JPH01246371A - Manufacture of oxide superconducting film - Google Patents
Manufacture of oxide superconducting filmInfo
- Publication number
- JPH01246371A JPH01246371A JP63019557A JP1955788A JPH01246371A JP H01246371 A JPH01246371 A JP H01246371A JP 63019557 A JP63019557 A JP 63019557A JP 1955788 A JP1955788 A JP 1955788A JP H01246371 A JPH01246371 A JP H01246371A
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- cuo
- superconducting
- layer
- cuo layer
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000000758 substrate Substances 0.000 claims abstract description 34
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 3
- 229910002480 Cu-O Inorganic materials 0.000 claims abstract 2
- 239000010408 film Substances 0.000 claims description 10
- 239000010409 thin film Substances 0.000 claims description 6
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 150000002602 lanthanoids Chemical class 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical group 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 9
- 239000013078 crystal Substances 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052593 corundum Inorganic materials 0.000 abstract description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 5
- 150000004703 alkoxides Chemical class 0.000 abstract description 3
- 229910002370 SrTiO3 Inorganic materials 0.000 abstract description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 abstract 1
- 238000000034 method Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000002887 superconductor Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、各種の素子に適用可能な、酸化物超伝導膜の
作製方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing an oxide superconducting film that can be applied to various devices.
［従来技術］
現在、超伝導膜の作製技術としてプラズマ溶射法、蒸着
法およびスパッタ法などのような気相法、スクリーン法
およびスビーナ法などのように基板の上に超伝導材料を
塗布する方法が検討されている。[Prior art] At present, superconducting film manufacturing techniques include vapor phase methods such as plasma spraying, vapor deposition, and sputtering, and methods of applying superconducting material onto a substrate such as screen method and subina method. is being considered.
［発明が解決しようとする課題］
しかしながら、これらの方法はそれぞれいくつかの問題
点を有している。[Problems to be Solved by the Invention] However, each of these methods has several problems.
例えば、蒸着法およびスパッタ法で作った膜の組成は原
料の組成とは異なることが多く、また、膜形成後加熱処
理を行う必要がある。For example, the composition of films made by vapor deposition and sputtering methods often differs from the composition of the raw materials, and it is also necessary to perform heat treatment after film formation.
また、スクリーン法では、例えばＬｎＢａ２Ｃｕ３０７
−×（ＬｎはＹまたはランタノイド元素）超伝導膜をセ
ラミックス基板上に形成すると、電流の流れる結晶軸。In addition, in the screen method, for example, LnBa2Cu307
-x (Ln is Y or a lanthanide element) When a superconducting film is formed on a ceramic substrate, the crystal axis through which current flows.
、ｂを基板に対して平行に配向させることができず、こ
のため臨界電流値を大きくとることができないという問
題点があった。, b cannot be oriented parallel to the substrate, and therefore a large critical current value cannot be obtained.
さらに、Ａｌ２Ｏ３あるいはＳｒＴｉＯ３を基板とする
場合、加熱処理するとぎに塗布した超伝導材料と基板材
料との反応により組成ずれを起こし、超伝導相を形成す
ることが出来ないなどという問題も生じ、使用すること
のできる基板も限られていた。Furthermore, when Al2O3 or SrTiO3 is used as a substrate, there is a problem that a composition shift occurs due to a reaction between the applied superconducting material and the substrate material after heat treatment, making it impossible to form a superconducting phase. There were also a limited number of substrates that could be used.
本発明の目的は、上述の問題点を解決し、スクリーン法
、スプレー法およびスピーチ法等によって、基板上に超
伝導材料を塗布し、これを加熱処理する際に結晶配向を
起こさせ、かつ、超伝導材料を塗布する基板の種類を広
げることができる酸化物超伝導膜の作製方法を提供する
ものである。An object of the present invention is to solve the above-mentioned problems, to coat a superconducting material on a substrate by a screen method, a spray method, a speech method, etc., and to cause crystal orientation when heat-treating the superconducting material, and The present invention provides a method for producing an oxide superconducting film that can expand the types of substrates on which superconducting materials can be applied.
［課題を解決するための手段］
このような目的を達成するために、本発明は、基板上に
ＣｕＯ層を少なくとも一層形成し、ＣｕＯ層上にＬｎ−
Ｒ−Ｃｕ−０系（ＬｎはＹまたはランタノイド元素、Ｒ
はアルカリ土類金属元素）からなる酸化物薄膜を形成す
ることを特徴とするものである。[Means for Solving the Problem] In order to achieve such an object, the present invention forms at least one CuO layer on a substrate, and Ln-
R-Cu-0 system (Ln is Y or a lanthanoid element, R
is characterized by forming an oxide thin film consisting of an alkaline earth metal element).
［作 用］
本発明は、基板上にＣｕＯ層を少なくとも一層形成後、
その上にＬｎ−Ｒ−Ｃｕ−０系からなる酸化物薄膜を形
成することを特徴とするもので、この方法により、以下
の利点が明らかになった。[Function] In the present invention, after forming at least one CuO layer on a substrate,
This method is characterized by forming an oxide thin film of Ln-R-Cu-0 system thereon, and the following advantages have been revealed by this method.
■ ＣｕＯ層を最初に形成することにより、ＣｕＯが多
い超伝導材料組成になり、このため、イツトリウム安定
化ジルコニア（ＹＳＺ）等のようなセラミックス基板上
で超伝導薄膜を、Ｃ軸が基板に垂直になる方向に配向さ
せることができる。■ Forming the CuO layer first results in a CuO-rich superconducting material composition, which allows the superconducting thin film to be deposited on a ceramic substrate such as yttrium stabilized zirconia (YSZ) with the C axis perpendicular to the substrate. It can be oriented in the direction of
このように配向する理由は必ずしも明確ではないが、Ｃ
ｕが多い組成では、配向する傾向の強いことが本発明者
により確認されている。すなわち、ＣｕＯ，ＢａＯおよ
びＹ２Ｏ３の融点がそれぞれ１２３２℃、 １９２３℃
および２４４０℃であることを考えると、ＣｕＯが最も
早く反応を起こし、配向の原因になるものと思われる。The reason for this orientation is not necessarily clear, but C
The present inventor has confirmed that a composition with a large amount of u has a strong tendency to be oriented. That is, the melting points of CuO, BaO, and Y2O3 are 1232°C and 1923°C, respectively.
Considering that the temperature is 2440° C., it is thought that CuO reacts most quickly and becomes the cause of orientation.
■従来、塗布などの手段で薄膜を形成すると、超伝導材
料であるＬｎ−Ｒ−Ｃｕ−０と基板との反応が起こるた
めに用いることができなかった基板でも、ＣｕＯ層を基
板表面に設けることにより、これが保護膜として働き、
その上に超伝導相を形成で参る。■ Conventionally, forming a thin film by means such as coating could not be used because a reaction between the superconducting material Ln-R-Cu-0 and the substrate occurred, but a CuO layer is provided on the surface of the substrate. This acts as a protective film,
A superconducting phase is then formed on top of that.
［実施例］ 以下、図面を参照して本発明の詳細な説明する。[Example] Hereinafter, the present invention will be described in detail with reference to the drawings.
衷Ｊ０江１
まず、ＣｕのアルコキシドであるＣｕ （ＯＣ２Ｈ５）
２にエチレングリコールを添加してペースト状にした
ものを、スクリーン法によってＹＳＺ基板上に塗布し、
これを温度を変えて加熱処理した。第１図はｙｓｚ基板
とＣｕＯとの反応状態を、Ｘ線回折装置で測定した結果
を示す。ここでは、特にＣｕＯとＹｓｚ基板との反応性
を見るため、ＹＳＺとＣｕＯの回折ピークが近接してい
る部分を図示している。加熱処理の温度を上げるにした
がい、ＣｕＯピークに比較してＹＳＺのピークが増加し
ていることから、ＹＳＺ基板とＣｕＯの反応が進行して
いることを示唆している。しかし、９５０℃以下の高温
処理では、ＹＳＺとＣｕＯのピークは別々に分離して現
れており、望ましくない化合物は形成されていないこと
がわかった。First, Cu alkoxide of Cu (OC2H5)
A paste made by adding ethylene glycol to 2 was applied onto the YSZ substrate by a screen method.
This was heat treated at different temperatures. FIG. 1 shows the results of measuring the reaction state between the ysz substrate and CuO using an X-ray diffraction device. Here, in order to particularly examine the reactivity between CuO and the Ysz substrate, a portion where the diffraction peaks of YSZ and CuO are close to each other is illustrated. As the heat treatment temperature increases, the YSZ peak increases compared to the CuO peak, suggesting that the reaction between the YSZ substrate and CuO is progressing. However, in the high-temperature treatment at 950° C. or lower, the peaks of YSZ and CuO appeared separately, indicating that no undesirable compounds were formed.
次に、ＹＢａ２Ｃｕ３０Ｘの組成になるように秤量した
超伝導材料をＣｕＯ＠の上に、さらに塗布した。これを
９５０℃３０分の条件で加熱処理したサンプルのＸ線回
折図を、第２図に示す。本図において（）内の数字は結
晶の面指数を表している。第２図から明らかなように、
基板上にＹＢａ２Ｃｕ３０７−Ｘの結晶がＣ軸配向して
いることがわかる。これらの膜の抵抗の温度変化を、四
端子法により測定し、Ｔｃ”８５Ｋ”？？低抵抗なるこ
とを確認した。Next, a superconducting material weighed so as to have a composition of YBa2Cu30X was further applied onto the CuO@. An X-ray diffraction diagram of a sample heat-treated at 950° C. for 30 minutes is shown in FIG. In this figure, the numbers in parentheses represent the surface index of the crystal. As is clear from Figure 2,
It can be seen that the crystals of YBa2Cu307-X are C-axis oriented on the substrate. The temperature change in the resistance of these films was measured using the four-terminal method, and Tc "85K"? ? It was confirmed that the resistance was low.
衷１０辻ス
まず、Ａｌ２Ｏ，基板（純度９２ｔ）の上にＣｕのアル
コキシドＣｕ （ＯＣＪｓ） ２を塗布し、８５０℃で
加熱処理し、基板表面にＣｕＯ層を形成した。次に、そ
の上にＹＢａ２Ｃｕ３０．ペーストを塗布し、９５０℃
で３０分間加熱処理した。第３図は、このサンプルのＸ
線回折を示す。本図においては、超伝導結晶相ＹＢａ２
Ｃｕ３０ｙ−ｘのみのピークが見られる。First, Cu alkoxide Cu (OCJs) 2 was applied onto an Al2O substrate (purity 92t) and heat treated at 850°C to form a CuO layer on the substrate surface. Next, YBa2Cu30. Apply paste and heat to 950℃
The mixture was heat-treated for 30 minutes. Figure 3 shows the X of this sample.
Shows line diffraction. In this figure, the superconducting crystal phase YBa2
A peak of only Cu30y-x is seen.
一方、Ａｌ２Ｏ３基板に直接ＹＢａ２Ｃｕ、、Ｏｘペー
ストを塗布し、９５０℃で加熱処理したサンプルのＸ線
回折を第４図に示す。この図には、Ａｌ２Ｏ３。On the other hand, FIG. 4 shows the X-ray diffraction of a sample in which YBa2Cu, Ox paste was directly applied to an Al2O3 substrate and heat-treated at 950°C. In this figure, Al2O3.
ＹＢａ２ＣＬＩｓＯ２−ｘのピーク、および同定できな
い多くのピークが混在しており、超伝導特性も確認する
ことができなかった。The YBa2CLIsO2-x peak and many unidentified peaks were mixed, and superconducting properties could not be confirmed.
去妻ＩＩユ
まず、一つの表面を露出し他の面をセラミックス系接着
剤でカバーしたＣｕ金属板を、酸素を含有する雰囲気下
で加熱処理（９００℃、１時間）し、露出表面を酸化し
てＣｕＯ層を形成した。次に、このＣｕＯ層の上にＹＢ
ａ、Ｃｕ３０．のそル比になるように秤量混合したペー
ストを塗布し、９００℃３０分間、酸素τ囲気下で加熱
処理を施し、その後徐冷した。First, a Cu metal plate with one surface exposed and the other surface covered with a ceramic adhesive was heat treated (900°C, 1 hour) in an oxygen-containing atmosphere to oxidize the exposed surface. A CuO layer was formed. Next, YB is placed on top of this CuO layer.
a, Cu30. The pastes were weighed and mixed so as to have the same ratio as above, and then heat-treated at 900° C. for 30 minutes in an atmosphere of oxygen τ, and then slowly cooled.
第５図はこのサンプルのＸ線回折を示す。第５図に見ら
れるように、超伝導相ＹＢａ、Ｃｕ３０．．が成長して
おり、ＣｕＯ層を表面に形成することにより、Ｃｕ金属
板も、基板として使用できることが明らかになった。ま
た、この結果は、ＣｕＯ膜がＹＢａ２Ｃｕ、０×を加熱
処理する間、拡散等により超伝導相の形成に悪い影響を
与えることがないことを示している。Figure 5 shows the X-ray diffraction of this sample. As seen in FIG. 5, superconducting phases YBa, Cu30. ．． It has become clear that a Cu metal plate can also be used as a substrate by forming a CuO layer on the surface. This result also shows that the CuO film does not have a negative effect on the formation of a superconducting phase due to diffusion or the like during the heat treatment of YBa2Cu, 0x.
以上の実施例においては、Ｙ−Ｂａ−Ｃｕ−０系超伝導
体を例にとって説明したが、他のＬｎ−Ｒ−Ｃｕ−０系
でも同様に基板表面にＣｕＯ層を形成し、その上に超伝
導材料を塗布し、加熱することによって本発明の実施例
の効果は確認できるので、広く他の組成に適用できるこ
とはもちろんである。In the above embodiments, the Y-Ba-Cu-0 based superconductor was used as an example, but for other Ln-R-Cu-0 based superconductors, a CuO layer is similarly formed on the substrate surface, and a CuO layer is formed on the substrate surface. Since the effects of the embodiments of the present invention can be confirmed by applying a superconducting material and heating it, it is of course applicable to a wide range of other compositions.
［発明の効果］
以上説明したように、本発明においては、基板上にＣｕ
Ｏ層を少なくとも一層形成し、その上に超伝導酸化物薄
膜を形成するようにしたので、基板上に結晶をＣ軸配向
させることができ、しかも、従来は超伝導材料との反応
のために用いることができなかったＡｌ２Ｏ，、ＢｅＯ
および５ｒＴｉ０３も基板として使用することができる
という効果がある。[Effects of the Invention] As explained above, in the present invention, Cu is deposited on the substrate.
By forming at least one O layer and forming a superconducting oxide thin film on top of it, the crystals can be oriented along the C axis on the substrate. Al2O, BeO that could not be used
and 5rTi03 can also be used as a substrate.
第１図および第２図は本発明の第１の実施例によるＸ線
回折を示す図、
第３図は本発明の第２の実施例によるＸ線回′折を示す
図、
第４図は本発明の第２の実施例との比較を示すためのＸ
線回折図、
第５図は本発明の第３の実施例によるＸ線回折を示す図
である。
特許出願人 日本電信電話株式会社1 and 2 are diagrams showing X-ray diffraction according to the first embodiment of the present invention, FIG. 3 is a diagram showing X-ray diffraction according to the second embodiment of the present invention, and FIG. 4 is a diagram showing X-ray diffraction according to the second embodiment of the present invention. X to show comparison with the second embodiment of the invention
Ray Diffraction Diagram, FIG. 5 is a diagram showing X-ray diffraction according to the third embodiment of the present invention. Patent applicant Nippon Telegraph and Telephone Corporation
Claims (1)
Ｏ層上にＬｎ−Ｒ−Ｃｕ−Ｏ系（ＬｎはＹまたはランタ
ノイド元素、Ｒはアルカリ土類金属元素）からなる酸化
物薄膜を形成することを特徴とする酸化物超伝導膜の作
製方法。1) Form at least one CuO layer on the substrate, and
A method for producing an oxide superconducting film, which comprises forming an oxide thin film of Ln-R-Cu-O system (Ln is Y or a lanthanide element, R is an alkaline earth metal element) on an O layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63019557A JPH01246371A (en) | 1988-02-01 | 1988-02-01 | Manufacture of oxide superconducting film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63019557A JPH01246371A (en) | 1988-02-01 | 1988-02-01 | Manufacture of oxide superconducting film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01246371A true JPH01246371A (en) | 1989-10-02 |
Family
ID=12002616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63019557A Pending JPH01246371A (en) | 1988-02-01 | 1988-02-01 | Manufacture of oxide superconducting film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01246371A (en) |
-
1988
- 1988-02-01 JP JP63019557A patent/JPH01246371A/en active Pending
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