JPH0264020A - Bi-sr-ca-cu-o-based superconducting oxide - Google Patents
Bi-sr-ca-cu-o-based superconducting oxideInfo
- Publication number
- JPH0264020A JPH0264020A JP63213537A JP21353788A JPH0264020A JP H0264020 A JPH0264020 A JP H0264020A JP 63213537 A JP63213537 A JP 63213537A JP 21353788 A JP21353788 A JP 21353788A JP H0264020 A JPH0264020 A JP H0264020A
- Authority
- JP
- Japan
- Prior art keywords
- superconducting oxide
- oxide
- superconducting
- phase
- based superconducting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910015901 Bi-Sr-Ca-Cu-O Inorganic materials 0.000 title claims abstract 6
- 239000002184 metal Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 6
- 239000010408 film Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-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
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
この発明はアモルファス状のＢ １−Ｓｒ−（：ａ−Ｃ
ｕ−０系酸化物から製造した高Ｔｃ（電気抵抗が０にな
る絶対温度、以下Ｔｃ）の厚膜超電導酸化物に関する。[Detailed Description of the Invention] [Industrial Application Field] This invention relates to amorphous B 1-Sr-(:a-C
The present invention relates to a high Tc (absolute temperature at which electrical resistance becomes 0, hereinafter referred to as Tc) thick film superconducting oxide manufactured from u-0 type oxide.
なお、厚膜とはｌ Ｏｕｍ以上の厚みを持った薄膜であ
る。Note that a thick film is a thin film having a thickness of 1 Oum or more.
［従来の技術］
ＢｅｄｎｏｒｚおよびＭｕｌｌｅｒによりＬａ−Ｂａ−
Ｃｕ−０系の高温超電導酸化物が報告（Ｐｈｙｓ、 ８
６４（１９８６）１８９）されてから、Ｔｃが約９０に
のＹ−Ｂａ−（：ｕ−０系の超電導酸化物の報告（Ｐｈ
ｙｓ、、Ｒｅｗ、 Ｌｅｔｔ、 ５８（＋９８７）９０
８）かなされるにおよんで高温超電導酸化物の開発競争
が熾烈をきわめている。[Prior Art] La-Ba- by Bednorz and Muller
A Cu-0-based high-temperature superconducting oxide has been reported (Phys, 8
64 (1986) 189), a report (Ph
ys,, Rew, Lett, 58(+987)90
8) The competition to develop high-temperature superconducting oxides is intensifying.
さらにまた、最近になってＢｉ−Ｓｒ−Ｃａ−Ｃｕ−０
系のＴｃ約１０５にを有する新高温超電導酸化物が報告
（Ｊ。Furthermore, recently Bi-Sr-Ca-Cu-0
A new high-temperature superconducting oxide with a Tc of about 105 has been reported (J.
Ａｐｐｌ、 ｌ’ｈｙｓ、 ２７（１９８８）Ｌ２０９
）された。しかしながら、このＢ １−Ｓｒ−［：ａ−
Ｃｕ−０系超電導酸化物にはＴｃが１０５にの酸化物と
７５にの酸化物の２つの相を持っており、この高Ｔｃ相
をいかに多く晶出させるかがこのＢ １−Ｓｒ−（：ａ
−Ｃｕ−０系の超電導酸化物の課題である。この課題を
解決するために高野等はＢｉ−Ｓｒ−Ｃａ−（：ｕ−０
系超電導酸化物のＢｉの１部をｐｂに置換することによ
り高Ｔｃ相の比率が急激に増加することを報告（Ｊｐｎ
、 Ｊ、 Ａｐｐｌ、 Ｐｈｙｓ、 ２７（１９８８）
Ｌ１０４１） した。Appl, l'hys, 27 (1988) L209
) was done. However, this B 1-Sr-[:a-
The Cu-0 superconducting oxide has two phases, an oxide with a Tc of 105 and an oxide with a Tc of 75, and how to crystallize as much of this high Tc phase as possible depends on the B 1-Sr-( :a
This is a problem with -Cu-0-based superconducting oxides. To solve this problem, Takano et al.
It has been reported that the proportion of high Tc phase increases rapidly by replacing a part of Bi in superconducting oxides with PB (Jpn
, J. Appl, Phys, 27 (1988)
L1041) I did.
一方、上記超電導酸化物は焼結工程で作るバルク材や基
板上に薄膜を形成する方法が盛んに研究されている。バ
ルク材はこの超電導材が酸化物であるため加工性が悪く
所望の形状としにくいこと、気孔を多く含むなどの理由
のためＪｃ（臨界電流密度、以下Ｊｃ）が低いという問
題点があり、また薄膜についてはＴｃがバルク材に比較
して低下するという問題があった。これらの観点からＴ
ｃを低下させずに実際に流せる電流値の大きい厚膜を基
板上に形成した製品を開発することが望まれていた。On the other hand, methods for forming thin films on bulk materials and substrates made using the superconducting oxides through a sintering process are being actively studied. Bulk materials have the problem of low Jc (critical current density, hereinafter referred to as Jc) due to the fact that this superconducting material is an oxide and has poor workability and is difficult to form into the desired shape, and contains many pores. As for thin films, there is a problem that Tc is lower than that of bulk materials. From these points of view, T
It has been desired to develop a product in which a thick film with a large current value that can actually be passed without reducing c is formed on a substrate.
薄膜と厚膜とでは用途が異なり、薄膜では、ＮＩＳ、５
１５などのジョセフソン接合を利用した超電導素子が中
心になるのに対し厚膜ではマクロな例えばプリント基板
のような回路あるいはテープなどの用途が考えられる。Thin films and thick films have different uses, and for thin films, NIS, 5
While superconducting devices using Josephson junctions such as No. 15 are the main focus, thick films can be used for macroscopic circuits such as printed circuit boards or tapes.
また、Ｄｉ−Ｓｒ−Ｃａ−Ｃｕ−０系の超電導酸化物は
急冷によりアモルファス（非晶質、以下アモルファス）
化する性質があり、小松等により急冷厚膜を作る方法（
Ｊｐｎ、 Ｊ、 Ａｐｐｌ、 Ｐｈｙｓ、 ２７（１９
８８）Ｌ５３３）が報告されている。しかしなからこの
方法は基板上に形成するものでないため、このままでは
実用化は困難であるなどの問題点があった。In addition, the Di-Sr-Ca-Cu-0 system superconducting oxide becomes amorphous (non-crystalline, hereinafter referred to as amorphous) by rapid cooling.
Komatsu et al.'s method for making quenched thick films (
Jpn, J, Appl, Phys, 27(19
88) L533) has been reported. However, since this method does not involve forming on a substrate, there are problems in that it is difficult to put it into practical use as it is.
［発明が解決しようとする課題］
本発明は基板上に厚膜を形成するに際し、Ｔｃの低下の
少ない超電導酸化物を提供することを目的とする。[Problems to be Solved by the Invention] An object of the present invention is to provide a superconducting oxide that exhibits less decrease in Tc when forming a thick film on a substrate.
［課題を解決するための手段］
本発明は９１−Ｓｒ−Ｃａ−Ｃｕ−０系超電導酸化物に
おいて、金属原子に対し１〜９原子亀のＣｄを添加する
ことを特徴とする。またＢｉ２Ｓｒ２（：Ｂ２Ｃｕ３０
．の組成をもった超電導酸化物において、ＣａをＣｄで
置換しＢｉ２Ｓｒ２Ｃａ２−ｘｃｄＸＣｕ３０ｙ （た
だし、ｘ＝ ０．１〜０．８）とすることを特徴とす
る。[Means for Solving the Problems] The present invention is characterized in that 1 to 9 atoms of Cd are added to the metal atoms in a 91-Sr-Ca-Cu-0 based superconducting oxide. Also, Bi2Sr2(:B2Cu30
．． In the superconducting oxide having the composition, Ca is replaced with Cd to give Bi2Sr2Ca2-xcdXCu30y (where x=0.1 to 0.8).
［作用］
以下、本発明について詳細に説明する。Ｂｉ−Ｓｒ−Ｃ
ａ−Ｃｕ−０系超電導酸化物は高Ｔｃ相としてＢｉ２Ｓ
ｒ２Ｃａ２Ｃｕ３０．相が、Ｔｃの低い相としてＢｉ２
Ｓｒ２ＣａＣｕ２０゜相、またはＢ １４ｓｒ３ｃａ３
ｃｕ４０ｙ相があるといわれている。このようにＢｉ−
Ｓｒ−Ｃａ−Ｃｕ−０系超電導酸化物には高Ｔｅ相、低
Ｔｃ相が共存しているため原料の配合を高Ｔｃ相のＢ
１２Ｓｒ２（：Ｂ２Ｃｕ３０．にあわせて焼成しても、
電気抵抗が低下し始めるＴ、 （ｏｎ ５ｅｔ）が変動
し、電気抵抗が０となるＴｃ（ｅｎｄ）も１０５により
さらに低温側に移行するとともに、Ｔｃ（ｏｎ ５ｅｔ
）からＴ。[Function] Hereinafter, the present invention will be explained in detail. Bi-Sr-C
The a-Cu-0 superconducting oxide has Bi2S as a high Tc phase.
r2Ca2Cu30. The phase is Bi2 as a phase with low Tc.
Sr2CaCu20° phase, or B14sr3ca3
It is said that there is a cu40y phase. In this way Bi-
Since high Te phase and low Tc phase coexist in Sr-Ca-Cu-0-based superconducting oxide, the raw material composition was changed to B of high Tc phase.
Even if fired according to 12Sr2(:B2Cu30.),
T, (on 5et), where the electrical resistance begins to decrease, changes, and Tc (end), where the electrical resistance becomes 0, shifts further to the lower temperature side due to 105, and Tc (on 5et) changes.
) to T.
（ｅｎｄ）までの温度範囲が広がる傾向がある。先に記
載したように、このような問題点を解決するために［］
ｉの１部をｐｂに置換した焼結体でＴｃ（ｏｎ ５ｅｔ
）１２５に、 Ｔｃ（ｅｎｄ） １０７にの値のものが
得られている。There is a tendency for the temperature range up to (end) to widen. As mentioned earlier, in order to solve these problems []
Tc (on 5et
) 125 and Tc(end) 107 are obtained.
しかしながら、上記組成を有する超電導酸化物をアモル
ファス化した厚膜をＭｇＯ単結晶基板上で熱処理すると
第１図の（ｂ）曲線のようにＴｃが低下し上記のような
高Ｔｃは得られないことが判明した。However, when a thick film made of an amorphous superconducting oxide having the above composition is heat-treated on an MgO single crystal substrate, the Tc decreases as shown in curve (b) in Figure 1, and the high Tc described above cannot be obtained. There was found.
発明者等はこのような知見に基づき種々の合金系につい
て検討した結果、Ｂ １−Ｓｒ−Ｃａ−Ｇｕ−０系超電
導酸化物のＣａの１部をＣｄに置換すればＴｃの高い超
電導酸化物厚膜を基板上に作ることが可能であることを
見出した。すなわち、Ｂ １−Ｓｒ−Ｃａ−Ｃｕ−０系
超電導酸化物に金属原子に対し１〜９原子亀のＧｄを添
加すればよい。Ｃｄの添加率が９原子亀を超えると超電
導相が得られず絶縁相となり、１原子亀未満では低ＴＣ
相が増加して基板上のＢｉ−Ｓｒ−にａ−Ｃｕ−０系超
電導酸化物の厚膜Ｔｃか低下する。最も望ましい範囲は
Ｂｉ２Ｓｒ２Ｃａ２−１ｌＣｄｘＣｕ３０．ｆにおいて
ｘ＝０．１〜０．８とする組成か安定的に高いＴｏを有
する厚膜となる。この結果の１例を第１図の（ａ）およ
び第２図に示す。Based on this knowledge, the inventors studied various alloy systems and found that if a part of Ca in the B1-Sr-Ca-Gu-0 system superconducting oxide is replaced with Cd, a superconducting oxide with high Tc can be obtained. We have found that it is possible to create thick films on substrates. That is, Gd may be added to the B1-Sr-Ca-Cu-0 based superconducting oxide in an amount of 1 to 9 atoms per metal atom. When the Cd addition rate exceeds 9 atoms, a superconducting phase cannot be obtained and an insulating phase occurs, and when it is less than 1 atom, a low TC occurs.
As the phase increases, the thickness of the thick film Tc of the a-Cu-0 based superconducting oxide on the Bi-Sr- substrate decreases. The most desirable range is Bi2Sr2Ca2-11CdxCu30. A composition in which x=0.1 to 0.8 at f results in a thick film having a stably high To. An example of this result is shown in FIG. 1(a) and FIG. 2.
［実ｔＪへ例］
Ｂｉ２Ｏ，、ＣａＣ０，、、Ｃｕｂ、 ＳｒＣＯ，、、
ｐｂｏおよびＣｄＯをＢｉ（、，７Ｐｂｏ３ＳｒＣａＣ
ｕ、８０Ｙ、 Ｂｉ２Ｓｒ２Ｃ：Ｂ２−、ＣｄＸＣｕ
３０Ｙ。[Example to real tJ] Bi2O,, CaC0,, Cub, SrCO,,,
pbo and CdO as Bi(,,7Pbo3SrCaC
u, 80Y, Bi2Sr2C:B2-, CdXCu
30Y.
ｘ＝０．０．２．０．４．０．８．１．０．１．４．２
．０となるように配合し、メノウ乳鉢でメタノールとと
もに４時間混合し、空気中８００℃で１２時間仮焼した
。これを粉砕し、ＣＩＰにより直径２．５ｍｍ径、長さ
＋５０１１Ｉｍの棒状に成形した。この棒の先端をキセ
ノンランプを用いたアークイメージ炉で溶解し、双ロー
ラ−（２０００ｒｐｍ）超急冷して、厚さ約２０μｍの
薄片試料を得た。この試料をＭｇＯ単結晶の（１００）
”Ａ開面上に乗せて８００℃〜８９０℃で熱処理を行
ない厚膜を形成した。その結果の１例を第１図にしめし
た。この図からも明らかにように、Ｂｔｏ、 ７ＰＥｌ
ｏ３ＳｒＣａ（：ｕ＋、 ａｎｙ系（第１図（ｂ））で
はＴｃが低いのに対し、Ｂｉ２Ｓｒ２Ｃａ２−、ＣｄＸ
Ｃｕ３０ｙ系（第１図（ａ））ではＴｃ（ｏｎ ５ｅｔ
）１００に以上、ｘ＝０．２でＴｃ（ｅｎｄ） ８４に
、Ｘ＝０．４で８７にのものかえられた。Ｔｅが高く良
好な超電導性を示すＸの範囲は０．１〜０．８で、Ｋが
１．０を超えると絶縁相となった。x=0.0.2.0.4.0.8.1.0.1.4.2
．． 0, mixed with methanol in an agate mortar for 4 hours, and calcined in air at 800°C for 12 hours. This was crushed and molded into a rod shape with a diameter of 2.5 mm and a length of +5011 Im by CIP. The tip of this rod was melted in an arc image furnace using a xenon lamp and ultra-quenched using twin rollers (2000 rpm) to obtain a thin sample with a thickness of about 20 μm. This sample is a MgO single crystal (100)
A thick film was formed by heat treatment at 800°C to 890°C on the open surface of A.An example of the result is shown in Figure 1.As is clear from this figure, Bto, 7PEl
o3SrCa(:u+, any system (Fig. 1(b)) has a low Tc, whereas Bi2Sr2Ca2-, CdX
In the Cu30y system (Fig. 1 (a)), Tc (on 5et
) 100 or more, Tc(end) was changed to 84 at x=0.2, and 87 at X=0.4. The range of X that exhibits high Te and good superconductivity is 0.1 to 0.8, and when K exceeds 1.0, it becomes an insulating phase.
［発明の効果］
Ｂｉ−Ｓｒ−Ｃａ−１１：ｕ−０系超電導酸化物のＣａ
の１部をＣｄで置換することにより、基板上に形成した
厚膜のＴｃをＴｃ（ｏｎ ５ｅｔ）で１００に、Ｔｃ（
ｅｎｄ） ８７にのものを得ることが可能となり、大電
流を流せる超電導体素子の開発の可能性が得られた。[Effect of the invention] Bi-Sr-Ca-11: Ca of u-0 based superconducting oxide
By replacing a part of with Cd, the Tc of the thick film formed on the substrate becomes 100 with Tc(on 5et) and Tc(on 5et) with Cd.
end) It became possible to obtain 87 items, and the possibility of developing superconductor elements capable of passing large currents was obtained.
第１図は本発明に係わるＢｉ２Ｓｒ２（：ａ、−、（：
ｄ、ｃｕ３０．。
系超電導酸化物においてｘ＝０．２の場合と比較材の電
気抵抗の変化を示した図、第２図はｘ ＝ ０．４のと
きの電気抵抗の変化を示す図である。FIG. 1 shows Bi2Sr2(:a, -, (:
d, cu30. . A diagram showing the change in electrical resistance of the superconducting oxide based on x=0.2 and a comparative material, and FIG. 2 is a diagram showing the change in electrical resistance when x=0.4.
Claims (1)
て、金属原子に対し１〜９原子％のＣｄを添加すること
を特徴とするＢｉ−Ｓｒ−Ｃａ−Ｃｕ−Ｏ系超電導酸化
物。 ２、Ｂｉ−Ｓｒ−Ｃａ−Ｃｕ−Ｏ系超電導酸化物におい
て、Ｂｉ＿２Ｓｒ＿２Ｃａ＿２＿−＿ｘＣｄ＿ｘＣｕ＿
３Ｏ＿ｙ（ただし、ｘ＝０．１〜０．８）とすることを
特徴とするＢｉ−Ｓｒ−Ｃａ−Ｃｕ−Ｏ系超電導酸化物
。[Claims] 1. Bi-Sr-Ca-Cu-O based superconducting oxide, characterized in that 1 to 9 atomic % of Cd is added to the metal atoms. O-based superconducting oxide. 2. In Bi-Sr-Ca-Cu-O superconducting oxide, Bi_2Sr_2Ca_2_-_xCd_xCu_
A Bi-Sr-Ca-Cu-O based superconducting oxide characterized by 3O_y (where x=0.1 to 0.8).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63213537A JPH075312B2 (en) | 1988-08-30 | 1988-08-30 | Bi-Sr-Ca-Cu-O-based superconducting oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63213537A JPH075312B2 (en) | 1988-08-30 | 1988-08-30 | Bi-Sr-Ca-Cu-O-based superconducting oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0264020A true JPH0264020A (en) | 1990-03-05 |
| JPH075312B2 JPH075312B2 (en) | 1995-01-25 |
Family
ID=16640832
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63213537A Expired - Lifetime JPH075312B2 (en) | 1988-08-30 | 1988-08-30 | Bi-Sr-Ca-Cu-O-based superconducting oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH075312B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04198026A (en) * | 1990-11-29 | 1992-07-17 | Chodendo Hatsuden Kanren Kiki Zairyo Gijutsu Kenkyu Kumiai | Bi-sr-ca-cu-o superconductor material |
-
1988
- 1988-08-30 JP JP63213537A patent/JPH075312B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04198026A (en) * | 1990-11-29 | 1992-07-17 | Chodendo Hatsuden Kanren Kiki Zairyo Gijutsu Kenkyu Kumiai | Bi-sr-ca-cu-o superconductor material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH075312B2 (en) | 1995-01-25 |
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