏｒｒ（１．０×１３３．３Ｐａ）以上の酸素を含有させることにより、塗布膜中に存在する炭素を酸素と反応させて炭酸ガスとして効果的に排除することができる。 Thereby, even if the temperature of heat processing is less than 800 degreeC (for example, 780 degreeC), the production | generation of RE123 type | system | group superconductor film | membrane with biaxial orientation is possible. Hydrogen fluoride generated when processing a metal organic acid salt containing fluorine is toxic, so a treatment facility is required for its exhaust, but the coating film does not contain an organic acid salt containing fluorine No such equipment is necessary. Further, by containing oxygen of 1.0 Torr (1.0 × 133.3 Pa) or more, carbon existing in the coating film can be reacted with oxygen and effectively eliminated as carbon dioxide gas.

本発明の方法では、第２工程においては、水素分圧が３０Ｔｏｒｒ（３０×１３３．３Ｐａ）より大きく、又は、酸素分圧が６０Ｔｏｒｒ（６０×１３３．３Ｐａ）より大きいとグロー放電プラズマの発生が困難となる。これらの適正な範囲の水素分圧、酸素分圧を有するグロー放電プラズマを生成するために、ヘリウムガスを混合して全圧力が１００〜１５００Ｔｏｒｒ（１００×１３３．３Ｐａ〜１５００×１３３．３Ｐａ）の範囲を満たすようにすることがよい。より好ましくは、水素分圧は２〜１５Ｔｏｒｒ（２×１３３．３Ｐａ〜１５×１３３．３Ｐａ）の範囲、酸素分圧は４〜３０Ｔｏｒｒ（４×１３３．３Ｐａ〜３０×１３３．３Ｐａ）の範囲、そのときの全圧力は４００〜９００Ｔｏｒｒ（４００×１３３．３Ｐａ〜９００×１３３．３Ｐａ）の範囲である。 In the method of the present invention, in the second step, if the hydrogen partial pressure is greater than 30 Torr (30 × 133.3 Pa) or the oxygen partial pressure is greater than 60 Torr (60 × 133.3 Pa), glow discharge plasma is generated. It becomes difficult. In order to generate a glow discharge plasma having a hydrogen partial pressure and an oxygen partial pressure in the proper ranges, helium gas is mixed and the total pressure is 100 to 1500 Torr (100 × 133.3 Pa to 1500 × 133.3 Pa). It is better to satisfy the range. More preferably, the hydrogen partial pressure is in the range of 2 to 15 Torr (2 × 133.3 Pa to 15 × 133.3 Pa), the oxygen partial pressure is in the range of 4 to 30 Torr (4 × 133.3 Pa to 30 × 133.3 Pa), The total pressure at that time is in the range of 400 to 900 Torr (400 × 133.3 Pa to 900 × 133.3 Pa).

本発明の方法では、第２工程において原料塗布テープ状基板をグロー放電プラズマ中を通過させるに際し、基板加熱手段によって原料塗布テープ状基板を加熱することがよい。原料塗布テープ状基板を加熱すると、加熱しない場合に比べて、プラズマ処理時間を短縮できるという効果がある。これは、加熱によって塗布膜中の炭素を効果的に蒸発させることができるためであり、炭素を除去するに要する時間分だけプラズマ処理の時間を短くすることができる。なお、原料塗布テープ状基板の温度は、５００℃以下となるようにすることがよい。５００℃を超えると、得られる前駆体膜中にＹがリッチ（ｒｉｃｈ）の非超電導酸化物が生成し、後の熱処理工程（第３工程）においてＲＥ１２３系超電導体膜の良好な生成（良好な結晶成長）が阻害される。   In the method of the present invention, when the raw material-coated tape substrate is passed through the glow discharge plasma in the second step, the raw material-coated tape substrate is preferably heated by the substrate heating means. When the raw material-coated tape-shaped substrate is heated, there is an effect that the plasma processing time can be shortened as compared with the case where it is not heated. This is because carbon in the coating film can be effectively evaporated by heating, and the plasma processing time can be shortened by the time required to remove the carbon. The temperature of the raw material coated tape substrate is preferably 500 ° C. or lower. When the temperature exceeds 500 ° C., a non-superconducting oxide rich in Y is formed in the resulting precursor film, and the RE123-based superconductor film is favorably formed (good) in the subsequent heat treatment step (third step). Crystal growth) is inhibited.

本発明の方法の第２工程の実施に用いるプラズマ処理装置としては、反応容器内に平行平板型の電極、あるいは、ドラム状の回転電極を備えたプラズマ処理装置を用いることができる。ドラム状回転電極を備えたプラズマ処理装置は、電界の集中がないためアーク放電が起き難いなどの利点がある。   As a plasma processing apparatus used for carrying out the second step of the method of the present invention, a plasma processing apparatus having a parallel plate type electrode or a drum-shaped rotating electrode in the reaction vessel can be used. The plasma processing apparatus provided with the drum-like rotating electrode has an advantage that arc discharge is difficult to occur because there is no concentration of the electric field.

図１は本発明の方法の実施に用いるプラズマ処理装置の構成を概略的に示す図である。   FIG. 1 is a diagram schematically showing the configuration of a plasma processing apparatus used for carrying out the method of the present invention.

図１に示すプラズマ処理装置は、箱状をなす反応容器（チャンバー）１１を備えており、反応容器１１内には、グロー放電プラズマを発生させるための平行平板型電極として、上部電極１８と下部電極１９との二つの平板状電極が所定距離を隔てて対向配置されている。グロー放電プラズマの安定化を図るため、電極１８，１９それぞれの表面には、ガラス板からなる誘電体板２０が固着されている。上部電極１８は、整合器１５を介して高周波電源１４に接続されている。下部電極１９は接地されている。   The plasma processing apparatus shown in FIG. 1 includes a reaction container (chamber) 11 having a box shape, and an upper electrode 18 and a lower electrode are formed in the reaction container 11 as parallel plate electrodes for generating glow discharge plasma. Two flat electrodes with the electrode 19 are arranged to face each other with a predetermined distance. In order to stabilize the glow discharge plasma, a dielectric plate 20 made of a glass plate is fixed to the surface of each of the electrodes 18 and 19. The upper electrode 18 is connected to the high frequency power supply 14 through the matching unit 15. The lower electrode 19 is grounded.

下部電極１９の内部には、後述する送り出しロール１６からの原料塗布テープ状基板１を加熱する基板加熱手段としての加熱用ヒータ２１が設けられており、原料塗布テープ状基板１の温度を調節できるようになっている。反応容器１１には、ガス成分ごとに所定圧力に調整されたプラズマ生成ガスを導入する複数のガス導入管１２（１つだけ図示）が接続され、また、ガスの排気管１３が接続されている。   Inside the lower electrode 19 is provided a heating heater 21 as a substrate heating means for heating the raw material application tape-like substrate 1 from a feed roll 16 described later, and the temperature of the raw material application tape-like substrate 1 can be adjusted. It is like that. The reaction vessel 11 is connected to a plurality of gas introduction pipes 12 (only one is shown) for introducing a plasma generation gas adjusted to a predetermined pressure for each gas component, and to a gas exhaust pipe 13. .

また、反応容器１１内には、送り出しロール１６と巻き取りロール１７が設けられている。送り出しロール１６に巻回された長尺の原料塗布テープ状基板１は、巻き取りロール１７が駆動モータ（図示せず）によって回転されることで、送り出しロール１６から連続的に引き出されてプラズマ発生領域Ｐへ導かれる。そして、プラズマ発生領域Ｐを通過して得られた前駆体膜形成テープ状基板１’は、巻き取りロール１７に連続的に巻き取られるようになっている。送り出しロール１６及び巻き取りロール１７は、搬送手段を構成している。   In the reaction vessel 11, a feed roll 16 and a take-up roll 17 are provided. The long material-coated tape-like substrate 1 wound around the delivery roll 16 is continuously drawn out from the delivery roll 16 by the take-up roll 17 being rotated by a drive motor (not shown) to generate plasma. Guided to region P. The precursor film-forming tape-like substrate 1 ′ obtained by passing through the plasma generation region P is continuously wound around the winding roll 17. The delivery roll 16 and the take-up roll 17 constitute a conveying means.

図２は本発明の方法の実施に用いる別のプラズマ処理装置の構成を概略的に示す図である。ここで、前記図１に示すプラズマ処理装置と共通する部分には同一の符号を付して説明を省略し、異なる点について説明する。   FIG. 2 is a diagram schematically showing the configuration of another plasma processing apparatus used for carrying out the method of the present invention. Here, parts common to those in the plasma processing apparatus shown in FIG. 1 are denoted by the same reference numerals, description thereof is omitted, and different points will be described.

図２に示すように、反応容器１１内には、ドラム状の対向ロール２３が回転自在に設けられており、この対向ロール２３の上方に、これと所定距離を隔てて対向するように、ドラム状回転電極２２が設けられている。グロー放電プラズマを発生させるためのドラム状回転電極２２は、グロー放電プラズマの安定化を図るため、その円筒状外周面にアルミナ（誘電体）が溶射されている。   As shown in FIG. 2, a drum-shaped counter roll 23 is rotatably provided in the reaction vessel 11, and the drum is disposed above the counter roll 23 with a predetermined distance therebetween. A rotating electrode 22 is provided. The drum-like rotating electrode 22 for generating glow discharge plasma is sprayed with alumina (dielectric) on its cylindrical outer peripheral surface in order to stabilize the glow discharge plasma.

このドラム状回転電極２２の両側の回転軸は、それぞれ、軸受によって電気的に絶縁された状態で軸支されている。そして、ドラム状回転電極２２の一方側の回転軸は、反応容器１１の外側面に取り付けられた回転電極用駆動モータの駆動軸に電気的に絶縁された状態で連結されており、他方側の回転軸は、整合器１５を介して高周波電源１４に電気的に接続されている。接地されている前記対向ロール２３は、電極を兼用しており、その円筒状外周面にアルミナ（誘電体）が溶射されている。グロー放電プラズマは、ドラム状回転電極２２と対向ロール２３の間に発生する。   The rotating shafts on both sides of the drum-shaped rotating electrode 22 are respectively supported in a state of being electrically insulated by bearings. The rotating shaft on one side of the drum-shaped rotating electrode 22 is electrically connected to the driving shaft of the rotating electrode drive motor attached to the outer surface of the reaction vessel 11, and is connected to the other side. The rotating shaft is electrically connected to the high frequency power supply 14 through the matching unit 15. The opposed roll 23 that is grounded also serves as an electrode, and alumina (dielectric) is sprayed on the cylindrical outer peripheral surface thereof. Glow discharge plasma is generated between the drum-shaped rotating electrode 22 and the opposing roll 23.

そして、長尺の原料塗布テープ状基板１は、巻き取りロール１７が駆動モータ（図示せず）によって回転されることで、送り出しロール１６から送り出されてプラズマ発生領域Ｐへ導かれる。そして、プラズマ発生領域Ｐを通過して得られた前駆体膜形成テープ状基板１’は、巻き取りロール１７に巻き取られるようになっている。なお、送り出しロール１６から対向ロール２３に至る搬送ラインの近傍には、送り出しロール１６からの原料塗布テープ状基板１を加熱する基板加熱手段としての加熱用ランプ２４が設けられている。   And the long raw material application | coating tape-like board | substrate 1 is sent out from the sending roll 16, and is guide | induced to the plasma generation area | region P, when the winding roll 17 is rotated by a drive motor (not shown). The precursor film-forming tape-like substrate 1 ′ obtained by passing through the plasma generation region P is wound around the winding roll 17. A heating lamp 24 is provided as a substrate heating means for heating the raw material-coated tape-like substrate 1 from the delivery roll 16 in the vicinity of the conveyance line from the delivery roll 16 to the opposing roll 23.

以下、本発明の実施例について、比較例を含めて説明する。   Examples of the present invention will be described below including comparative examples.

まず、比較例１について説明する。   First, Comparative Example 1 will be described.

基板として、厚み０．０５０ｍｍ、幅１０ｍｍのハステロイ基板上にＧｄ２Ｚｒ２Ｏ７及びＣｅＯ２を順次形成した複合基板を用いた。また、Ｙ及びＢａのトリフルオロ酢酸塩（フッ素を含む金属有機酸塩）とＣｕのナフテン酸塩をＹ：Ｂａ：Ｃｕのモル比が１：２：３となるように２−オクタノン中に金属含有量が１．５ｍｏｌ／Ｌの濃度に溶解し、これを原料溶液とした。そして、前記基板上に前記原料溶液を塗布し、これを１２０℃で乾燥させた。この塗布と乾燥のサイクルをさらに２回繰り返して表面に塗布膜が形成された原料塗布テープ状基板を作製した。 As a substrate, a composite substrate in which Gd 2 Zr 2 O 7 and CeO 2 were sequentially formed on a Hastelloy substrate having a thickness of 0.050 mm and a width of 10 mm was used. Further, Y and Ba trifluoroacetate (a metal organic acid salt containing fluorine) and Cu naphthenate are mixed in 2-octanone so that the molar ratio of Y: Ba: Cu is 1: 2: 3. The content was dissolved to a concentration of 1.5 mol / L, and this was used as a raw material solution. And the said raw material solution was apply | coated on the said board | substrate, and this was dried at 120 degreeC. This coating and drying cycle was further repeated twice to prepare a raw material coated tape substrate having a coating film formed on the surface.

次いで、電気炉を使用し、圧力１ａｔｍ（１．０１×１０５Ｐａ）であって、水蒸気濃度２．１％、酸素ガス濃度９７．９％というガス雰囲気中において、前記原料塗布テープ状基板に、温度勾配２℃／ｍｉｎで室温から５００℃まで加熱する処理（仮焼）を施すことにより（加熱処理時間：２４０分）、ＹＢａ２Ｃｕ３Ｏｙ（以下、Ｙ１２３と記す）超電導体の前駆体膜が形成された前駆体膜形成テープ状基板を作製した。このとき、加熱処理中に発生したフッ化水素ガスは、水に溶かした後、強アルカリと中和反応させることによって処理した。 Next, using an electric furnace, in a gas atmosphere having a pressure of 1 atm (1.01 × 10 5 Pa), a water vapor concentration of 2.1%, and an oxygen gas concentration of 97.9%, The precursor of YBa 2 Cu 3 O y (hereinafter referred to as Y123) superconductor is obtained by performing a treatment (calcination) for heating from room temperature to 500 ° C. at a temperature gradient of 2 ° C./min (heat treatment time: 240 minutes). A precursor film-formed tape-like substrate on which a body film was formed was produced. At this time, the hydrogen fluoride gas generated during the heat treatment was dissolved in water and then treated by neutralizing with a strong alkali.

次いで、電気炉を使用し、濃度１３．５％の水蒸気と濃度０．０９％の酸素とが混合された圧力１ａｔｍ（１．０１×１０５Ｐａ）のアルゴンガス雰囲気中において、前記の前駆体膜形成テープ状基板を、温度勾配３℃／ｍｉｎで５００℃から７６０℃まで昇温し、７６０℃にて９０分保持することにより、結晶格子が正方晶のＹ１２３超電導膜が形成されたＹ１２３超電導テープ線材を得た（中間熱処理なし）。その後、４００℃まで冷却し、圧力１ａｔｍ（１．０１×１０５Ｐａ）の純酸素雰囲気において温度４００℃にて３０分保持することにより、正方晶から斜方晶へ相変態させて、斜方晶の結晶格子を持つＹ１２３超電導膜とした。Ｙ１２３超電導膜の厚みは、２．８μｍであった。 Next, the precursor is used in an argon gas atmosphere having a pressure of 1 atm (1.01 × 10 5 Pa) in which an electric furnace is used and water vapor having a concentration of 13.5% and oxygen having a concentration of 0.09% are mixed. The film-formed tape-like substrate is heated from 500 ° C. to 760 ° C. at a temperature gradient of 3 ° C./min and held at 760 ° C. for 90 minutes, thereby forming a Y123 superconducting film having a tetragonal crystal Y123 superconducting film. A tape wire was obtained (no intermediate heat treatment). Then, it is cooled to 400 ° C., and maintained in a pure oxygen atmosphere at a pressure of 1 atm (1.01 × 10 5 Pa) at a temperature of 400 ° C. for 30 minutes to transform the phase from tetragonal to orthorhombic. A Y123 superconducting film having a crystal lattice was formed. The thickness of the Y123 superconducting film was 2.8 μm.

このようにして得られた比較例１のＹ１２３超電導テープ線材について、その所定寸法の切断片を温度７７．３Ｋの液体窒素に浸漬して、自己磁場中で１．０μＶ／ｃｍの電界基準を用いて、単位幅当たりの臨界電流Ｉｃを測定した。   The Y123 superconducting tape wire of Comparative Example 1 thus obtained was immersed in liquid nitrogen at a temperature of 77.3 K using a cut piece having a predetermined size, and an electric field standard of 1.0 μV / cm was used in a self magnetic field. Thus, the critical current Ic per unit width was measured.

その結果、臨界電流Ｉｃは、１２０Ａ／ｃｍという低い値にとどまった。また、Ｙ１２３超電導膜には、その表面を電子顕微鏡で観察したところ、ボイドやクラックが多数観察された。   As a result, the critical current Ic remained as low as 120 A / cm. Further, when the surface of the Y123 superconducting film was observed with an electron microscope, many voids and cracks were observed.

次に、参考例１について説明する。 Next, Reference Example 1 will be described.

基板として、厚み０．０５０ｍｍ，幅１０ｍｍのハステロイ基板上にＧｄ２Ｚｒ２Ｏ７及びＣｅＯ２を順次形成した複合基板を用いた。また、Ｙ及びＢａのイソノナン酸塩とＣｕのプロピオン酸塩（ともにフッ素を含まない金属有機酸塩）をＹ：Ｂａ：Ｃｕのモル比が１：２：３となるように酢酸n-ブチル中に金属含有量が１．５ｍｏｌ／Ｌの濃度に溶解し、これを原料溶液とした。そして、前記基板上に前記原料溶液を塗布し、これを１２０℃で乾燥させた。この塗布と乾燥のサイクルをさらに２回繰り返して表面に塗布膜が形成された原料塗布テープ状基板を作製した。 As the substrate, a composite substrate in which Gd 2 Zr 2 O 7 and CeO 2 were sequentially formed on a Hastelloy substrate having a thickness of 0.050 mm and a width of 10 mm was used. Also, Y and Ba isononanoate and Cu propionate (both metal organic acid salts containing no fluorine) in n-butyl acetate so that the molar ratio of Y: Ba: Cu is 1: 2: 3. The metal content was dissolved in a concentration of 1.5 mol / L, and this was used as a raw material solution. And the said raw material solution was apply | coated on the said board | substrate, and this was dried at 120 degreeC. This coating and drying cycle was further repeated twice to prepare a raw material coated tape substrate having a coating film formed on the surface.

次いで、電気炉を使用し、圧力１ａｔｍ（１．０１×１０５Ｐａ）で酸素ガス雰囲気中において、前記原料塗布テープ状基板に、温度勾配２℃／ｍｉｎで室温から５００℃まで加熱する処理（仮焼）を施すことにより、Ｙ１２３超電導体の前駆体膜が形成された前駆体膜形成テープ状基板を作製した。 Next, using an electric furnace, the raw material coated tape substrate is heated from room temperature to 500 ° C. at a temperature gradient of 2 ° C./min in an oxygen gas atmosphere at a pressure of 1 atm (1.01 × 10 5 Pa) ( By carrying out (calcination), a precursor film-formed tape-shaped substrate on which a precursor film of Y123 superconductor was formed was produced.

次いで、電気炉を使用し、濃度０．０９％の酸素が混合された圧力１ａｔｍ（１．０１×１０５Ｐａ）のアルゴン雰囲気中において、前記の前駆体膜形成テープ状基板を、温度勾配３℃／ｍｉｎで５００℃から７８０℃まで昇温し、７８０℃にて９０分保持することにより、結晶格子が正方晶のＹ１２３超電導膜が形成されたＹ１２３超電導テープ線材を得た（中間熱処理なし）。その後、４００℃まで冷却し、圧力１ａｔｍ（１．０１×１０５Ｐａ）で純酸素雰囲気において温度４００℃にて３０分保持することにより、正方晶から斜方晶へ相変態させて、斜方晶の結晶格子を持つＹ１２３超電導膜とした。Ｙ１２３超電導膜の厚みは、２．８μｍであった。 Next, using an electric furnace, the precursor film-forming tape-like substrate was subjected to a temperature gradient of 3 in an argon atmosphere at a pressure of 1 atm (1.01 × 10 5 Pa) mixed with oxygen having a concentration of 0.09%. The temperature was raised from 500 ° C. to 780 ° C. at ℃ / min and held at 780 ° C. for 90 minutes to obtain a Y123 superconducting tape wire with a Y123 superconducting film having a tetragonal crystal lattice (no intermediate heat treatment) . Then, it is cooled to 400 ° C., and held at a temperature of 400 ° C. for 30 minutes in a pure oxygen atmosphere at a pressure of 1 atm (1.01 × 10 5 Pa), thereby transforming the phase from tetragonal to orthorhombic. A Y123 superconducting film having a crystal lattice was formed. The thickness of the Y123 superconducting film was 2.8 μm.

このようにして得られた比較例２のＹ１２３超電導テープ線材について、その所定寸法の切断片を温度７７．３Ｋの液体窒素に浸漬して、自己磁場中で１．０μＶ／ｃｍの電界基準を用いて、単位幅当たりの臨界電流Ｉｃを測定した。   The Y123 superconducting tape wire of Comparative Example 2 thus obtained was immersed in liquid nitrogen at a temperature of 77.3 K using a cut piece having a predetermined size, and an electric field reference of 1.0 μV / cm was used in a self magnetic field. Thus, the critical current Ic per unit width was measured.

その結果、臨界電流Ｉｃは、１２６Ａ／ｃｍという低い値にとどまった。また、Ｙ１２３超電導膜には、その表面を電子顕微鏡で観察したところ、ボイドやクラックが多数観察された。   As a result, the critical current Ic remained as low as 126 A / cm. Further, when the surface of the Y123 superconducting film was observed with an electron microscope, many voids and cracks were observed.

次に、実施例１について説明する。   Next, Example 1 will be described.

第１工程について説明する。前記比較例１と同様に、厚み０．０５０ｍｍ，幅１０ｍｍ，長さ１０ｍの複合基板上に塗布膜（フッ素を含む）が形成された原料塗布テープ状基板１を２本作製した。   The first step will be described. As in Comparative Example 1, two raw material coated tape-like substrates 1 each having a coating film (including fluorine) formed on a composite substrate having a thickness of 0.050 mm, a width of 10 mm, and a length of 10 m were produced.

次に、第２工程について説明する。第２工程は前述した図１に示すプラズマ処理装置を用いて実施した。反応容器１１の概略寸法は、高さ４００ｍｍ×奥行き５００ｍｍ×長さ１０００ｍｍである。電極１８，１９はステンレス鋼製であり、電極１８，１９間の距離は１５ｍｍである。   Next, the second step will be described. The second step was performed using the plasma processing apparatus shown in FIG. The approximate dimensions of the reaction vessel 11 are height 400 mm × depth 500 mm × length 1000 mm. The electrodes 18 and 19 are made of stainless steel, and the distance between the electrodes 18 and 19 is 15 mm.

前記２本のうち、まず、１本の前記原料塗布テープ状基板１を使用し、原料塗布テープ状基板１が巻回された送り出しロール１６から引き出されたテープ状基板先端部を、電極１８，１９間を経て巻き取りロール１７に固定して、プラズマ処理装置に原料塗布テープ状基板１をセットした。   Of the two, first, one of the raw material-coated tape-like substrates 1 is used, and the tip of the tape-like substrate drawn out from the feed roll 16 around which the raw material-coated tape-like substrate 1 is wound is connected to the electrodes 18, After 19 spaces, the material was fixed to the take-up roll 17 and the raw material-coated tape-like substrate 1 was set in the plasma processing apparatus.

反応容器１１内にＨ２ガスとＨｅガスを導入して、Ｈ２ガス分圧：７Ｔｏｒｒ（７×１３３．３Ｐａ）、Ｈｅガス分圧：６９３Ｔｏｒｒ（６９３×１３３．３Ｐａ）となるように各ガス流量を調整した。この導入ガスによる７００Ｔｏｒｒ（７００×１３３．３Ｐａ）の圧力下、電極１８，１９間に周波数１３．５６ＭＨｚ,電圧３５０Ｖの高周波電力を供給して、グロー放電プラズマを発生させた。また、ヒータ２１により、原料塗布テープ状基板１の温度が２００℃になるように原料塗布テープ状基板１を加熱するようにした。 H 2 gas and He gas are introduced into the reaction vessel 11 so that the H 2 gas partial pressure is 7 Torr (7 × 133.3 Pa) and the He gas partial pressure is 693 Torr (693 × 133.3 Pa). The flow rate was adjusted. Under the pressure of 700 Torr (700 × 133.3 Pa) with the introduced gas, high-frequency power with a frequency of 13.56 MHz and a voltage of 350 V was supplied between the electrodes 18 and 19 to generate glow discharge plasma. Further, the raw material-coated tape-like substrate 1 was heated by the heater 21 so that the temperature of the raw-material-coated tape-like substrate 1 was 200 ° C.

そして、プラズマ発生領域Ｐを原料塗布テープ状基板１を通過させることで加熱処理することにより、前駆体膜形成テープ状基板（前駆体膜形成テープ線材）１’を作製した。この場合、原料塗布テープ状基板１の走行速度を変えることにより、プラズマ中で加熱処理される時間（プラズマ発生領域Ｐに原料塗布テープ状基板１が進入し退出するまでの時間）を変化させて、それぞれの条件で前駆体膜形成テープ状基板１’を作製した。なお、処理中に発生したフッ化水素ガスは、水に溶かした後、強アルカリと中和反応させることにより処理した。   Then, the precursor film-forming tape-shaped substrate (precursor film-forming tape wire) 1 ′ was produced by heat treatment by passing the plasma generation region P through the raw material-coated tape-shaped substrate 1. In this case, by changing the traveling speed of the raw material-coated tape-like substrate 1, the time during which heat treatment is performed in plasma (time until the raw material-coated tape-like substrate 1 enters and exits the plasma generation region P) is changed. A precursor film-formed tape-like substrate 1 ′ was produced under each condition. The hydrogen fluoride gas generated during the treatment was dissolved in water and then treated by neutralizing with a strong alkali.

続いて、前記２本のうち、他の１本の原料塗布テープ状基板１については、これをヒータ２１による加熱なし（室温）とした点以外は、前記と同様にして前駆体膜形成テープ状基板１’を作製した。   Subsequently, with respect to the other raw material-coated tape-like substrate 1 out of the two, the precursor film-forming tape-like shape is the same as described above except that this is not heated by the heater 21 (room temperature). A substrate 1 ′ was produced.

次に、第３工程について説明する。電気炉を使用し、濃度０．０９％の酸素が混合された圧力１ａｔｍのアルゴン雰囲気中において、前記のようにして得られた各前駆体膜形成テープ状基板１’を、温度勾配５℃／ｍｉｎで２００℃から７６０℃まで昇温し、７６０℃にて９０分保持することにより、結晶格子が正方晶のＹ１２３超電導膜が形成されたＹ１２３超電導テープ線材を得た。その後、４００℃まで冷却し、圧力１ａｔｍ（１．０１×１０５Ｐａ）で純酸素雰囲気において温度４００℃にて３０分保持することにより、正方晶から斜方晶へ相変態させて、斜方晶の結晶格子を持つＹ１２３超電導膜とした。Ｙ１２３超電導膜の厚みは、２．８μｍであった。 Next, the third step will be described. Using an electric furnace, each precursor film-formed tape-like substrate 1 ′ obtained as described above was placed in an argon atmosphere with a pressure of 1 atm mixed with 0.09% oxygen and a temperature gradient of 5 ° C. / The temperature was raised from 200 ° C. to 760 ° C. for min and held at 760 ° C. for 90 minutes to obtain a Y123 superconducting tape wire in which a Y123 superconducting film having a tetragonal crystal lattice was formed. Then, it is cooled to 400 ° C., and held at a temperature of 400 ° C. for 30 minutes in a pure oxygen atmosphere at a pressure of 1 atm (1.01 × 10 5 Pa), thereby transforming the phase from tetragonal to orthorhombic. A Y123 superconducting film having a crystal lattice was formed. The thickness of the Y123 superconducting film was 2.8 μm.

そして、このようにして得られた実施例１のＹ１２３超電導テープ線材について、比較例１と同様にして、その所定寸法の切断片を温度７７．３Ｋの液体窒素に浸漬して、自己磁場中で１．０μＶ／ｃｍの電界基準を用いて、単位幅当たりの臨界電流Ｉｃを測定した。その結果を図３に示す。図３は、実施例１で作製したＹ１２３超電導テープ線材についてのプラズマ処理時間と単位幅当たりの臨界電流との関係を示すグラフ図である。   And about the Y123 superconducting tape wire material of Example 1 obtained in this way, the cut piece of the predetermined dimension was immersed in liquid nitrogen at a temperature of 77.3 K in the same manner as in Comparative Example 1, and in a self-magnetic field. The critical current Ic per unit width was measured using an electric field standard of 1.0 μV / cm. The result is shown in FIG. FIG. 3 is a graph showing the relationship between the plasma processing time and the critical current per unit width for the Y123 superconducting tape wire produced in Example 1.

図３に示すように、原料塗布テープ状基板１のプラズマによる加熱処理に際し、ヒータ２１によって原料塗布テープ状基板１を２００℃に加熱したもの（図３において黒い四角印で示す）では、プラズマ処理時間が３分間のときに臨界電流Ｉｃが最大値に達して５０１Ａ／ｃｍが得られており、比較例１に比べて４倍以上という高い臨界電流Ｉｃが得られた。また、Ｙ１２３超電導膜には、その表面を電子顕微鏡で観察したところ、ボイドやクラックは全く観察されなかった。   As shown in FIG. 3, when the raw material-coated tape-like substrate 1 is heat-treated with plasma, the material 21 is heated to 200 ° C. by the heater 21 (indicated by black square marks in FIG. 3). When the time was 3 minutes, the critical current Ic reached the maximum value to obtain 501 A / cm, and a critical current Ic that was 4 times or more higher than that of Comparative Example 1 was obtained. Further, when the surface of the Y123 superconducting film was observed with an electron microscope, no voids or cracks were observed.

また、図３に示すようにヒータ２１による原料塗布テープ状基板１の加熱を行わないもの（図３において黒い菱形印で示す）でも、原料塗布テープ状基板１を２００℃に加熱したもの比べて、同じ値の臨界電流を得るために必要な時間が長くなるものの、５分間のプラズマ処理にて３６８Ａ／ｃｍという臨界電流Ｉｃが得られ、比較例１に比べて３倍以上という高い臨界電流Ｉｃが得られた。また、Ｙ１２３超電導膜には、その表面を電子顕微鏡で観察したところ、ボイドやクラックは全く観察されなかった。   Further, as shown in FIG. 3, even when the material-coated tape-like substrate 1 is not heated by the heater 21 (indicated by the black rhombus marks in FIG. 3), the material-coated tape-like substrate 1 is heated to 200 ° C. The critical current Ic of 368 A / cm is obtained by the plasma treatment for 5 minutes, although the time required to obtain the same value of critical current is long, and the critical current Ic is three times higher than that of Comparative Example 1. was gotten. Further, when the surface of the Y123 superconducting film was observed with an electron microscope, no voids or cracks were observed.

次に、実施例２について説明する。   Next, Example 2 will be described.

第１工程について説明する。前記比較例１と同様に、厚み０．０５０ｍｍ，幅１０ｍｍ，長さ１０ｍの複合基板上に塗布膜（フッ素を含む）が形成された原料塗布テープ状基板１を作製した。   The first step will be described. Similarly to Comparative Example 1, a raw material coated tape-like substrate 1 in which a coating film (including fluorine) was formed on a composite substrate having a thickness of 0.050 mm, a width of 10 mm, and a length of 10 m was produced.

次に、第２工程について説明する。第２工程は、前記図２の、ドラム状回転電極２２を備えたプラズマ処理装置を用いて実施した。反応容器１１の概略寸法は、高さ４００ｍｍ×奥行き５００ｍｍ×長さ１０００ｍｍである。ドラム状回転電極２２及び対向ロール２３は、ステンレス鋼製である。ドラム状回転電極２２の直径（外径）は、１５０ｍｍである。 Next, the second step will be described. The second step of FIG. 2, was performed by using the plasma processing apparatus having a drum-shaped rotating electrode 22. The approximate dimensions of the reaction vessel 11 are height 400 mm × depth 500 mm × length 1000 mm. The drum-shaped rotating electrode 22 and the counter roll 23 are made of stainless steel. The diameter (outer diameter) of the drum-shaped rotating electrode 22 is 150 mm.

原料塗布テープ状基板１が巻回された送り出しロール１６から引き出されたテープ状基板先端部を、対向ロール２３を経て巻き取りロール１７に固定して、プラズマ処理装置に原料塗布テープ状基板１をセットした。   The tip of the tape-shaped substrate drawn out from the feed roll 16 on which the raw material-coated tape-shaped substrate 1 is wound is fixed to the take-up roll 17 via the opposing roll 23, and the raw-material-coated tape-shaped substrate 1 is attached to the plasma processing apparatus. I set it.

反応容器１１内にＨ２ガスとＨｅガスを導入して、Ｈ２ガス分圧：７Ｔｏｒｒ（７×１３３．３Ｐａ）、Ｈｅガス分圧：６９３Ｔｏｒｒ（６９３×１３３．３Ｐａ）となるように各ガス流量を調整した。この導入ガスによる７００Ｔｏｒｒ（７００×１３３．３Ｐａ）の圧力下、ドラム状回転電極２２に周波数１３．５６ＭＨｚ,電圧３５０Ｖの高周波電力を供給するとともに、ドラム状回転電極２２を１５００回／分の速度で回転させて、ドラム状回転電極２２と対向ロール２３間にグロー放電プラズマを発生させた。また、加熱用ランプ２４により、原料塗布テープ状基板１の温度が２００℃になるように原料塗布テープ状基板１を加熱するようにした。 H 2 gas and He gas are introduced into the reaction vessel 11 so that the H 2 gas partial pressure is 7 Torr (7 × 133.3 Pa) and the He gas partial pressure is 693 Torr (693 × 133.3 Pa). The flow rate was adjusted. Under the pressure of 700 Torr (700 × 133.3 Pa) by the introduced gas, high-frequency power having a frequency of 13.56 MHz and a voltage of 350 V is supplied to the drum-shaped rotating electrode 22 and the drum-shaped rotating electrode 22 is supplied at a rate of 1500 times / minute. By rotating, glow discharge plasma was generated between the drum-shaped rotating electrode 22 and the opposing roll 23. Further, the raw material coated tape substrate 1 was heated by the heating lamp 24 so that the temperature of the raw material coated tape substrate 1 was 200 ° C.

そして、プラズマ発生領域Ｐを原料塗布テープ状基板１を通過させることで加熱処理することにより、前駆体膜形成テープ状基板（前駆体膜形成テープ線材）１’を作製した。この場合、プラズマ中で加熱処理される時間（プラズマ発生領域Ｐに原料塗布テープ状基板１が進入し退出するまでの時間）が３分となるように、原料塗布テープ状基板１の走行速度を調節した。なお、処理中に発生したフッ化水素ガスは、水に溶かした後、強アルカリと中和反応させることにより処理した。   Then, the precursor film-forming tape-shaped substrate (precursor film-forming tape wire) 1 ′ was produced by heat treatment by passing the plasma generation region P through the raw material-coated tape-shaped substrate 1. In this case, the traveling speed of the raw material-coated tape-like substrate 1 is set so that the time for the heat treatment in plasma (the time until the raw material-coated tape-like substrate 1 enters and exits the plasma generation region P) is 3 minutes. Adjusted. The hydrogen fluoride gas generated during the treatment was dissolved in water and then treated by neutralizing with a strong alkali.

次に、第３工程について説明する。電気炉を使用し、濃度０．０９％の酸素が混合された圧力１ａｔｍ（１．０１×１０５Ｐａ）のアルゴン雰囲気中において、前記のようにして得られた前駆体膜形成テープ状基板１’を、温度勾配５℃／ｍｉｎで２００℃から７６０℃まで昇温し、７６０℃にて９０分保持することにより、結晶格子が正方晶のＹ１２３超電導膜が形成されたＹ１２３超電導テープ線材を得た。その後、４００℃まで冷却し、圧力１ａｔｍ（１．０１×１０５Ｐａ）で純酸素雰囲気において温度４００℃にて３０分保持することにより、正方晶から斜方晶へ相変態させて、斜方晶の結晶格子を持つＹ１２３超電導膜とした。Ｙ１２３超電導膜の厚みは、２．８μｍであった。 Next, the third step will be described. Precursor film-forming tape-like substrate 1 obtained as described above in an argon atmosphere at a pressure of 1 atm (1.01 × 10 5 Pa) mixed with 0.09% oxygen using an electric furnace. Is heated from 200 ° C. to 760 ° C. at a temperature gradient of 5 ° C./min and held at 760 ° C. for 90 minutes to obtain a Y123 superconducting tape wire in which a Y123 superconducting film having a tetragonal crystal lattice is formed. It was. Then, it is cooled to 400 ° C., and held at a temperature of 400 ° C. for 30 minutes in a pure oxygen atmosphere at a pressure of 1 atm (1.01 × 10 5 Pa), thereby transforming the phase from tetragonal to orthorhombic. A Y123 superconducting film having a crystal lattice was formed. The thickness of the Y123 superconducting film was 2.8 μm.

そして、このようにして得られた実施例２のＹ１２３超電導テープ線材について、比較例１と同様にして、その所定寸法の切断片を温度７７．３Ｋの液体窒素に浸漬して、自己磁場中で１．０μＶ／ｃｍの電界基準を用いて、単位幅当たりの臨界電流Ｉｃを測定した。 And about the Y123 superconducting tape wire material of Example 2 obtained in this way, the cut piece of the predetermined dimension was immersed in liquid nitrogen at a temperature of 77.3 K in the same manner as in Comparative Example 1, and in a self-magnetic field. The critical current Ic per unit width was measured using an electric field standard of 1.0 μV / cm.

その結果、前記実施例１よりもさらに高い５４５Ａ／ｃｍという臨界電流Ｉｃが得られた。また、Ｙ１２３超電導膜には、その表面を電子顕微鏡で観察したところ、ボイドやクラックは全く観察されなかった。   As a result, a higher critical current Ic of 545 A / cm than that of Example 1 was obtained. Further, when the surface of the Y123 superconducting film was observed with an electron microscope, no voids or cracks were observed.

ここで、先の実施例１で用いたプラズマ処理装置の平行平板型の対向電極１８，１９では、プラズマ中のストリーマが電極１８，１９のある一部分に集中する傾向があって、それが原因でプラズマが空間的に不均一になり、原料塗布テープ状基板１がそのようなプラズマ発生領域を通過することで、形成されるＹ１２３前駆体膜が高エネルギーで微小なダメージを受けることになる。   Here, in the parallel plate type counter electrodes 18 and 19 of the plasma processing apparatus used in the first embodiment, the streamer in the plasma tends to concentrate on a part of the electrodes 18 and 19, which is the cause. The plasma is spatially non-uniform, and the raw material-coated tape-like substrate 1 passes through such a plasma generation region, so that the formed Y123 precursor film is damaged with high energy.

これに対し、ドラム状回転電極２２では、ストリーマが発生してもプラズマ発生電極としては常にフレッシュな面が提供されるので、そのストリーマが回転電極２２のある一部分に集中することがなく、高エネルギーによるダメージの少ない良質なＹ１２３前駆体が形成されるためと考えられる。   On the other hand, since the drum-shaped rotating electrode 22 always provides a fresh surface as a plasma generating electrode even if a streamer is generated, the streamer does not concentrate on a certain part of the rotating electrode 22 and high energy This is considered to be because a good-quality Y123 precursor with little damage due to the formation of the Y123 precursor is formed.

次に、参考例２について説明する。 Next, Reference Example 2 will be described.

第１工程について説明する。前記参考例１と同様に、厚み０．０５０ｍｍ，幅１０ｍｍ，長さ１０ｍの複合基板上にフッ素を含まない塗布膜が形成された原料塗布テープ状基板１を２本作製した。 The first step will be described. In the same manner as in Reference Example 1 , two raw material coated tape-like substrates 1 each having a coating film containing no fluorine on a composite substrate having a thickness of 0.050 mm, a width of 10 mm, and a length of 10 m were produced.

次に、第２工程について説明する。第２工程は、前記実施例２と同じプラズマ処理装置を用いて実施した。前記２本のうち、まず、１本の前記原料塗布テープ状基板１をプラズマ処理装置にセットした。   Next, the second step will be described. The second step was performed using the same plasma processing apparatus as in Example 2. Of the two, first, the one raw material coated tape substrate 1 was set in a plasma processing apparatus.

反応容器１１内にＨｅガスを導入して、Ｈｅガスによる圧力が７００Ｔｏｒｒ（７００×１３３．３Ｐａ）となるように流量を調整した。圧力７００Ｔｏｒｒ（７００×１３３．３Ｐａ）のＨｅガス雰囲気下、ドラム状回転電極２２に周波数１３．５６ＭＨｚ,電圧３５０Ｖの高周波電力を供給するとともに、ドラム状回転電極２２を１５００回／分の速度で回転させて、ドラム状回転電極２２と対向ロール２３間にグロー放電プラズマを発生させた。また、加熱用ランプ２４により、原料塗布テープ状基板１の温度が２００℃になるように原料塗布テープ状基板１を加熱するようにした。   He gas was introduced into the reaction vessel 11 and the flow rate was adjusted so that the pressure of He gas was 700 Torr (700 × 133.3 Pa). In a He gas atmosphere at a pressure of 700 Torr (700 × 133.3 Pa), high-frequency power with a frequency of 13.56 MHz and a voltage of 350 V is supplied to the drum-shaped rotating electrode 22 and the drum-shaped rotating electrode 22 is rotated at a speed of 1500 times / minute. Thus, glow discharge plasma was generated between the drum-shaped rotating electrode 22 and the opposing roll 23. Further, the raw material coated tape substrate 1 was heated by the heating lamp 24 so that the temperature of the raw material coated tape substrate 1 was 200 ° C.

そして、プラズマ発生領域Ｐを原料塗布テープ状基板１を通過させることで加熱処理することにより、前駆体膜形成テープ状基板（前駆体膜形成テープ線材）１’を作製した。この場合、原料塗布テープ状基板１の走行速度を変えることにより、プラズマ中で加熱処理される時間（プラズマ発生領域Ｐに原料塗布テープ状基板１が進入し退出するまでの時間）を変化させて、それぞれの条件で前駆体膜形成テープ状基板１’を作製した。   Then, the precursor film-forming tape-shaped substrate (precursor film-forming tape wire) 1 ′ was produced by heat treatment by passing the plasma generation region P through the raw material-coated tape-shaped substrate 1. In this case, by changing the traveling speed of the raw material-coated tape-like substrate 1, the time during which heat treatment is performed in plasma (time until the raw material-coated tape-like substrate 1 enters and exits the plasma generation region P) is changed. A precursor film-formed tape-like substrate 1 ′ was produced under each condition.

続いて、前記２本のうち、他の１本の原料塗布テープ状基板１については、これを加熱用ランプ２４よる加熱なし（室温）とした点以外は、前記と同様にして前駆体膜形成テープ状基板１’を作製した。   Subsequently, with respect to the other one of the two raw material coated tape-like substrates 1, the precursor film formation was performed in the same manner as described above except that this was not heated by the heating lamp 24 (room temperature). A tape-shaped substrate 1 ′ was produced.

次に、第３工程について説明する。電気炉を使用し、濃度０．０９％の酸素が混合された圧力１ａｔｍ（１．０１×１０５Ｐａ）のアルゴン雰囲気中において、前記のようにして得られた各前駆体膜形成テープ状基板１’を、温度勾配５℃／ｍｉｎで２００℃から７８０℃まで昇温し、７８０℃にて９０分保持することにより、結晶格子が正方晶のＹ１２３超電導膜が形成されたＹ１２３超電導テープ線材を得た。その後、４００℃まで冷却し、圧力１ａｔｍ（１．０１×１０５Ｐａ）で純酸素雰囲気において温度４００℃にて３０分保持することにより、正方晶から斜方晶へ相変態させて、斜方晶の結晶格子を持つＹ１２３超電導膜とした。Ｙ１２３超電導膜の厚みは、２．８μｍであった。 Next, the third step will be described. Each precursor film-formed tape-shaped substrate obtained as described above in an argon atmosphere at a pressure of 1 atm (1.01 × 10 5 Pa) mixed with 0.09% oxygen using an electric furnace 1 ′ was heated from 200 ° C. to 780 ° C. at a temperature gradient of 5 ° C./min, and held at 780 ° C. for 90 minutes to obtain a Y123 superconducting tape wire material in which a Y123 superconducting film having a tetragonal crystal lattice was formed. Obtained. Then, it is cooled to 400 ° C., and held at a temperature of 400 ° C. for 30 minutes in a pure oxygen atmosphere at a pressure of 1 atm (1.01 × 10 5 Pa), thereby transforming the phase from tetragonal to orthorhombic. A Y123 superconducting film having a crystal lattice was formed. The thickness of the Y123 superconducting film was 2.8 μm.

そして、このようにして得られた参考例２のＹ１２３超電導テープ線材について、比較例１と同様にして、その所定寸法の切断片を温度７７．３Ｋの液体窒素に浸漬して、自己磁場中で１．０μＶ／ｃｍの電界基準を用いて、単位幅当たりの臨界電流Ｉｃを測定した。その結果を図４に示す。図４は、参考例２で作製したＹ１２３超電導テープ線材についてのプラズマ処理時間と単位幅当たりの臨界電流との関係を示すグラフ図である。 And about the Y123 superconducting tape wire material of Reference Example 2 obtained in this way, the cut piece of the predetermined dimension was immersed in liquid nitrogen at a temperature of 77.3 K in the same manner as in Comparative Example 1, and in a self-magnetic field. The critical current Ic per unit width was measured using an electric field standard of 1.0 μV / cm. The result is shown in FIG. FIG. 4 is a graph showing the relationship between the plasma processing time and the critical current per unit width for the Y123 superconducting tape wire produced in Reference Example 2 .

図４に示すように、原料塗布テープ状基板１のプラズマによる加熱処理に際し、加熱用ランプ２４によって原料塗布テープ状基板１を２００℃に加熱したもの（図４において黒い四角印で示す）では、プラズマ処理時間が１．５分間のときに臨界電流Ｉｃが最大値に達して４８０Ａ／ｃｍが得られており、参考例１に比べて３．８倍以上という高い臨界電流Ｉｃが得られた。また、Ｙ１２３超電導膜には、その表面を電子顕微鏡で観察したところ、ボイドやクラックは全く観察されなかった。 As shown in FIG. 4, when the raw material-coated tape-like substrate 1 is heated by plasma, the material-coated tape-like substrate 1 is heated to 200 ° C. by the heating lamp 24 (indicated by black square marks in FIG. 4). When the plasma treatment time was 1.5 minutes, the critical current Ic reached the maximum value and 480 A / cm was obtained, and a high critical current Ic of 3.8 times or more compared to the reference example 1 was obtained. Further, when the surface of the Y123 superconducting film was observed with an electron microscope, no voids or cracks were observed.

また、図４に示すように加熱用ランプ２４による原料塗布テープ状基板１の加熱を行わないもの（図４において黒い菱形印で示す）でも、原料塗布テープ状基板１を２００℃に加熱したもの比べて、同じ値の臨界電流を得るために必要な時間が長くなるものの、５分間のプラズマ処理にて４７４Ａ／ｃｍという臨界電流Ｉｃが得られ、参考例１に比べて３．７倍以上という高い臨界電流Ｉｃが得られた。また、Ｙ１２３超電導膜には、その表面を電子顕微鏡で観察したところ、ボイドやクラックは全く観察されなかった。 In addition, as shown in FIG. 4, even when the raw material-coated tape-like substrate 1 is not heated by the heating lamp 24 (indicated by black rhombus marks in FIG. 4), the raw-material-coated tape-like substrate 1 is heated to 200 ° C. In comparison, although the time required to obtain the same value of critical current is longer, a critical current Ic of 474 A / cm is obtained by the plasma treatment for 5 minutes, which is 3.7 times or more that of Reference Example 1. A high critical current Ic was obtained. Further, when the surface of the Y123 superconducting film was observed with an electron microscope, no voids or cracks were observed.

なお、この参考例２ではプラズマ生成ガスとしてＨｅガスのみを用いたが、Ｏ２ガスを用いるようにしても、Ｈｅガスの場合と同様に、高い臨界電流Ｉｃが得られる。プラズマ中に酸素を含めることにより、原料塗布テープ状基板１の塗布膜中に存在する炭素は酸素と反応して炭酸ガスとして効果的に排除でき、プラズマ処理時間を短縮できるという効果がある。 In Reference Example 2 , only He gas is used as the plasma generation gas. However, even when O 2 gas is used, a high critical current Ic is obtained as in the case of He gas. By including oxygen in the plasma, the carbon present in the coating film of the raw material coated tape-like substrate 1 reacts with oxygen and can be effectively excluded as carbon dioxide gas, and the plasma processing time can be shortened.

また、本発明では、基板として、ハステロイ基板上にＧｄ２Ｚｒ２Ｏ７及びＣｅＯ２を順次形成した前記複合基板の他に、配向性Ｎｉ合金基板の上にＣｅＯ２、イットリウム安定化ジルコニア（ＹＳＺ）、ＣｅＯ２を順次形成した複合基板を用いるようにしてもよい。また、プラズマ処理装置の電極間に、高周波電力に代えて、直流電力をパルス状に供給する（例えばパルス幅１μｓ、周期１００μｓ）ようにしてもよい。 In the present invention, in addition to the composite substrate in which Gd 2 Zr 2 O 7 and CeO 2 are sequentially formed on a Hastelloy substrate, CeO 2 and yttrium stabilized zirconia (YSZ) are formed on an oriented Ni alloy substrate. Alternatively, a composite substrate in which CeO2 is sequentially formed may be used. Further, instead of the high frequency power, DC power may be supplied in a pulse form between the electrodes of the plasma processing apparatus (for example, a pulse width of 1 μs and a period of 100 μs).

また、前記実施例１，２及び参考例２では、金属有機酸塩として、トリフルオロ酢酸塩、ナフテン酸塩、イソノナン酸塩、プロピオン酸塩を用い、溶媒として２−オクタノンや酢酸ｎ−ブチルを用いたが、金属有機酸塩と溶媒との混合溶液として、トリフルオロ酢酸塩、ジクロロ酢酸塩、ナフテン酸塩、オクチル酸塩、ネオデカン酸塩、イソノナン酸塩、プロピオン酸塩、酢酸塩及びアセチルアセトナート系錯体のうちいずれか１種以上と、有機溶媒との混合溶液を用いても、実施例１，２及び参考例２と同等の効果が得られる。 In Examples 1 and 2 and Reference Example 2 , trifluoroacetate, naphthenate, isononanoate, and propionate were used as metal organic acid salts, and 2-octanone and n-butyl acetate were used as solvents. As a mixed solution of metal organic acid salt and solvent, trifluoroacetate, dichloroacetate, naphthenate, octylate , neodecanoate, isononanoate, propionate, acetate and acetylacetate Even when any one or more of the nate-based complexes and a mixed solution of an organic solvent are used, the same effects as in Examples 1 and 2 and Reference Example 2 can be obtained.

本発明の方法の実施に用いるプラズマ処理装置の構成を概略的に示す図である。It is a figure which shows roughly the structure of the plasma processing apparatus used for implementation of the method of this invention. 本発明の方法の実施に用いる別のプラズマ処理装置の構成を概略的に示す図である。It is a figure which shows schematically the structure of another plasma processing apparatus used for implementation of the method of this invention. 実施例１で作製したＹ１２３超電導テープ線材についてのプラズマ処理時間と単位幅当たりの臨界電流との関係を示すグラフ図である。It is a graph which shows the relationship between the plasma processing time about the Y123 superconducting tape wire produced in Example 1, and the critical current per unit width. 参考例２で作製したＹ１２３超電導テープ線材についてのプラズマ処理時間と単位幅当たりの臨界電流との関係を示すグラフ図である。It is a graph which shows the relationship between the plasma processing time about the Y123 superconducting tape wire produced by the reference example 2 , and the critical current per unit width.

符号の説明Explanation of symbols

１…原料塗布テープ状基板
１’…前駆体膜形成テープ状基板（前駆体膜形成テープ線材）
１１…反応容器
１２…ガス導入管
１３…排気管
１４…高周波電源
１５…整合器
１６…送り出しロール
１７…巻き取りロール
１８…上部電極
１９…下部電極
２０…誘電体板
２１…ヒータ
２２…ドラム状回転電極
２３…対向ロール
２４…加熱用ランプ 1 ... Raw material coated tape substrate 1 '... Precursor film forming tape substrate (precursor film forming tape wire)
DESCRIPTION OF SYMBOLS 11 ... Reaction container 12 ... Gas introduction pipe 13 ... Exhaust pipe 14 ... High frequency power supply 15 ... Matching device 16 ... Sending roll 17 ... Winding roll 18 ... Upper electrode 19 ... Lower electrode 20 ... Dielectric plate 21 ... Heater 22 ... Drum form Rotating electrode 23 ... Opposite roll 24 ... Heating lamp

Claims (6)

テープ状基板上に、ＲＥＢａ２Ｃｕ３Ｏｙ（ＲＥは、Ｙ、Ｎｄ、Ｓｍ、Ｇｄ、Ｅｕ、Ｙｂ、Ｐｒ及びＨｏのうち少なくとも１種の元素、６．４≦ｙ≦７．０）系超電導体を構成する各金属元素を所定の組成比で含む金属有機酸塩を混合してなる原料溶液を塗布し、該原料溶液を乾燥して、原料塗布テープ状基板を作製する第１工程と、グロー放電プラズマ中を前記原料塗布テープ状基板を通過させることにより、前記超電導体の前駆体膜が形成された前駆体膜形成テープ状基板を得る第２工程と、得られた前記前駆体膜形成テープ状基板に前記超電導体を生成させる熱処理を施す第３工程とを備え、前記金属有機酸塩がフッ素を含むものであり、前記グロー放電プラズマのプラズマ生成ガスが水素を含むものであることを特徴とするＲＥ−Ｂａ−Ｃｕ−Ｏ系超電導テープ線材の製造方法。 REBa 2 Cu 3 O y (RE is at least one element of Y, Nd, Sm, Gd, Eu, Yb, Pr and Ho, 6.4 ≦ y ≦ 7.0) system on a tape-like substrate A first step of applying a raw material solution obtained by mixing metal organic acid salt containing each metal element constituting the superconductor at a predetermined composition ratio, and drying the raw material solution to produce a raw material-coated tape-like substrate; A second step of obtaining a precursor film-formed tape-like substrate on which the precursor film of the superconductor is formed by passing the raw material-coated tape-like substrate through glow discharge plasma, and the obtained precursor film And a third step of performing a heat treatment for generating the superconductor on the formed tape-shaped substrate , wherein the metal organic acid salt contains fluorine, and a plasma generation gas of the glow discharge plasma contains hydrogen. RE Ba-Cu-O based superconducting manufacturing method of the tape wire. 前記第２工程において、円筒状外周面を有する回転電極に高周波電力又は直流電力を供給して前記グロー放電プラズマを発生させることを特徴とする請求項１記載のＲＥ−Ｂａ−Ｃｕ−Ｏ系超電導テープ線材の製造方法。 In the second step, RE-Ba-Cu-O based superconducting according to claim 1, wherein the rotating electrode by supplying a high-frequency power or DC power, characterized in that for generating the glow discharge plasma having a cylindrical outer peripheral surface Tape wire manufacturing method. 前記第２工程において、前記原料塗布テープ状基板を加熱しながら、前記グロー放電プラズマ中を通過させることを特徴とする請求項１又は２記載のＲＥ−Ｂａ−Ｃｕ−Ｏ系超電導テープ線材の製造方法。 3. The RE-Ba-Cu-O-based superconducting tape wire according to claim 1 or 2 , wherein in the second step, the raw material-coated tape-like substrate is passed through the glow discharge plasma while being heated. Method. 請求項１、２又は３記載のＲＥ−Ｂａ−Ｃｕ−Ｏ系超電導テープ線材の製造方法における前記第２工程に用いられるプラズマ処理装置であって、グロー放電プラズマを発生させるための電極と、長尺の前記原料塗布テープ状基板を前記グロー放電プラズマ中を通過させ、該プラズマ中を通過させて得られた前記前駆体膜形成テープ状基板を引き取る搬送手段と、プラズマ生成ガスを導入するガス導入管を有するとともに、前記電極及び前記搬送手段を内部に収容する反応容器とを備えたことを特徴とするプラズマ処理装置。 A plasma processing apparatus used in the second step in the method for producing a RE-Ba-Cu-O-based superconducting tape wire according to claim 1, 2, or 3, comprising an electrode for generating glow discharge plasma, A carrier means for passing the raw material-coated tape-like substrate through the glow discharge plasma and taking the precursor film-forming tape-like substrate obtained by passing through the plasma, and a gas introduction for introducing a plasma generating gas A plasma processing apparatus comprising a tube and a reaction container that accommodates the electrode and the transfer means therein. 前記電極は、回転駆動され、円筒状外周面を有するドラム状の回転電極であることを特徴とする請求項４記載のプラズマ処理装置。 The plasma processing apparatus according to claim 4 , wherein the electrode is a drum-shaped rotating electrode that is driven to rotate and has a cylindrical outer peripheral surface. 前記反応容器内に、前記グロー放電プラズマへ搬送されている前記原料塗布テープ状基板を加熱する基板加熱手段を備えていることを特徴とする請求項４又は５記載のプラズマ処理装置。 6. The plasma processing apparatus according to claim 4, further comprising a substrate heating means for heating the raw material-coated tape-shaped substrate transported to the glow discharge plasma in the reaction vessel.
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