JPH075312B2 - Bi-Sr-Ca-Cu-O-based superconducting oxide - Google Patents
Bi-Sr-Ca-Cu-O-based superconducting oxideInfo
- Publication number
- JPH075312B2 JPH075312B2 JP63213537A JP21353788A JPH075312B2 JP H075312 B2 JPH075312 B2 JP H075312B2 JP 63213537 A JP63213537 A JP 63213537A JP 21353788 A JP21353788 A JP 21353788A JP H075312 B2 JPH075312 B2 JP H075312B2
- Authority
- JP
- Japan
- Prior art keywords
- superconducting oxide
- phase
- based superconducting
- oxide
- thick film
- 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 - Lifetime
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
- Inorganic Compounds Of Heavy Metals (AREA)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
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Bi−Sr−Ca−Cu−Ｏ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 field of application] The present invention has a high T c (absolute temperature at which electric resistance becomes zero, hereinafter T 1) manufactured from an amorphous Bi—Sr—Ca—Cu—O-based oxide. c ) The thick film superconducting oxide.
なお、厚膜とは10μｍ以上の厚みを持った膜である。The thick film is a film having a thickness of 10 μm or more.
［従来の技術］ BednorzおよびMullerによりLa−Ba−Cu−Ｏ系の高温超
電導酸化物が報告（Phys.B64（1986）189）されてか
ら、Tcが約90KのＹ−Ba−Cu−Ｏ系の超電導酸化物の報
告（Phys.Rew.Lett.58（1987）908）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] Since Bednorz and Muller reported a high-temperature superconducting oxide of the La-Ba-Cu-O system (Phys.B64 (1986) 189), Y-Ba-Cu-O with a T c of about 90K was reported. As a result of reports on superconducting oxides (Phys. Rew. Lett. 58 (1987) 908), the competition for the development of high temperature superconducting oxides is extremely fierce.
さらにまた、最近になってBi−Sr−Ca−Cu−Ｏ系のTc約
105Kを有する新高温超電導酸化物が報告（J.Appl.Phys.
27（1988）L209）された。しかしながら、このBi−Sr−
Ca−Cu−Ｏ系超電導酸化物にはTcが105Kの酸化物と75K
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Bi−Sr−Ca−Cu−Ｏ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−Cu−Ｏ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。Furthermore, recently, the T c of Bi-Sr-Ca-Cu-O system
A new high temperature superconducting oxide with 105K is reported (J.Appl.Phys.
27 (1988) L209). However, this Bi-Sr-
Ca-Cu-O-based superconducting oxides have T c of 105K and 75K.
The Bi-Sr-Ca-Cu-O-based superconducting oxide has a problem in how much the high Tc phase is crystallized. In order to solve this problem, Takano et al. Reported that the ratio of the high T c phase rapidly increased by substituting Pb for a part of Bi in the Bi-Sr-Ca-Cu-O-based superconducting oxide ( Jpn.J.Appl.Phys.27 (1988) L1041).
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Tc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る。On the other hand, a method of forming a thin film on a bulk material or a substrate formed by a sintering process has been actively researched for the superconducting oxide. The bulk material has problems that the superconducting material is an oxide, so that it is difficult to form into a desired shape due to poor workability, and that it has a low J c (critical current density, hereinafter J c ) due to the fact that it contains many pores. Moreover, there is a problem that T c of the thin film is lower than that of the bulk material. From these viewpoints, it is desired to develop a product in which a thick film having a large current value that can be actually flowed without lowering T 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、SIS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。The thin film and thick film have different uses.For thin films, superconducting devices using Josephson junctions such as NIS and SIS are the main, whereas thick films are macro, for example, circuits such as printed circuit boards or tapes. Can be considered.
また、Bi−Sr−Ca−Cu−Ｏ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.Ap
pl.Phys.27（1988）L533）が報告されている。しかしな
が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。Further, the Bi-Sr-Ca-Cu-O-based superconducting oxide has the property of becoming amorphous (amorphous, hereinafter referred to as "amorphous") by rapid cooling, and a method of making a rapidly thick film by Komatsu et al. (Jpn.
pl.Phys.27 (1988) L533) has been reported. However, since this method is not formed on the substrate, there is a problem 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] It is an object of the present invention to provide a superconducting oxide having a small decrease in T c when forming a thick film on a substrate.
［課題を解決するための手段］ 本発明はBi2Sr2Ca2Cu3OY組成をもった超電導酸化物にお
いて、CaをCdで置換しBi2Sr2Ca2-xCdxCu3OY（ただし、
ｘ＝0.2〜0.4）とすることを特徴とする。[Means for Solving the Problems] The present invention is directed to a superconducting oxide having a Bi 2 Sr 2 Ca 2 Cu 3 O Y composition, in which Ca is replaced by Cd and Bi 2 Sr 2 Ca 2-x Cd x Cu 3 O is added. Y (However,
x = 0.2 to 0.4).
［作用］ 以下、本発明について詳細に説明する。Bi−Sr−Ca−Cu
−Ｏ系超電導酸化物は高Tc相としてBi2Sr2Ca2Cu3OY相
が、Tcの低い相としてBi2Sr2CaCu2OY相、またはBi4Sr3C
a3Cu4OY相があるといわれている。このようにBi−Sr−C
a−Cu−Ｏ系超電導酸化物には高Tc相、低Tc相が共存し
ているため原料の配合を高Tc相のBi2Sr2Ca2Cu3OYにあわ
せて焼成しても、電気抵抗が低下し始めるTc（on set）
が変動し、電気抵抗が０となるTc（end）も105Kよりさ
らに低温測に移行するとともに、Tc（on set）からT
c（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Biの１
部をPbに置換した焼結体でTc（on set）125K、Tc（en
d）107Kの値のものが得られている。[Operation] Hereinafter, the present invention will be described in detail. Bi-Sr-Ca-Cu
The Bi-O-based superconducting oxide has a Bi 2 Sr 2 Ca 2 Cu 3 O Y phase as a high T c phase and a Bi 2 Sr 2 CaCu 2 O Y phase as a low T c phase, or Bi 4 Sr 3 C.
It is said that there is a 3 Cu 4 O Y phase. Thus Bi-Sr-C
Since a high T c phase and a low T c phase coexist in the a-Cu-O superconducting oxide, the raw material composition is fired in accordance with the high T c phase Bi 2 Sr 2 Ca 2 Cu 3 O Y. Even if T c (on set)
Fluctuates, and T c (end) at which the electric resistance becomes 0 shifts to a low temperature measurement from 105 K, and T c (on set) changes to T
The temperature range up to c (end) tends to widen. As mentioned above, Bi 1
Tc (on set) 125K, T c (en
d) A value of 107K is 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, high T c as described above T c decreases as the superconducting oxide of FIG. 1 when the amorphized thick heat-treated on a MgO single crystal substrate (b) curve having the above composition
Turned out not to get.
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、Bi−Sr−Ca−Cu−Ｏ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、Bi−Sr−Ca−Cu−Ｏ系超電導酸化物に金属原子に対
して１〜９原子％のCdを添加すればよい。Cdの添加率が
９原子％を超えると超電導相が得られず絶縁相となり、
１原子％未満では低Tc相が増加して基板上のBi−Sr−Ca
−Cu−Ｏ系超電導酸化物の厚膜Tcが低下する。最も望ま
しい範囲はBi2Sr2Ca2-xCdxCu3OYにおいてｘ＝0.1〜0.8
とする組成が安定的に高いTc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。The inventors have studied various alloy systems based on such findings, and as a result, have found that the Bi-Sr-Ca-Cu-O-based superconducting oxide
It has been found that a superconducting oxide thick film having a high T c can be formed on the substrate by substituting Cd for a part of Ca. That is, 1 to 9 atom% of Cd with respect to the metal atom may be added to the Bi-Sr-Ca-Cu-O-based superconducting oxide. If the addition rate of Cd exceeds 9 atomic%, a superconducting phase cannot be obtained and becomes an insulating phase.
If it is less than 1 atomic%, the low T c phase increases and Bi-Sr-Ca on the substrate
The thick film T c of the —Cu—O-based superconducting oxide decreases. The most desirable range is Bi 2 Sr 2 Ca 2-x Cd x Cu 3 O Y where x = 0.1 to 0.8
The composition is a thick film having a stable high T c . An example of this result is shown in FIG. 1 (a) and FIG.
［実施例］ Bi2O3，CaCO3,CuO,SrCO3,PbOおよびCdOをBi0.7Pb0.3SrC
aCu1.8OY，Bi2Sr2Ca2-xCdxCu3OY、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150m
m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融解し、双ローラー（2000rp
m）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）劈開面上に乗せて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、Bi
0.7Pb0.3SrCaCu1.8OY系（第１図（ｂ））ではTcが低い
のに対し、Bi2Sr2Ca2-xCdxCu3OY系（第１図（ａ））で
はTc（on set）100K以上、ｘ＝0.2でTc（end）84K、ｘ
＝0.4で87Kのものがえられた。Tcが高く良好な超電導性
を示すｘの範囲は0.1〜0.8でｘが1.0を超えると絶縁相
となった。[Example] Bi 0.7 Pb 0.3 SrC was added to Bi 2 O 3 , CaCO 3 , CuO, SrCO 3 , PbO and CdO.
aCu 1.8 O Y , Bi 2 Sr 2 Ca 2-x Cd x Cu 3 O Y , x = 0, 0.2, 0.4, 0.8,
The ingredients were blended so as to be 1.0, 1.4 and 2.0, mixed with methanol in an agate mortar for 4 hours, and calcined in air at 800 ° C for 12 hours. This is crushed and the diameter is 2.5mm and the length is 150m by CIP.
It was formed into a rod shape of m. The tip of this rod was melted in an arc image furnace using a xenon lamp and twin rollers (2000rp
m) Ultra-quenched to obtain a thin sample with a thickness of about 20 μm. This sample is placed on the (100) cleavage plane of MgO single crystal and the temperature is 800 ℃ ～ 890
A thick film was formed by heat treatment at ℃. An example of the result is shown in FIG. As is clear from this figure, Bi
In the 0.7 Pb 0.3 SrCaCu 1.8 O Y system (Fig. 1 (b)), T c is low, whereas in the Bi 2 Sr 2 Ca 2-x Cd x Cu 3 O Y system (Fig. 1 (a)), T c is low. c (on set) 100K or more, Tc (end) 84K, x at x = 0.2
= 0.4 gives 87K. The range of x having a high T c and exhibiting good superconductivity is 0.1 to 0.8, and when x exceeds 1.0, it becomes an insulating phase.
［発明の効果］ Bi−Sr−Ca−Cu−Ｏ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
set）で100K、Tc（end）87K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。1 part of Ca of Bi-Sr-Ca-Cu- O based superconducting oxide [Effect of the invention] by replacing Cd, the T c of the thick film formed on the substrate T c (on
It was possible to obtain 100K and T c (end) 87K with a set), and the possibility of developing a superconductor element capable of passing a large current was obtained.
第１図は本発明に係わるBi2Sr2Ca2-xCdxCu3OY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 is a diagram showing a change in electric resistance of a comparative material in the case of x = 0.2 in a Bi 2 Sr 2 Ca 2 -x Cd x Cu 3 O Y based superconducting oxide according to the present invention, and FIG. It is a figure which shows the change of electric resistance when = 0.4.
Claims (1)
て、Bi2Sr2Ca2-xCdxCu3OY（ただし、ｘ＝0.2〜0.4）と
することを特徴とするBi−Sr−Ca−Cu−Ｏ系超電導酸化
物。1. A Bi-Sr-Ca-Cu- O based superconducting oxide, Bi 2 Sr 2 Ca 2- x Cd x Cu 3 O Y ( provided that, x = 0.2 to 0.4), characterized in that the Bi-Sr-Ca-Cu-O-based superconducting oxide.
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 JPH0264020A (en) | 1990-03-05 |
| JPH075312B2 true 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) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2749194B2 (en) * | 1990-11-29 | 1998-05-13 | 超電導発電関連機器・材料技術研究組合 | Method for producing Bi-Sr-Ca-Cu-O-based superconductor |
-
1988
- 1988-08-30 JP JP63213537A patent/JPH075312B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0264020A (en) | 1990-03-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0339801B1 (en) | Superconductive ceramics laminates and method for production thereof | |
| CN1022654C (en) | Tunnel type Josephson device and manufacturing method thereof | |
| CA1341616C (en) | High-temperature oxide superconductor | |
| US5145831A (en) | High-tc oxide superconductor and method for producing the same | |
| KR970002894B1 (en) | Superconducting metal oxide compositions | |
| US5389603A (en) | Oxide superconductors, and devices and systems comprising such a superconductor | |
| JPH075312B2 (en) | Bi-Sr-Ca-Cu-O-based superconducting oxide | |
| JP2817048B2 (en) | Method for producing Bi-Sr-Ca-Cu-O-based superconducting film by screen printing | |
| JP2501035B2 (en) | Superconducting thin film | |
| JPH0772086B2 (en) | Method for producing thick film of Bi-Sr-Ca-Cu-O-based superconducting oxide | |
| JP2517085B2 (en) | Superconducting thin film | |
| US5378682A (en) | Dense superconducting bodies with preferred orientation | |
| JPH01192758A (en) | Superconducting ceramic | |
| JP2569055B2 (en) | Preparation method of oxide superconductor thin film | |
| JPH04292420A (en) | Superconducting compound and method for its preparation | |
| JPS63239740A (en) | Manufacture for superconductive compound thin film | |
| JPH10330117A (en) | Oxide superconductor, its production and current lead using the same | |
| JP3272349B2 (en) | Manufacturing method of superconducting wiring | |
| JPH0745357B2 (en) | Superconducting fibrous single crystal and method for producing the same | |
| JPH01219023A (en) | Production of thin superconductor film | |
| JP3284010B2 (en) | Metal oxide material and superconducting device using the same | |
| JPH07100610B2 (en) | Manufacturing method of superconducting material | |
| JP2671881B2 (en) | Superconducting material | |
| Häuser et al. | Study of the Preparation and Properties of YBaCuO-Films | |
| JPS63230524A (en) | Superconductive material |