JPH0764679B2 - Method for producing ceramics superconductor thin film - Google Patents
Method for producing ceramics superconductor thin filmInfo
- Publication number
- JPH0764679B2 JPH0764679B2 JP62200630A JP20063087A JPH0764679B2 JP H0764679 B2 JPH0764679 B2 JP H0764679B2 JP 62200630 A JP62200630 A JP 62200630A JP 20063087 A JP20063087 A JP 20063087A JP H0764679 B2 JPH0764679 B2 JP H0764679B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- substrate
- ceramics superconductor
- superconductor thin
- substance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
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
Landscapes
- Chemical Vapour Deposition (AREA)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は基体上に化学蒸着法によりセラミックス超電導
体薄膜を製造する方法に関する。TECHNICAL FIELD The present invention relates to a method for producing a ceramics superconductor thin film on a substrate by a chemical vapor deposition method.
化学蒸着法（以下CVD法と略記）は、必要な元素を含む
原料を加熱しそこから発生する気体元素を反応管中に導
いて適当な温度で基体上に析出・反応させて所定の化合
物を形成する方法で、特に薄膜の製造に適した方法であ
る。ところが、例えばＹ−Ba−Cu−Ｏ系の超電導体の薄
膜を製造する場合、上記超電導体の構成元素であるY,B
a,Cu,Oはそれぞれ蒸気圧が異なるため、原料を同一の温
度で加熱したのでは、所定の組成の化合物即ちY1Ba2Cu3
O7-δ（δ≒0.1〜0.5）を得ることができず、臨界電流
密度（以下Jcと略記）等の特性の低いものとなり、また
所定の組成のものを得ようとした場合、構成元素中に蒸
気圧が極端に低いBa等の元素があると成膜時間がその元
素の蒸発速度に律速され製造に長時間を要し実用的でな
くなる等の問題がある。The chemical vapor deposition method (hereinafter abbreviated as CVD method) heats a raw material containing necessary elements, introduces a gas element generated from the raw material into a reaction tube, and deposits and reacts on a substrate at an appropriate temperature to form a predetermined compound. It is a method of forming and is particularly suitable for manufacturing a thin film. However, for example, when a thin film of a Y-Ba-Cu-O-based superconductor is manufactured, Y, B, which are the constituent elements of the superconductor, are used.
Since a, Cu, and O have different vapor pressures, if the raw materials were heated at the same temperature, a compound with a predetermined composition, that is, Y 1 Ba 2 Cu 3
O 7- δ (δ ≈ 0.1 to 0.5) cannot be obtained, and the characteristics such as critical current density (hereinafter abbreviated as J c ) are low, and when a composition of a predetermined composition is obtained, the composition If there is an element such as Ba having an extremely low vapor pressure among the elements, there is a problem that the film formation time is controlled by the evaporation rate of the element, the manufacturing takes a long time, and is not practical.
本発明はかかる状況に鑑みなされたもので、その目的と
するところは、CVD法により基体上にJCの高いセラミッ
クス超電導体の薄膜を効率よく製造する方法を提供する
ことにある。即ち本発明は、基体上に化学蒸着法により
セラミックス超電導体薄膜を製造するにあたり、予め基
体表面にセラミックス超電導体を構成する少なくとも１
種の元素又は該元素を含有する物質層を形成し、ついで
この物質層をなす物質を活性化する処理を行い、この後
セラミックス超電導体薄膜を形成することを特徴とする
ものである。The present invention has been made in view of such circumstances, and an object thereof is to provide a method for efficiently producing a thin film of a ceramic superconductor having a high J C on a substrate by a CVD method. That is, according to the present invention, when a ceramics superconductor thin film is manufactured on a substrate by a chemical vapor deposition method, at least one ceramics superconductor is previously formed on the substrate surface.
It is characterized in that a seed element or a substance layer containing the element is formed, a treatment for activating the substance forming the substance layer is performed, and then a ceramics superconductor thin film is formed.
本発明は、Ｙ−Ba−Cu−Ｏ系、Ｙ−Ba−Sr−Cu−Ｏ系、
La−Sr−Cu−Ｏ系等のセラミックス超電導体の薄膜の製
造に適用される。本発明にていう基体には安定化ジルコ
ニア、アルミナ、SrTiO3等からなる任意形状の成形体が
用いられ、この基体表面には、予めセラミックス超電導
体の構成元素のうち蒸気圧の低いBaのような元素又はそ
の化合物が形成せしめられるものであるが、この形成の
させ方としては基体としてこれらの構成元素又はその化
合物が被覆されたものを用いることにより形成させる他
に、基体に前処理としてこれらの構成元素又はその化合
物を被覆することにより形成させてもよい。また形成さ
せられた物質層をなす物質を活性化する処理を行うこと
により基体上での酸化物超電導体の析出・反応が速やか
になされる。前記物質を活性化する処理法としては、活
性蒸着やプラズマ放電等により、前記物質をイオン化又
は励起状態する方法が用いられる。The present invention includes a Y-Ba-Cu-O system, a Y-Ba-Sr-Cu-O system,
It is applied to the production of thin films of ceramic superconductors such as La-Sr-Cu-O system. As the substrate in the present invention, a molded body of an arbitrary shape made of stabilized zirconia, alumina, SrTiO 3 or the like is used. An element or a compound thereof is formed, and as a method for forming this, in addition to forming it by using a substrate coated with these constituent elements or a compound thereof, it is possible to form the element by a pretreatment on the substrate. You may form by coating a constituent element or its compound. Further, by performing the treatment for activating the substance forming the formed substance layer, the deposition / reaction of the oxide superconductor on the substrate is promptly performed. As a treatment method for activating the substance, a method of ionizing or exciting the substance by active vapor deposition, plasma discharge or the like is used.
CVD法において、Baのような蒸気圧の低い元素を、予め
基体表面に被覆し活性化処理を行っておくので、セラミ
ックス超電導体の構成元素の析出に要する時間が大巾に
短縮される。In the CVD method, since an element having a low vapor pressure such as Ba is coated on the surface of the substrate in advance and activation treatment is performed, the time required for the deposition of the constituent elements of the ceramic superconductor can be greatly shortened.
以下に本発明を、基体上にＹ−Ba−Cu−Ｏ系セラミック
ス超電導体薄膜を製造する例にて具体的に説明する。Hereinafter, the present invention will be specifically described with reference to an example of manufacturing a Y-Ba-Cu-O ceramics superconductor thin film on a substrate.
実施例−１ CVD装置の反応管の一端側に気相発生用原料であるシク
ロペンタジエニル銅トリエチルリン及びアセチルアセト
ンイットリウムを配置し、これを170℃に加熱してCu及
びＹを蒸発させ、一方反応管の原料側の端部から50％Ar
＋50％O2のキャリアガスを導入しこれを他端からロータ
リーポンプで吸引した。反応管中央には、予め、金属Ba
を１μｍの厚さに真空蒸着法により付着させた25×25×
1mmの安定化Zr板を配置し、この安定化Zr板に付着させ
た金属Baにアルゴンプラズマ放電を印加して活性化処理
を行い、しかるのち、これを抵抗加熱により750℃に保
持し、この基体上に前記のキャリアガスで運ばれたCu,
Y,Oを析出させ、基体上のBaとの間で反応をおこさせ
て、厚さ２μｍのＹ−Ba−Cu−Ｏ系セラミックス超電導
体薄膜を得た。Example 1 Cyclopentadienyl copper triethyl phosphorus and yttrium acetylacetone, which are raw materials for vapor phase generation, are arranged on one end side of a reaction tube of a CVD apparatus, and this is heated to 170 ° C. to evaporate Cu and Y, while 50% Ar from the raw material end of the reaction tube
A carrier gas of + 50% O 2 was introduced, and this was sucked from the other end by a rotary pump. In the center of the reaction tube, metal Ba
25 × 25 × with a thickness of 1μm deposited by vacuum deposition
Arrange a 1 mm stabilizing Zr plate, apply an argon plasma discharge to the metal Ba attached to the stabilizing Zr plate to perform activation treatment, and then hold it at 750 ° C. by resistance heating, Cu carried by the carrier gas on the substrate,
Y and O were deposited and reacted with Ba on the substrate to obtain a Y-Ba-Cu-O-based ceramics superconductor thin film having a thickness of 2 μm.
比較例−１ 実施例−１において、安定化Zr板に付着させた金属Baに
活性化処理を行わなかった他は、実施例１と同じ方法に
よりＹ−Ba−Cu−Ｏ系セラミックス超電導体薄膜を得
た。Comparative Example-1 A Y-Ba-Cu-O-based ceramics superconductor thin film was prepared in the same manner as in Example 1 except that the activation treatment was not performed on the metal Ba deposited on the stabilized Zr plate. Got
比較例−２ 実施例−１で用いた気相発生用原料に更にアセチルアセ
トンバリウムを加え、基体には安定化ジルコニア板をそ
のまま用い、他は比較例−１と同じ方法によりＹ−Ba−
Cu−Ｏ系セラミックス超電導体薄膜を得た。Comparative Example-2 Acetylacetone barium was further added to the raw material for vapor phase generation used in Example-1, and a stabilized zirconia plate was used as a substrate as it was.
A Cu-O ceramics superconductor thin film was obtained.
上記３種の試料を酸素気流中で800℃12時間加熱し次い
で２℃/minの速度で冷却して、結晶構造と酸素量の調整
を行ったのち各々について臨界温度（TC）及びJCの測定
を行った。結果は、製造条件を併記して第１表に示し
た。The three types of samples were heated in an oxygen stream at 800 ° C for 12 hours and then cooled at a rate of 2 ° C / min to adjust the crystal structure and oxygen content, and then the critical temperature (T C ) and J C Was measured. The results are shown in Table 1 together with the production conditions.
第１表より明らかなように本発明方法品（No.1）は、比
較例方法品（No.2,3）に較べてTc、Jcとも高い値を示し
ている。これは、Zr板に付着させた金属Baをプラズマ放
電により活性化させた為である。 As is clear from Table 1, the method product of the present invention (No. 1) shows higher values for both Tc and Jc than the comparative method products (No. 2, 3). This is because the metal Ba attached to the Zr plate was activated by plasma discharge.
比較例方法品のNo.3は、所定の組成に対しBa濃度が低か
ったためTCが液体窒素温度（77K）未満となり、従ってJ
Cは、77Kにおいて零、又4.2Kの液体ヘリウム温度におい
ても極めて低い値となった。尚、本発明において基体と
セラミックス超電導体間に介在される層（基体上に形成
される層）は、例えばBaのようにＹ−Ba−Cu−Ｏ系セラ
ミックス超電導体の構成元素単独でもよく、又BaCo3やB
aO等の化合物を用いてもよい。又上記元素又は化合物の
被覆層を活性化する方法としては、5000V程度の高電圧
を印加する方法等も適用される。No. 3 of the comparative example method product had a low Ba concentration for a given composition, so T C was below the liquid nitrogen temperature (77K), and therefore J
C was zero at 77K and extremely low at a liquid helium temperature of 4.2K. In the present invention, the layer interposed between the substrate and the ceramics superconductor (layer formed on the substrate) may be a single constituent element of the Y-Ba-Cu-O-based ceramics superconductor, such as Ba, Also BaCo 3 and B
A compound such as aO may be used. Further, as a method of activating the coating layer of the above-mentioned element or compound, a method of applying a high voltage of about 5000 V or the like is also applied.
以上述べたように本発明によれば基体上に、TCが液体窒
素温度以上で且つJCの高いセラミックス超電導体の薄膜
が効率よく得られるので、工業上顕著な効果を奏する。As described above, according to the present invention, since a thin film of a ceramics superconductor having T C equal to or higher than the liquid nitrogen temperature and high J C can be efficiently obtained on the substrate, an industrially remarkable effect is exhibited.
Claims (2)
電導体薄膜を製造するにあたり、予め基体表面にセラミ
ックス超電導体を構成する少なくとも１種の元素又は該
元素を含有する物質層を形成し、ついでこの物質層をな
す物質を活性化する処理を行い、この後セラミックス超
電導体薄膜を形成することを特徴とするセラミックス超
電導体薄膜の製造方法。1. When a ceramics superconductor thin film is produced on a substrate by a chemical vapor deposition method, at least one element constituting the ceramics superconductor or a substance layer containing the element is formed on the surface of the substrate in advance. A method for producing a ceramics superconductor thin film, which comprises performing a treatment for activating a substance forming a material layer and thereafter forming a ceramics superconductor thin film.
バリウム元素又はバリウム元素を含有する物質であるこ
とを特徴とする特許請求の範囲第１項記載のセラミック
ス超電導体薄膜の製造方法。2. The method for producing a ceramics superconductor thin film according to claim 1, wherein the substance forming the substance layer formed on the surface of the substrate is a barium element or a substance containing a barium element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62200630A JPH0764679B2 (en) | 1987-08-11 | 1987-08-11 | Method for producing ceramics superconductor thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62200630A JPH0764679B2 (en) | 1987-08-11 | 1987-08-11 | Method for producing ceramics superconductor thin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6443926A JPS6443926A (en) | 1989-02-16 |
| JPH0764679B2 true JPH0764679B2 (en) | 1995-07-12 |
Family
ID=16427576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62200630A Expired - Fee Related JPH0764679B2 (en) | 1987-08-11 | 1987-08-11 | Method for producing ceramics superconductor thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0764679B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2575442B2 (en) * | 1988-02-04 | 1997-01-22 | 株式会社フジクラ | Method for producing oxide-based superconducting wire |
| JPH0623960Y2 (en) * | 1991-05-16 | 1994-06-22 | 株式会社町田製作所 | Optical inspection probe |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63279515A (en) * | 1987-05-08 | 1988-11-16 | Fujikura Ltd | Superconductor structure |
| JP2506798B2 (en) * | 1987-07-29 | 1996-06-12 | 松下電器産業株式会社 | Superconductor |
-
1987
- 1987-08-11 JP JP62200630A patent/JPH0764679B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6443926A (en) | 1989-02-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |