JPH0710734B2 - Method for producing oxide superconductor thin film - Google Patents
Method for producing oxide superconductor thin filmInfo
- Publication number
- JPH0710734B2 JPH0710734B2 JP2224418A JP22441890A JPH0710734B2 JP H0710734 B2 JPH0710734 B2 JP H0710734B2 JP 2224418 A JP2224418 A JP 2224418A JP 22441890 A JP22441890 A JP 22441890A JP H0710734 B2 JPH0710734 B2 JP H0710734B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- oxide superconductor
- cuo
- superconductor thin
- 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.)
- Expired - Fee Related
Links
- 239000010409 thin film Substances 0.000 title claims description 21
- 239000002887 superconductor Substances 0.000 title claims description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 14
- 239000010408 film Substances 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000238366 Cephalopoda Species 0.000 description 2
- 229910002480 Cu-O Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000005292 diamagnetic effect Effects 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 230000005291 magnetic effect Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052594 sapphire Inorganic materials 0.000 description 2
- 239000010980 sapphire Substances 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 2
- 229910015901 Bi-Sr-Ca-Cu-O Inorganic materials 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
- LPHBARMWKLYWRA-UHFFFAOYSA-N thallium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tl+3].[Tl+3] LPHBARMWKLYWRA-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 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)
- Crystals, And After-Treatments Of Crystals (AREA)
- Physical Vapour Deposition (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］ 本発明は、各種の超伝導応用装置や超伝導素子に使用さ
れる酸化物超伝導体薄膜の製造方法に関する。TECHNICAL FIELD The present invention relates to a method for producing an oxide superconductor thin film used in various superconducting application devices and superconducting elements.
［従来の技術］ 金属・合金系超伝導材料、化合物超伝導材料は、ジェセ
フソン素子や超伝導マグネットの線材として既に広く利
用されている。ジョセフソン接合はその磁場に対する高
い感度のためSQUIDを初めとする精密計測に応用されて
いるほか、その高速性から電子計算機への応用が期待さ
れている。また、通常導体では得られないような高磁場
を発生できる超伝導マグネットは、NMR-CTなどの医療機
器や浮上型リニアモーターカー等にも応用されている。[Prior Art] Metal / alloy based superconducting materials and compound superconducting materials are already widely used as wire rods for Josephson devices and superconducting magnets. Due to its high sensitivity to the magnetic field, the Josephson junction has been applied to precision measurement including SQUID, and due to its high speed, it is expected to be applied to electronic computers. In addition, superconducting magnets that can generate high magnetic fields that cannot be obtained with ordinary conductors have been applied to medical equipment such as NMR-CT and floating linear motor cars.
超伝導体の応用を考えた場合、超伝導転移温度Tcはでき
る限り高いことが望まれる。金属・合金系超伝導体や化
合物系超伝導体は、冷媒として高価で希少な液体ヘリウ
ムを用いなければならず、このことがこれらの超伝導体
の広い分野への応用を妨げる一因となっている。この点
では銅酸化物系超伝導体は、従来の超伝導体よりもはる
かに優れており、1987年にBa-Y-Cu-O系超伝導体が発見
されて以来、Bi-Sr-Ca-Cu-O系、Tl-Ba-Ca-Cu-O系などの
液体窒素温度を越えるTcをもつ超伝導体が相次いで発見
されている。これらの酸化物超伝導体が実用化されれ
ば、今まで考えられなかったような分野にまでその応用
の可能性が広がるとして、現在も研究開発が盛んに行わ
れている。Considering the application of superconductors, the superconducting transition temperature Tc is desired to be as high as possible. For metal / alloy superconductors and compound superconductors, expensive and rare liquid helium must be used as a refrigerant, which is one of the factors that hinder the application of these superconductors to a wide range of fields. ing. In this respect, copper oxide superconductors are far superior to conventional superconductors, and since the discovery of Ba-Y-Cu-O superconductors in 1987, Bi-Sr-Ca -Cu-O system, Tl-Ba-Ca-Cu-O system, and other superconductors with Tc above liquid nitrogen temperature have been discovered one after another. If these oxide superconductors are put to practical use, the possibility of their application will be expanded to fields that were previously unthinkable, and research and development are still being actively conducted.
［発明が解決しようとする課題］ 現在研究されている酸化物超伝導体試料のほとんどは多
結晶体である。超伝導体の多結晶試料では、その結晶粒
界に無数の超伝導の弱結合が存在するため、望む特性を
持つジョセフソン接合を制御性良く作ることが困難であ
る。また、多結晶体が含んでいる各種の欠陥や不均質性
が超伝導特性の安定性に悪い影響を与えることも考えら
れるため、デバイスなどへの応用には単結晶薄膜を用い
ることが望ましい。[Problems to be Solved by the Invention] Most of the oxide superconductor samples currently being studied are polycrystalline. In a polycrystalline superconductor sample, it is difficult to make a Josephson junction with desired characteristics with good controllability because there are countless weak superconducting bonds at the grain boundaries. Further, various defects and inhomogeneities contained in the polycrystal may adversely affect the stability of superconducting properties, so that it is desirable to use a single crystal thin film for application to devices and the like.
しかし、タリウム（Tl）を含む超伝導体の薄膜化におい
ては、蒸気圧の高いタリウムの蒸発が大きな問題とな
る。通常の薄膜作製法では組成のズレのために、求める
組成、構造を持った超伝導体薄膜を得ることが難しい。However, evaporation of thallium, which has a high vapor pressure, becomes a serious problem in thinning a superconductor containing thallium (Tl). It is difficult to obtain a superconductor thin film having a desired composition and structure due to the compositional deviation by the ordinary thin film manufacturing method.
本発明の目的は、良質なTl2Ba2CuO6薄膜の製造方法を提
供することにある。An object of the present invention is to provide a method for producing a good quality Tl 2 Ba 2 CuO 6 thin film.
［課題を解決するための手段］ 本発明は、Ba2CuOx（但し、２≦ｘ≦５）なる組成を持
つ薄膜を作製し、得られた薄膜をTl2O3とともに封入す
るか、もしくは密閉性の高い容器にいれて、600〜900℃
で10分〜10時間熱処理することによりTl2Ba2CuO6で表さ
れる酸化物超伝導体薄膜を得ることを特徴とする酸化物
超伝導体薄膜の製造方法である。[Means for Solving the Problems] In the present invention, a thin film having a composition of Ba 2 CuO x (where 2 ≦ x ≦ 5) is prepared, and the obtained thin film is enclosed with Tl 2 O 3 , or Put in a highly airtight container, 600-900 ℃
The method for producing an oxide superconductor thin film is characterized in that an oxide superconductor thin film represented by Tl 2 Ba 2 CuO 6 is obtained by heat treatment for 10 minutes to 10 hours.
本発明において、Ba2CuOxで表される薄膜は、真空蒸
着、スパッタリング等、通常の薄膜形成手段で作製する
ことができる。また、ｘの範囲は２≦ｘ≦５であり、通
常は３≦ｘ≦４である。In the present invention, the thin film represented by Ba 2 CuO x can be produced by a usual thin film forming means such as vacuum deposition and sputtering. The range of x is 2 ≦ x ≦ 5, and usually 3 ≦ x ≦ 4.
本発明によって得られる酸化物超伝導体薄膜は、Ｘ線回
折の結果から、Tl2Ba2CuO6の単一相であることが確認さ
れており、従来のものよりも、より単結晶に近いもので
ある。The oxide superconductor thin film obtained by the present invention has been confirmed to be a single phase of Tl 2 Ba 2 CuO 6 from the result of X-ray diffraction, and is closer to a single crystal than the conventional one. It is a thing.
［実施例］ 以下実施例により、本発明を具体的に説明する。[Examples] The present invention will be specifically described with reference to Examples below.
実施例１〜11 スパッタリングによる成膜 Ba:Cu＝2:1なるモル比を持つ酸化物を焼結したものをス
パッタリングターゲツトとし、室温のサファイアまたは
マグネシア基板上にBa2CuOx膜を堆積させた。得られた
膜の組成がBa:Cu＝2:1となっていることをEPMAで確認し
た後、直径20mm、深さ25mmの金坩堝に、純度99.9％以上
の酸化タリウム（Tl2O3）粉末と共に封入し、600〜900
℃で10分〜10時間熱処理を行った。Examples 1 to 11 Films formed by sputtering Ba 2 CuO x film was deposited on a sapphire or magnesia substrate at room temperature by using a sintered oxide target having a molar ratio of Ba: Cu = 2: 1 as a sputtering target. . After confirming with EPMA that the composition of the obtained film was Ba: Cu = 2: 1, thallium oxide (Tl 2 O 3 ) with a purity of 99.9% or more was placed on a metal crucible with a diameter of 20 mm and a depth of 25 mm. Enclose with powder, 600-900
The heat treatment was performed at 10 ° C for 10 minutes to 10 hours.
蒸着による成膜 蒸着源として金属BaとCuOを用い、多元電子ビーム蒸着
装置により、Ba2CuOxなる組成を持つ薄膜を、室温のサ
ファイアまたはマグネシア基板上に合成した。上記と同
様の条件でTl2O3と共に熱処理を行った。Deposition by evaporation Using metal Ba and CuO as evaporation sources, a thin film with the composition Ba 2 CuO x was synthesized on a sapphire or magnesia substrate at room temperature using a multi-source electron beam evaporation system. Heat treatment was performed with Tl 2 O 3 under the same conditions as above.
いずれの場合も、得られた薄膜の抵抗率、反磁性磁化率
の測定、組成分析、Ｘ線回折測定を行った。抵抗率は金
線をリードとする４端子法で、反磁性磁化率はSQUIDマ
グネットメーターでそれぞれ測定した。組成分析はEPMA
を用いて行った。In each case, the resistivity and diamagnetic susceptibility of the obtained thin film were measured, the composition was analyzed, and the X-ray diffraction was measured. The resistivity was measured by a 4-terminal method using a gold wire as a lead, and the diamagnetic susceptibility was measured by a SQUID magnetometer. Composition analysis is EPMA
Was performed using.
Ｘ線回折の結果から、得られた超伝導薄膜はいずれもTl
2Ba2CuO6構造をしており、ｃ軸配向していることが確認
された。第１表に、基板の種類、成膜方法、熱処理温
度、時間とTcの関係を示す。Ba2CuOx膜を蒸着で作った
場合もスパッタリングで作った場合も同様の超伝導特性
が得られている。From the result of X-ray diffraction, all the obtained superconducting thin films were Tl.
It was confirmed that it had a 2 Ba 2 CuO 6 structure and was c-axis oriented. Table 1 shows the relationship between substrate type, film forming method, heat treatment temperature, time and Tc. Similar superconducting properties are obtained regardless of whether the Ba 2 CuO x film is formed by vapor deposition or sputtering.
熱処理温度が900℃を超えると膜の分解が始まり、超伝
導特性が劣化する。また、600℃未満では、Ba2CuOx膜と
Tl2O3の反応が充分に起こらず、Tl2Ba2CuO6の生成が進
まない。When the heat treatment temperature exceeds 900 ° C, the film begins to decompose and the superconducting properties deteriorate. In addition, at temperatures below 600 ° C, a Ba 2 CuO x film
The reaction of Tl 2 O 3 does not sufficiently occur, and the formation of Tl 2 Ba 2 CuO 6 does not proceed.
［発明の効果］ 以上説明したように、本発明の製造方法によれば、Tl2B
a2CuO6の良質な薄膜を得ることができるため、超伝導材
料の工業利用にとって極めて有用なものである。 As described above, according to the manufacturing method of the present invention, Tl 2 B
Since it is possible to obtain a good quality thin film of a 2 CuO 6 , it is extremely useful for industrial use of superconducting materials.
フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０１Ｂ 13/00 ５６５ Ｄ 7244−5Ｇ Ｈ０１Ｌ 39/24 ＺＡＡ Ｂ 9276−4Ｍ Continuation of front page (51) Int.Cl. 6 Identification number Office reference number FI Technical display location H01B 13/00 565 D 7244-5G H01L 39/24 ZAA B 9276-4M
Claims (1)
持つ薄膜を作製し、得られた薄膜をTl2O3とともに封入
するか、もしくは密閉性の高い容器にいれて、600〜900
℃で10分〜10時間熱処理することによりTl2Ba2CuO6で表
される酸化物超伝導体薄膜を得ることを特徴とする酸化
物超伝導体薄膜の製造方法。1. A thin film having a composition of Ba 2 CuO x (where 2 ≦ x ≦ 5) is prepared, and the obtained thin film is sealed together with Tl 2 O 3 or put in a highly hermetic container. , 600 to 900
A method for producing an oxide superconductor thin film, which comprises obtaining an oxide superconductor thin film represented by Tl 2 Ba 2 CuO 6 by heat treatment at ℃ for 10 minutes to 10 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2224418A JPH0710734B2 (en) | 1990-08-28 | 1990-08-28 | Method for producing oxide superconductor thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2224418A JPH0710734B2 (en) | 1990-08-28 | 1990-08-28 | Method for producing oxide superconductor thin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04108612A JPH04108612A (en) | 1992-04-09 |
| JPH0710734B2 true JPH0710734B2 (en) | 1995-02-08 |
Family
ID=16813468
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2224418A Expired - Fee Related JPH0710734B2 (en) | 1990-08-28 | 1990-08-28 | Method for producing oxide superconductor thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0710734B2 (en) |
-
1990
- 1990-08-28 JP JP2224418A patent/JPH0710734B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04108612A (en) | 1992-04-09 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |