JP2012221922A - Raw material solution for formation of oxide superconducting thin film layer, oxide superconducting thin film layer, and oxide superconducting thin film wire material - Google Patents
Raw material solution for formation of oxide superconducting thin film layer, oxide superconducting thin film layer, and oxide superconducting thin film wire material Download PDFInfo
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Abstract
Description
本発明は、塗布熱分解法により高い超電導特性を有する酸化物超電導薄膜層の形成を可能とする酸化物超電導薄膜層形成用の原料溶液、前記原料溶液を用いて形成された酸化物超電導薄膜層、および前記酸化物超電導薄膜層が形成された酸化物超電導薄膜線材に関する。 The present invention relates to a raw material solution for forming an oxide superconducting thin film layer capable of forming an oxide superconducting thin film layer having high superconducting properties by a coating pyrolysis method, and an oxide superconducting thin film layer formed using the raw material solution And an oxide superconducting thin film wire on which the oxide superconducting thin film layer is formed.
液体窒素の温度で超電導性を有する高温超電導体の発見以来、ケーブル、限流器、マグネットなどの電力機器への応用を目指した高温超電導線材の開発が活発に行われている。中でも、基板上に酸化物超電導層を形成させた酸化物超電導薄膜線材が注目されている（例えば、特許文献１）。 Since the discovery of high-temperature superconductors that have superconductivity at the temperature of liquid nitrogen, development of high-temperature superconducting wires aimed at application to power devices such as cables, current limiters, and magnets has been actively conducted. Among these, an oxide superconducting thin film wire in which an oxide superconducting layer is formed on a substrate has attracted attention (for example, Patent Document 1).
酸化物超電導薄膜線材の製造方法の１つに、塗布熱分解法（Ｍｅｔａｌ Ｏｒｇａｎｉｃ Ｄｅｐｏｓｉｔｉｏｎ、略称：ＭＯＤ法）がある（特許文献１）。 One method for producing an oxide superconducting thin film wire is a coating pyrolysis method (Metal Organic Deposition, abbreviated as MOD method) (Patent Document 1).
この方法は、Ｙ（イットリウム）などのＲＥ（希土類元素）およびＢａ（バリウム）、Ｃｕ（銅）の各有機金属化合物（金属塩）を溶媒に溶解して製造された原料溶液（ＭＯＤ溶液）を基板に塗布して塗布膜を形成した後、例えば、５００℃付近で仮焼熱処理して、有機金属化合物を熱分解させ、熱分解した有機成分を除去することにより酸化物超電導薄膜の前駆体である仮焼膜を作製後、作製した仮焼膜をさらに高温（例えば７５０〜８００℃付近）で本焼熱処理することにより結晶化を行って、ＲＥＢａ２Ｃｕ３Ｏ７−Ｘで表されるＲＥ１２３超電導薄膜層を形成させて酸化物超電導薄膜線材を製造するものであり、主に真空中で製造される気相法（蒸着法、スパッタ法、パルスレーザ蒸着法等）に比較して製造設備が簡単で済み、また大面積や複雑な形状への対応が容易である等の特徴を有しているため、広く用いられている。 In this method, a raw material solution (MOD solution) produced by dissolving an RE (rare earth element) such as Y (yttrium) and an organometallic compound (metal salt) of Ba (barium) and Cu (copper) in a solvent. After forming the coating film by coating on the substrate, for example, by calcining heat treatment at around 500 ° C., the organometallic compound is thermally decomposed, and the thermally decomposed organic component is removed, thereby removing the precursor of the oxide superconducting thin film. After producing a certain calcined film, the produced calcined film is crystallized by subjecting the calcined film to a heat treatment at a higher temperature (for example, around 750 to 800 ° C.) to obtain RE123 represented by REBa 2 Cu 3 O 7-X. A superconducting thin film layer is formed to produce an oxide superconducting thin film wire. Compared with vapor phase methods (evaporation, sputtering, pulsed laser deposition, etc.) that are mainly produced in a vacuum, the production facilities are Easy, Because the response to a large area or a complicated shape has a characteristic equal is easy, it is widely used.
しかしながら、従来のＭＯＤ法を用いた酸化物超電導薄膜線材の製造においては、所定の組成で調製したＭＯＤ溶液を使用しているにも拘わらず、得られた酸化物超電導薄膜線材では所望する超電導特性に至っていないことがあった。 However, in the production of the oxide superconducting thin film wire using the conventional MOD method, the obtained oxide superconducting thin film wire has the desired superconducting properties despite using the MOD solution prepared with a predetermined composition. There were times when it was not reached.
このため、ＭＯＤ法を用いながらも、所望する高い超電導特性を有する酸化物超電導薄膜線材を製造することができる技術が望まれていた。 Therefore, there has been a demand for a technique that can produce an oxide superconducting thin film wire having desired high superconducting characteristics while using the MOD method.
本発明者は、上記課題の解決について検討するに際し、先ず、従来のＭＯＤ法を用いて形成された酸化物超電導薄膜層につき、分析を行ったところ、酸化物超電導薄膜層には、ＲＥ１２３の他に、ＲＥ２Ｂａ１Ｃｕ１Ｏ５（ＲＥ２１１）などの異相が形成されており、この異相の発生が、臨界電流密度Ｊｃを低下させ、臨界電流値Ｉｃの伸びを制限していることが分かった。 When examining the solution of the above problems, the present inventor first analyzed an oxide superconducting thin film layer formed by using the conventional MOD method. Further, it is understood that a different phase such as RE 2 Ba 1 Cu 1 O 5 (RE211) is formed, and the occurrence of this different phase decreases the critical current density Jc and limits the elongation of the critical current value Ic. It was.
次に、本発明者は、ＲＥ２１１の発生原因について、種々の実験、検討を行い、その結果、ＭＯＤ溶液の調製に原因があることが分かった。 Next, the present inventor conducted various experiments and studies on the cause of RE211 generation, and as a result, it was found that there was a cause in the preparation of the MOD solution.
即ち、従来のＭＯＤ法においては、所望する超電導薄膜の組成に合わせて、ＲＥ：Ｂａ：Ｃｕ＝１：２：３（モル比）の組成となるように各有機金属化合物を秤量し、溶媒に溶解することにより、原料溶液（ＭＯＤ溶液）を調製した後、配向金属基材上に形成された中間層の上に塗布し、仮焼熱処理、本焼熱処理を経て、ＲＥ１２３超電導薄膜層を形成していた。しかし、本焼熱処理の際、原料Ｂａの一部が中間層を構成する化合物と反応して消費されるため、ＲＥ１２３超電導薄膜層の形成に充分なＢａ量を確保することができず、原料ＹやＣｕの一部が、ＲＥ２１１やＣｕＯを生成する。そして、生成されたＲＥ２１１は、臨界電流密度Ｊｃを低下させるため、臨界電流値Ｉｃの伸びが制限されていた。 That is, in the conventional MOD method, each organometallic compound is weighed so as to have a composition of RE: Ba: Cu = 1: 2: 3 (molar ratio) according to the composition of the desired superconducting thin film, and used as a solvent. After preparing the raw material solution (MOD solution) by dissolution, it is applied on the intermediate layer formed on the oriented metal base material, and after undergoing calcination heat treatment and main heat treatment, the RE123 superconducting thin film layer is formed. It was. However, since a part of the raw material Ba reacts with the compound constituting the intermediate layer and is consumed during the main heat treatment, a sufficient amount of Ba for forming the RE123 superconducting thin film layer cannot be secured, and the raw material Y And a part of Cu produces | generates RE211 and CuO. Since the generated RE 211 reduces the critical current density Jc, the elongation of the critical current value Ic is limited.
具体的な一例としては、ＲＥとしてＹを用い、中間層としてＣｅＯ２を用いた場合、Ｙ１２３の形成と並行して、Ｙ２１１、ＢａＣｅＯ３、ＣｕＯが生成される。この内、Ｙ２１１はＪｃを大きく低下させるため、Ｉｃの伸びが制限される。 As a specific example, when Y is used as RE and CeO 2 is used as an intermediate layer, Y211, BaCeO 3 , and CuO are generated in parallel with the formation of Y123. Of these, Y211 greatly reduces Jc, so that the elongation of Ic is limited.
そこで、本発明者は、ＲＥ２１１を生成する余剰のＲＥが発生しないように、Ｂａの消費を見込んで、ＲＥの配合比率を低く抑えたＭＯＤ溶液を調製することに思い至り、適切なＲＥ量につき、さらに実験、検討を行った。 Accordingly, the present inventor has come up with the idea of preparing a MOD solution with a low RE blending ratio in anticipation of Ba consumption so as not to generate surplus RE that generates RE211. Further experiments and examinations were conducted.
この結果、ＭＯＤ溶液の調製における各原料の適切な比が、ＲＥ：Ｂａ：Ｃｕ＝Ｘ：２：３（０．８≦Ｘ＜１．０）であることが分かった。 As a result, it was found that an appropriate ratio of each raw material in the preparation of the MOD solution was RE: Ba: Cu = X: 2: 3 (0.8 ≦ X <1.0).
即ち、ＲＥの比率が０．８未満であると、ＲＥ２１１の形成は抑制されるものの、ＲＥの量が少なすぎるため、充分な量のＲＥ１２３を形成させることができない。このため、高い超電導特性の酸化物超電導薄膜線材を得ることができない。 That is, if the RE ratio is less than 0.8, formation of RE211 is suppressed, but the amount of RE is too small, and therefore a sufficient amount of RE123 cannot be formed. For this reason, an oxide superconducting thin film wire having high superconducting characteristics cannot be obtained.
一方、１以上であると、中間層を構成する化合物との反応に消費された残りのＢａ量に対してＲＥが過剰となるため、ＲＥ２１１の形成を抑制することができず、やはり、高い超電導特性の酸化物超電導薄膜線材を得ることができない。 On the other hand, if it is 1 or more, the RE becomes excessive with respect to the remaining amount of Ba consumed for the reaction with the compound constituting the intermediate layer, so that the formation of RE211 cannot be suppressed. A characteristic oxide superconducting thin film wire cannot be obtained.
本発明は、上記の知見に基づくものであり、請求項１に記載の発明は、
塗布熱分解法を用いて、配向金属基材上に形成された中間層の上に、酸化物超電導薄膜層を形成するに際して使用される酸化物超電導薄膜層形成用の原料溶液であって、
ＲＥ（希土類元素）およびＢａ（バリウム）、Ｃｕ（銅）の各有機金属化合物が、ＲＥ：Ｂａ：Ｃｕ＝Ｘ：２：３（０．８≦Ｘ＜１．０）の比率で、溶媒に溶解されている
ことを特徴とする酸化物超電導薄膜層形成用の原料溶液である。
The present invention is based on the above findings, and the invention according to claim 1
A raw material solution for forming an oxide superconducting thin film layer used in forming an oxide superconducting thin film layer on an intermediate layer formed on an oriented metal substrate using a coating pyrolysis method,
RE (rare earth element) and each organometallic compound of Ba (barium) and Cu (copper) are contained in a solvent at a ratio of RE: Ba: Cu = X: 2: 3 (0.8 ≦ X <1.0). It is a raw material solution for forming an oxide superconducting thin film layer, characterized by being dissolved.
本請求項の発明において、配向金属基材としては、２軸配向した配向金属基板が好ましく用いられ、具体的には、ＩＢＡＤ基板、Ｎｉ−Ｗ合金基板、ＳＵＳ等をベース金属としたクラッドタイプの金属基板等を挙げることができる。 In the present invention, a biaxially oriented oriented metal substrate is preferably used as the oriented metal substrate, and specifically, a clad type base metal made of IBAD substrate, Ni-W alloy substrate, SUS or the like. A metal substrate etc. can be mentioned.
中間層を形成する材料としては、酸化セリウム（ＣｅＯ２）、酸化イットリウム（Ｙ２Ｏ３）、イットリア安定化ジルコニア（ＹＳＺ）、チタン酸ストロンチウム（ＳｒＴｉＯ３）、酸化マグネシウム（ＭｇＯ）や、バリウムジルコネート（ＢａＺｒＯ３）、アルミン酸ランタン（ＬａＡｌＯ３）等を挙げることができる。 Materials for forming the intermediate layer include cerium oxide (CeO 2 ), yttrium oxide (Y 2 O 3 ), yttria stabilized zirconia (YSZ), strontium titanate (SrTiO 3 ), magnesium oxide (MgO), barium zirco Nate (BaZrO 3 ), lanthanum aluminate (LaAlO 3 ), and the like.
また、中間層は、一般的に、配向金属基材側から順に、種層（シード層）、拡散防止層（バリア層）、格子整合層（キャップ層）の３層構造で形成され、前記したＢａとの反応は、主にキャップ層で発生する。キャップ層には、格子整合性の面より、一般的に、ＣｅＯ２が用いられる。なお、ＬＳＭＯ、ＳＴＯなどをキャップ層に用いてもよい。なお、これらの中間層は、一般に、スパッタ法やＰＬＤ法などの気相法を用いて形成される。 Further, the intermediate layer is generally formed in a three-layer structure of a seed layer (seed layer), a diffusion prevention layer (barrier layer), and a lattice matching layer (cap layer) in order from the oriented metal substrate side. Reaction with Ba occurs mainly in the cap layer. CeO 2 is generally used for the cap layer from the viewpoint of lattice matching. Note that LSMO, STO, or the like may be used for the cap layer. These intermediate layers are generally formed using a vapor phase method such as a sputtering method or a PLD method.
請求項２に記載の発明は、
請求項１に記載の酸化物超電導薄膜層形成用の原料溶液を用いて形成されていることを特徴とする酸化物超電導薄膜層である。
The invention described in claim 2
An oxide superconducting thin film layer formed using the raw material solution for forming an oxide superconducting thin film layer according to claim 1.
前記したように、ＲＥの配合比率を低く抑えたＭＯＤ溶液を用いて形成された酸化物超電導薄膜層は、異相の発生が抑制されている。 As described above, in the oxide superconducting thin film layer formed using the MOD solution with the RE compounding ratio kept low, the occurrence of heterogeneous phases is suppressed.
請求項３に記載の発明は、
塗布熱分解法を用いて、配向金属基材上に形成された中間層の上に形成された酸化物超電導薄膜層であって、膜内にＲＥ２Ｂａ１Ｃｕ１Ｏ５相が形成されていないことを特徴とする酸化物超電導薄膜層である。
The invention according to claim 3
An oxide superconducting thin film layer formed on an intermediate layer formed on an oriented metal substrate using a coating pyrolysis method, in which a RE 2 Ba 1 Cu 1 O 5 phase is formed in the film There is no oxide superconducting thin film layer.
異相であるＲＥ２Ｂａ１Ｃｕ１Ｏ５（ＲＥ２１１）が形成されていない酸化物超電導薄膜層は、臨界電流密度Ｊｃが低下せず、臨界電流値Ｉｃの伸びを充分に得ることができる。 The oxide superconducting thin film layer in which the different phase RE 2 Ba 1 Cu 1 O 5 (RE211) is not formed does not decrease the critical current density Jc, and can sufficiently obtain the elongation of the critical current value Ic.
このような酸化物超電導薄膜層は、前記の酸化物超電導薄膜層形成用の原料溶液を用いることにより、得ることができる。 Such an oxide superconducting thin film layer can be obtained by using the raw material solution for forming the oxide superconducting thin film layer.
請求項４に記載の発明は、
配向金属基材上に形成された中間層の上に、請求項２または請求項３に記載の酸化物超電導薄膜層が形成されていることを特徴とする酸化物超電導薄膜線材である。
The invention according to claim 4
An oxide superconducting thin film wire comprising the oxide superconducting thin film layer according to claim 2 or 3 formed on an intermediate layer formed on an oriented metal substrate.
異相であるＲＥ２１１の形成がない酸化物超電導薄膜層が形成された酸化物超電導薄膜線材は、臨界電流密度Ｊｃが低下しないため、高いＩｃの酸化物超電導薄膜線材を提供することができる。 Since the oxide superconducting thin film wire formed with the oxide superconducting thin film layer without the formation of RE211 which is a different phase does not decrease the critical current density Jc, it can provide a high Ic oxide superconducting thin film wire.
本発明によれば、ＭＯＤ法を用いて、異相であるＲＥ２１１の形成がない酸化物超電導薄膜層を得て、所望する高い超電導特性を有する酸化物超電導薄膜線材を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the oxide superconducting thin film layer which does not form RE211 which is a different phase can be obtained using the MOD method, and the oxide superconducting thin film wire which has the desired high superconducting characteristic can be provided.
以下、本発明を実施例に基づいて説明する。 Hereinafter, the present invention will be described based on examples.
以下に、有機金属化合物の組成を変えたＭＯＤ溶液を用いて、配向金属基材上に中間層を設けた配向金属基板の上に、ＭＯＤ法により、Ｙ１２３酸化物超電導薄膜層を形成させたＹ１２３酸化物超電導薄膜線材を例に挙げ、本発明をより具体的に説明する。 Y123 oxide superconducting thin film layer was formed by the MOD method on an oriented metal substrate having an intermediate layer provided on an oriented metal substrate using a MOD solution having a different composition of the organometallic compound. The present invention will be described more specifically by taking an oxide superconducting thin film wire as an example.
１．Ｙ１２３酸化物超電導薄膜線材の構成
図１は、Ｙ１２３酸化物超電導薄膜線材の構成を模式的に示す断面図である。図１に示すように、配向金属基板３は、配向金属基材１上に、２１、２２、２３の３層からなる中間層２を設けて構成されている。そして、配向金属基板３の上に、Ｙ１２３酸化物超電導薄膜層４が形成されて、Ｙ１２３酸化物超電導薄膜線材が構成されている。
1. Configuration of Y123 Oxide Superconducting Thin Film Wire FIG. 1 is a cross-sectional view schematically showing a configuration of a Y123 oxide superconducting thin film wire. As shown in FIG. 1, the alignment metal substrate 3 is configured by providing an intermediate layer 2 composed of three layers 21, 22, and 23 on an alignment metal substrate 1. And the Y123 oxide superconducting thin film layer 4 is formed on the oriented metal substrate 3, and the Y123 oxide superconducting thin film wire is comprised.
２．Ｙ１２３酸化物超電導薄膜線材の作製
以下の手順により、実施例および比較例のＹ１２３酸化物超電導薄膜線材を作製した。
2. Production of Y123 oxide superconducting thin film wire Y123 oxide superconducting thin film wires of Examples and Comparative Examples were produced by the following procedure.
（１）配向金属基材の準備
配向金属基材１としては、２軸配向したＮｉ合金基板を用いた。
(1) Preparation of Oriented Metal Base Material As the oriented metal base material 1, a biaxially oriented Ni alloy substrate was used.
（２）中間層の作製
前記配向金属基材１の上に、スパッタ法を用いて、配向金属基板１側から、Ｙ２Ｏ３／ＹＳＺ／ＣｅＯ２の順で、３層からなる中間層２を形成して、配向金属基板３とした。なお、第１層目２１のＹ２Ｏ３は１２０ｎｍ、第２層目２２のＹＳＺは４４０ｎｍ、第３層目（キャップ層）２３のＣｅＯ２は６０ｎｍの厚さで成膜した。
(2) Production of intermediate layer Intermediate layer 2 consisting of three layers in the order of Y 2 O 3 / YSZ / CeO 2 on the oriented metal substrate 1 from the oriented metal substrate 1 side using the sputtering method. The alignment metal substrate 3 was formed. The Y 2 O 3 of the first layer 21 was 120 nm, the YSZ of the second layer 22 was 440 nm, and the CeO 2 of the third layer (cap layer) 23 was 60 nm.
（３）酸化物超電導薄膜層の作製
次に、中間層２の上に、ＭＯＤ法を用いて、以下の要領で、１２００ｎｍ厚の酸化物超電導薄膜層を作製した。
(3) Production of oxide superconducting thin film layer Next, an oxide superconducting thin film layer having a thickness of 1200 nm was produced on the intermediate layer 2 using the MOD method in the following manner.
（イ）ＭＯＤ溶液の作製
Ｙ、Ｂａ、Ｃｕの各アセチルアセトナート塩から出発してＹ：Ｂａ：Ｃｕ＝Ｘ：２：３の比率（モル比）で合成し、アルコールを溶媒としたＭＯＤ溶液を作製した。なお、Ｘは、表１の各実施例および比較例に示すＹの組成比である。
(A) Preparation of MOD Solution Starting from each acetylacetonate salt of Y, Ba, and Cu, the MOD solution was synthesized at a ratio (molar ratio) of Y: Ba: Cu = X: 2: 3 using alcohol as a solvent. Was made. X is a composition ratio of Y shown in each example and comparative example of Table 1.
（ロ）塗膜作製工程
形成された中間層２の上に、前記ＭＯＤ溶液を塗布し、乾燥させて塗膜を作製した。
(B) Coating film preparation process The MOD solution was applied onto the formed intermediate layer 2 and dried to prepare a coating film.
（ハ）仮焼熱処理工程
塗膜が形成された基板を、大気圧の空気雰囲気下、５００℃、１２０分間の仮焼熱処理を行い、Ｙ１２３仮焼膜を作製した。
(C) Calcination Heat Treatment Step The substrate on which the coating film was formed was subjected to calcination heat treatment at 500 ° C. for 120 minutes in an air atmosphere at atmospheric pressure to produce a Y123 calcination film.
前記塗膜作製工程と仮焼熱処理工程とを８回繰り返し、１２００ｎｍ厚のＹ１２３仮焼膜を作製した。 The coating film preparation step and the calcining heat treatment step were repeated 8 times to produce a 1200 nm thick Y123 calcined film.
（ニ）本焼熱処理工程
作製されたＹ１２３仮焼膜に対し、アルゴン・酸素混合ガス（酸素濃度１００ｐｐｍ）雰囲気下で、８００℃、９０分間の本焼熱処理を行い、１２００ｎｍ厚のＹ１２３超電導薄膜層４を作製し、各実施例および比較例のＹ１２３酸化物超電導薄膜線材を得た。
(D) Main heat treatment step The produced Y123 calcined film is subjected to a main heat treatment at 800 ° C. for 90 minutes in an argon / oxygen mixed gas (oxygen concentration: 100 ppm) atmosphere, and a Y123 superconducting thin film layer having a thickness of 1200 nm. 4 was obtained, and the Y123 oxide superconducting thin film wire of each Example and Comparative Example was obtained.
３．Ｙ１２３酸化物超電導薄膜線材の評価
得られた各実施例および比較例のＹ１２３酸化物超電導薄膜線材について、以下の評価を行った。
3. Evaluation of Y123 oxide superconducting thin film wire The following evaluations were performed on the obtained Y123 oxide superconducting thin film wires of Examples and Comparative Examples.
（１）Ｙ２１１相の発生率
各実施例および比較例のＹ１２３酸化物超電導薄膜線材（各１０個）について、それぞれ、Ｙ１２３酸化物超電導薄膜層の表面をＳＥＭにより観察して、Ｙ２１１相の発生状況を確認し、Ｙ２１１相が発生しているＹ１２３酸化物超電導薄膜線材の割合（Ｙ２１１発生率）を求めた。結果を表１に示す。
(1) Occurrence rate of Y211 phase About the Y123 oxide superconducting thin film wire (each 10 pieces) of each example and comparative example, the surface of the Y123 oxide superconducting thin film layer was observed by SEM, respectively, and the occurrence state of Y211 phase The Y123 oxide superconducting thin film wire ratio (Y211 generation rate) in which the Y211 phase was generated was determined. The results are shown in Table 1.
また、Ｙの組成比とＹ２１１発生率との関係を図２に示す。 FIG. 2 shows the relationship between the Y composition ratio and the Y211 generation rate.
（２）超電導特性（Ｊｃ）
実施例および比較例で得られたＹ１２３酸化物超電導薄膜線材の超電導特性として、７７Ｋ、自己磁場下におけるＪｃを測定した。結果を表１に示す。
(2) Superconducting properties (Jc)
As the superconducting properties of the Y123 oxide superconducting thin film wires obtained in the examples and comparative examples, 77 K, Jc under a self-magnetic field was measured. The results are shown in Table 1.
（３）考察
表１、図２より、Ｙの組成比が１．０以上であるか否かによって、Ｙ１２３酸化物超電導薄膜線材におけるＹ２１１発生率が大きく相違していることが分かる。即ち、Ｙの組成比が１．０未満の実施例１〜３の場合、全てのＹ１２３酸化物超電導薄膜線材にＹ２１１が発生せず、一方、Ｙの組成比が１．０以上の比較例１〜３の場合、全てのＹ１２３酸化物超電導薄膜線材にＹ２１１が発生している。そして、これに伴い、Ｊｃも大きく相違している。
(3) Consideration From Table 1 and FIG. 2, it can be seen that the Y211 generation rate in the Y123 oxide superconducting thin film wire is greatly different depending on whether or not the composition ratio of Y is 1.0 or more. That is, in Examples 1 to 3 in which the Y composition ratio is less than 1.0, Y211 does not occur in all Y123 oxide superconducting thin film wires, while the Y composition ratio is 1.0 or more. In the case of? 3, Y211 is generated in all the Y123 oxide superconducting thin film wires. Along with this, Jc is also greatly different.
なお、表１には示していないが、本発明者は、Ｙの組成比が０．８未満、例えば０．７５の場合、全てのＹ１２３酸化物超電導薄膜線材にＹ２１１の発生は見られないものの、Ｊｃは０．０ＭＡ／ｃｍ２となり、実施例１〜３に比べ、低下していることを確認している。これは、Ｙの組成比が低すぎ、生成されるＹ１２３結晶自体が少なくなったものと思われる。 Although not shown in Table 1, when the Y composition ratio is less than 0.8, for example, 0.75, the generation of Y211 is not observed in all Y123 oxide superconducting thin film wires. , Jc is 0.0 MA / cm 2 , which is confirmed to be lower than Examples 1-3. This is presumably because the Y composition ratio was too low and the produced Y123 crystal itself was reduced.
次に、実施例１および比較例１で得られたＹ１２３酸化物超電導薄膜層の表面のＳＥＭ写真を図３に示す。図３において、（ａ）は実施例１、（ｂ）は比較例１である。図３より、Ｙの組成比が適切なＭＯＤ溶液を用いて形成された実施例１のＹ１２３酸化物超電導薄膜層では、Ｙ２１１相が形成されていなく、一方、Ｙの組成比が過剰なＭＯＤ溶液を用いて形成された比較例１のＹ１２３酸化物超電導薄膜層では、細長い形状のＹ２１１が多数形成されていることが分かる。 Next, the SEM photograph of the surface of the Y123 oxide superconducting thin film layer obtained in Example 1 and Comparative Example 1 is shown in FIG. In FIG. 3, (a) is Example 1, and (b) is Comparative Example 1. From FIG. 3, in the Y123 oxide superconducting thin film layer of Example 1 formed using a MOD solution with an appropriate Y composition ratio, the Y211 phase was not formed, while the Y composition ratio was excessive. It can be seen that in the Y123 oxide superconducting thin film layer of Comparative Example 1 formed using, a large number of elongated Y211 are formed.
以上より、Ｙの組成比Ｘが、０．８≦Ｘ＜１．０であるＭＯＤ溶液を用いることにより、異相であるＹ２１１の発生が抑制されて、Ｊｃが向上したＹ１２３酸化物超電導薄膜線材を作製できることが分かる。 As described above, by using a MOD solution in which the Y composition ratio X is 0.8 ≦ X <1.0, the generation of Y211 which is a different phase is suppressed, and the Y123 oxide superconducting thin film wire with improved Jc is obtained. It can be seen that it can be produced.
以上、本発明を実施の形態に基づき説明したが、本発明は上記の実施の形態に限定されるものではない。本発明と同一および均等の範囲内において、上記の実施の形態に対して種々の変更を加えることが可能である。 As mentioned above, although this invention was demonstrated based on embodiment, this invention is not limited to said embodiment. Various modifications can be made to the above-described embodiment within the same and equivalent scope as the present invention.
１ 配向金属基材
２ 中間層
２１ 第１層目中間層
２２ 第２層目中間層
２３ 第３層目中間層
３ 配向金属基板
４ Ｙ１２３酸化物超電導薄膜層
DESCRIPTION OF SYMBOLS 1 Oriented metal base material 2 Intermediate layer 21 1st layer intermediate layer 22 2nd layer intermediate layer 23 3rd layer intermediate layer 3 Oriented metal substrate 4 Y123 oxide superconducting thin film layer
Claims (4)
ＲＥ（希土類元素）およびＢａ（バリウム）、Ｃｕ（銅）の各有機金属化合物が、ＲＥ：Ｂａ：Ｃｕ＝Ｘ：２：３（０．８≦Ｘ＜１．０）の比率で、溶媒に溶解されている
ことを特徴とする酸化物超電導薄膜層形成用の原料溶液。 A raw material solution for forming an oxide superconducting thin film layer used in forming an oxide superconducting thin film layer on an intermediate layer formed on an oriented metal substrate using a coating pyrolysis method,
RE (rare earth element) and each organometallic compound of Ba (barium) and Cu (copper) are contained in a solvent at a ratio of RE: Ba: Cu = X: 2: 3 (0.8 ≦ X <1.0). A raw material solution for forming an oxide superconducting thin film layer, characterized by being dissolved.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101429553B1 (en) | 2012-01-17 | 2014-09-22 | 주식회사 서남 | Superconducting wire and method of forming the same |
| WO2019098417A1 (en) * | 2017-11-16 | 2019-05-23 | 주식회사 서남 | Ceramic wire manufacturing method and manufacturing equipment therefor |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05208898A (en) * | 1991-06-14 | 1993-08-20 | Siemens Ag | Production of high-temperature superconductive component |
| WO2004038816A1 (en) * | 2002-10-23 | 2004-05-06 | Hamamatsu Foundation For Science And Technology Promotion | Oxide superconductor thin film element |
| JP2007115562A (en) * | 2005-10-21 | 2007-05-10 | Internatl Superconductivity Technology Center | Tape-shaped rare-earth group oxide superconductor and its manufacturing method |
| JP2007115561A (en) * | 2005-10-21 | 2007-05-10 | Internatl Superconductivity Technology Center | Tape-shaped rare-earth group oxide superconductor and its manufacturing method |
| JP2007188756A (en) * | 2006-01-13 | 2007-07-26 | Internatl Superconductivity Technology Center | Rare earth based tape shape oxide superconductor |
-
2011
- 2011-04-14 JP JP2011090178A patent/JP2012221922A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05208898A (en) * | 1991-06-14 | 1993-08-20 | Siemens Ag | Production of high-temperature superconductive component |
| WO2004038816A1 (en) * | 2002-10-23 | 2004-05-06 | Hamamatsu Foundation For Science And Technology Promotion | Oxide superconductor thin film element |
| JP2007115562A (en) * | 2005-10-21 | 2007-05-10 | Internatl Superconductivity Technology Center | Tape-shaped rare-earth group oxide superconductor and its manufacturing method |
| JP2007115561A (en) * | 2005-10-21 | 2007-05-10 | Internatl Superconductivity Technology Center | Tape-shaped rare-earth group oxide superconductor and its manufacturing method |
| JP2007188756A (en) * | 2006-01-13 | 2007-07-26 | Internatl Superconductivity Technology Center | Rare earth based tape shape oxide superconductor |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101429553B1 (en) | 2012-01-17 | 2014-09-22 | 주식회사 서남 | Superconducting wire and method of forming the same |
| WO2019098417A1 (en) * | 2017-11-16 | 2019-05-23 | 주식회사 서남 | Ceramic wire manufacturing method and manufacturing equipment therefor |
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