JP2523013B2 - Manufacturing method of oxide superconducting thin film - Google Patents
Manufacturing method of oxide superconducting thin filmInfo
- Publication number
- JP2523013B2 JP2523013B2 JP1072871A JP7287189A JP2523013B2 JP 2523013 B2 JP2523013 B2 JP 2523013B2 JP 1072871 A JP1072871 A JP 1072871A JP 7287189 A JP7287189 A JP 7287189A JP 2523013 B2 JP2523013 B2 JP 2523013B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- superconducting thin
- oxide
- oxide superconducting
- manufacturing
- 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
- 239000010409 thin film Substances 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229910014454 Ca-Cu Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 7
- 238000004544 sputter deposition Methods 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910002367 SrTiO Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000002887 superconductor Substances 0.000 description 2
- 238000000137 annealing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910001179 chromel Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 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
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000013077 target material Substances 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
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Physical Vapour Deposition (AREA)
Description
【発明の詳細な説明】 （イ） 産業上の利用分野 本発明は酸化物超電導薄膜の製造法に関し、特にTl−
Ba−Ca−Cuの酸化物の超電導薄膜の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a method for producing an oxide superconducting thin film, and particularly Tl-
The present invention relates to a method for manufacturing a Ba-Ca-Cu oxide superconducting thin film.
（ロ） 従来の技術 近年、Tl−Ba−Ca−Cuの酸化物が液体窒素の沸点（77
K）より高い臨界温度で超電導状態に入ることが見出さ
れて脚光を浴びている。(B) Conventional technology In recent years, the oxide of Tl-Ba-Ca-Cu has a boiling point (77%) of liquid nitrogen.
K) has been in the limelight since it was found to enter the superconducting state at a higher critical temperature.
（ハ） 発明が解決しようとする課題 ところで、現在、液体ヘリウムを用いてMRIなどに実
用化されているNb系の超電導体は熱的安定性あるいは磁
気的安定性のために全て薄膜化あるいは線材化して用い
られている。従って酸化物超電導体も各種分野に用いる
には同様の理由で薄膜化あるいは線材化しなければなら
ない。(C) Problems to be solved by the invention By the way, Nb-based superconductors currently used in MRI and the like using liquid helium are all thin films or wire rods for thermal stability or magnetic stability. It is used after being converted. Therefore, in order to use oxide superconductors in various fields, it is necessary to make them thin or wire for the same reason.
（ニ） 課題を解決するための手段 Tl−Ba−Ca−Cuの酸化物であって、その組成比が3:2:
2:3のものをターゲットとし、スパッタリング法により
基板上に薄膜を形成した後、酸化雰囲気中でアニール処
理することを特徴とする酸化物超電導薄膜の製造法にあ
る。(D) Means for Solving the Problems An oxide of Tl-Ba-Ca-Cu having a composition ratio of 3: 2:
A method for producing an oxide superconducting thin film is characterized in that a thin film is formed on a substrate by a sputtering method with a target of 2: 3 and then annealed in an oxidizing atmosphere.
（ホ） 作用 本発明によれば、Tl−Ba−Ca−Cuの酸化物からなる超
電導薄膜を簡単な方法で容易に得ることができる。特
に、ターゲットとしてTl−Ba−Ca−Cuの酸化物であっ
て、その組成比が3:2:2:3のものを使用したため、Tl系
の酸化物超電導薄膜を効果的に構成することができる。(E) Function According to the present invention, a superconducting thin film made of an oxide of Tl-Ba-Ca-Cu can be easily obtained by a simple method. In particular, since a Tl-Ba-Ca-Cu oxide having a composition ratio of 3: 2: 2: 3 was used as a target, it is possible to effectively form a Tl-based oxide superconducting thin film. it can.
（ヘ） 実施例 ［第１実施例］ 第１図は本発明超電導薄膜を得るための装置の一例を
示し、同図において（１）はスパッタリング装置のベル
ジャーであって、排気系（２）が連なっている。（３）
は該ベルジャー（１）内に放電ガスであるアルゴンガス
を供給するアルゴンガスボンベで、バリアブルリークバ
ルブ（４）並びにストップバルブ（５）を介してベルジ
ャー（１）に連なっている。（６）（７）はベルジャー
（１）内に可動自在のシャッター（８）を介して対向配
置された対向電極で、その陽極（６）は接地されるとと
もに、その表面上に超電導薄膜を堆積させるSrTiO3基板
（９）が置かれている。(F) Example [First Example] FIG. 1 shows an example of an apparatus for obtaining a superconducting thin film of the present invention. In FIG. 1, (1) is a bell jar of a sputtering apparatus, and an exhaust system (2) is It is in a row. (3)
Is an argon gas cylinder for supplying an argon gas as a discharge gas into the bell jar (1), which is connected to the bell jar (1) via a variable leak valve (4) and a stop valve (5). (6) and (7) are counter electrodes that are arranged to face each other in the bell jar (1) through a movable shutter (8), and the anode (6) is grounded and a superconducting thin film is deposited on the surface thereof. The SrTiO 3 substrate (9) is placed.
一方、陰極（７）は超電導材料であるTl−Ba−Ca−Cu
の酸化物（組成比は、Tl:Ba:Ca:Cu＝3:2:2:3）の焼結体
からなるターゲット材にて構成されており、この陰極
（７）には負の高い電圧が印加されている。（10）（1
1）は高真空計、低真空計である。On the other hand, the cathode (7) is Tl-Ba-Ca-Cu which is a superconducting material.
Of the oxide (composition ratio Tl: Ba: Ca: Cu = 3: 2: 2: 3) is used as the target material, and this cathode (7) has a high negative voltage. Is being applied. (10) (1
1) is a high vacuum gauge and a low vacuum gauge.
上記焼結体からなるターゲットは、高純度試薬の固相
反応により形成される。すなわち純度99.9％のTl2O3（3
4.3g）、純度99.99％のBaCO3（19.7g）、純度99.99％の
CaCO3（10.0g）、純度99.99％のCuO（11.9g）の粉末
を、仕込み組成でTl:Ba:Ca:Cu＝3:2:2:3となるようにメ
タノール、エタノールなどの有機溶媒に加えてスターラ
にて撹拌し、次いで有機溶媒を蒸発させた後、乳鉢にて
すりつぶして粉末状にする。この粉末をアルミナキャッ
プで覆われたアルミナボートに入れて電気炉にて930℃
で30分間仮焼成し、仮焼成された粉末を成形器に入れ、
成形圧力750kgf/cm2でプレス加工してペレット状に固め
る。次にこのペレットを空気中において925℃で１分間
焼結して直径10cm、厚さ0.5cmのTl3Ba2Ca2Cu3OXの焼結
ターゲットを得る。The target made of the above-mentioned sintered body is formed by a solid-phase reaction of a high-purity reagent. That is, Tl 2 O 3 (3
4.3g), 99.99% pure BaCO 3 (19.7g), 99.99% pure
Powder of CaCO 3 (10.0g) and CuO (11.9g) with a purity of 99.99% was added to an organic solvent such as methanol or ethanol so that the composition was Tl: Ba: Ca: Cu = 3: 2: 2: 3. In addition, the mixture is stirred with a stirrer, then the organic solvent is evaporated, and then ground in a mortar to give a powder. This powder was put in an alumina boat covered with an alumina cap and heated in an electric furnace at 930 ° C.
Temporarily calcine for 30 minutes, put the calcined powder in the molding machine,
It is pressed at a molding pressure of 750 kgf / cm 2 and solidified into pellets. Next, the pellets are sintered in air at 925 ° C. for 1 minute to obtain a Tl 3 Ba 2 Ca 2 Cu 3 O X sintering target having a diameter of 10 cm and a thickness of 0.5 cm.
而して、アルゴンガスボンベ（３）からベルジャー
（１）内に純度99.9995％のアルゴンガスを3.0〜30.0mt
orrの圧力で供給すると同時に、スパッタ出力を100〜25
0Wとしてスパッタリング処理し、基板（９）に0.5〜５
μｍの厚みの膜を形成する。Then, from the argon gas cylinder (3) to the bell jar (1), argon gas having a purity of 99.9995% is 3.0 to 30.0 mt.
Sputter output is 100 to 25 at the same time as supply at orr pressure
Sputtering treatment was performed at 0 W, and the substrate (9) was 0.5 to 5
A film with a thickness of μm is formed.
その後、スパッタ装置から取り出して電気炉に入れ、
流量、２／分の酸素雰囲気中において室温から１℃／
秒で940℃まで昇温し940℃で10分のアニール処理を行い
−20℃／秒で室温まで降温して冷却した。尚、発明者等
の実験によれば、アニール温度、時間、特に温度は上記
した温度が最適であったが、雰囲気は酸化雰囲気であれ
ば酸素に限定されるものではなく、また冷却条件も超電
導状態を得るのに余り影響がないことが判明している。After that, remove it from the sputtering device and put it in an electric furnace.
Flow rate of 2 / min in oxygen atmosphere from room temperature to 1 ° C /
The temperature was raised to 940 ° C. in 10 seconds, annealed at 940 ° C. for 10 minutes, cooled to room temperature at −20 ° C./second and cooled. According to the experiments conducted by the inventors, the annealing temperature and time, especially the above-mentioned temperatures were optimal, but the atmosphere is not limited to oxygen as long as it is an oxidizing atmosphere, and the cooling condition is also superconducting. It has been found to have little effect on gaining status.
第２図はこのようにして得られた、Tl−Ba−Ca−Cu−
Ｏの超電導薄膜の温度に対する抵抗変化を示すものであ
る。抵抗の温度依存性は標準的な四端子電極法にて測定
され、接続は薄膜上にインジウム電極を圧接させる。温
度は金＋0.07％鉄−クロメルサーモカップルにより測定
する。また流した電流の密度は、0.5〜5A/cm2とする。FIG. 2 shows Tl-Ba-Ca-Cu-obtained in this way.
It shows a resistance change of O superconducting thin film with respect to temperature. The temperature dependence of the resistance is measured by a standard four-terminal electrode method, and the connection is made by pressing an indium electrode on the thin film. Temperature is measured with gold + 0.07% iron-chromel thermocouple. The density of the applied current is 0.5 to 5 A / cm 2 .
零抵抗温度は86K（−187℃）であるが、110K前後で抵
抗減少が観察される。このことから薄膜の一部に110K級
の超電導相が含まれているものと思われる。The zero resistance temperature is 86K (-187 ℃), but the resistance decrease is observed around 110K. From this, it is considered that a part of the thin film contains a 110K-class superconducting phase.
第３図はこのようにして得られた超電導薄膜のＸ線回
折パターンである。FIG. 3 is an X-ray diffraction pattern of the superconducting thin film thus obtained.
一方、超電導状態を立証する他の要因であるマイスナ
ー効果は110K付近から反磁性を示し始めた。On the other hand, the Meissner effect, another factor that proves the superconducting state, began to show diamagnetism at around 110K.
また、SrTiO3基板（９）の代わりに、MgO、YSZも基板
として使用可能である。Further, instead of the SrTiO 3 substrate (9), MgO or YSZ can be used as the substrate.
（ト） 発明の効果 本発明によれば、ターゲットとしてTl−Ba−Ca−Cuの
酸化物であって、その組成比が3:2:2:3のものを使用し
たため、通常のスパッタリング装置を用いる簡単な方法
でTl−Ba−Ca−Cuの酸化物の超電導薄膜が得られ、その
工業的価値は極めて大である。(G) Effect of the Invention According to the present invention, an oxide of Tl-Ba-Ca-Cu having a composition ratio of 3: 2: 2: 3 was used as a target, and therefore a normal sputtering apparatus was used. A simple method is used to obtain a Tl-Ba-Ca-Cu oxide superconducting thin film, and its industrial value is extremely large.
第１図は本発明による酸化物超電導薄膜を得るためのス
パッタリング装置の概略図、第２図は本発明の第１実施
例によって得られた超電導薄膜の抵抗−温度特性図、第
３図は同じく第１実施例によって得られた超電動薄膜の
Ｘ線回折パターン図 （１）……ベルジャー、（６）（７）……対向電極、
（９）……基板。FIG. 1 is a schematic diagram of a sputtering apparatus for obtaining an oxide superconducting thin film according to the present invention, FIG. 2 is a resistance-temperature characteristic diagram of the superconducting thin film obtained by the first embodiment of the present invention, and FIG. 3 is the same. X-ray diffraction pattern diagram of the super-electric thin film obtained in the first embodiment (1) ... Bell jar, (6) (7) ... Counter electrode,
(9) ... substrate.
───────────────────────────────────────────────────── 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 Ｈ０１Ｌ 39/24 ＺＡＡ Ｈ０１Ｌ 39/24 ＺＡＡＢ // Ｈ０１Ｂ 12/06 ＺＡＡ Ｈ０１Ｂ 12/06 ＺＡＡ (72)発明者 根本 雅昭 大阪府守口市京阪本通２丁目18番地 三 洋電機株式会社内 (72)発明者 水上 敦夫 大阪府守口市京阪本通２丁目18番地 三 洋電機株式会社内 (56)参考文献 特開 平１−236663（ＪＰ，Ａ) 特開 平２−44014（ＪＰ，Ａ) Ｊｐｎ．Ｊ．Ａｐｐｌ．Ｐｈｙｓ，27 （５）（1988）Ｐ．Ｌ849−51 Ｊｐｎ．Ｊ．Ａｐｐｌ．Ｐｈｙｓ，27 （12）（1988）Ｐ．Ｌ2321−23─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location H01L 39/24 ZAA H01L 39/24 ZAAB // H01B 12/06 ZAA H01B 12/06 ZAA (72) Inventor Masaaki Nemoto, 2-18-18 Keihan Hondori, Moriguchi City, Osaka, Sanyo Electric Co., Ltd. (72) Inventor, Atsushi Mizukami 2--18, Keihan Hondori, Moriguchi City, Osaka (56) References JP-A-1-236663 (JP, A) JP-A-2-44014 (JP, A) Jpn. J. Appl. Phys, 27 (5) (1988) P.P. L849-51 Jpn. J. Appl. Phys, 27 (12) (1988) P.P. L2321-23
Claims (1)
し、スパッタリング法により基板上に薄膜を形成した
後、酸化雰囲気中でアニール処理して、目的物であるTl
−Ba−Ca−Cuの酸化物の酸化物超電導薄膜を製造する方
法であって、 上記ターゲットのTl−Ba−Ca−Cuの組成比率を3:2:2:3
とすることを特徴とする酸化物超電導薄膜の製造法。1. A Tl-Ba-Ca-Cu oxide is used as a target, a thin film is formed on a substrate by a sputtering method, and then annealed in an oxidizing atmosphere to obtain the target Tl.
A method for producing an oxide superconducting thin film of an oxide of -Ba-Ca-Cu, wherein the composition ratio of Tl-Ba-Ca-Cu of the target is 3: 2: 2: 3.
And a method for producing an oxide superconducting thin film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1072871A JP2523013B2 (en) | 1988-03-25 | 1989-03-24 | Manufacturing method of oxide superconducting thin film |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7239088 | 1988-03-25 | ||
| JP63-72390 | 1988-03-25 | ||
| JP63-291436 | 1988-11-17 | ||
| JP29143688 | 1988-11-17 | ||
| JP1072871A JP2523013B2 (en) | 1988-03-25 | 1989-03-24 | Manufacturing method of oxide superconducting thin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02229717A JPH02229717A (en) | 1990-09-12 |
| JP2523013B2 true JP2523013B2 (en) | 1996-08-07 |
Family
ID=27300939
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1072871A Expired - Lifetime JP2523013B2 (en) | 1988-03-25 | 1989-03-24 | Manufacturing method of oxide superconducting thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2523013B2 (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0244014A (en) * | 1987-11-25 | 1990-02-14 | Kawatetsu Mining Co Ltd | Production of electroconductive or superconducting thin film |
| JP2790459B2 (en) * | 1988-03-17 | 1998-08-27 | 松下電器産業株式会社 | Manufacturing method of superconducting wiring |
-
1989
- 1989-03-24 JP JP1072871A patent/JP2523013B2/en not_active Expired - Lifetime
Non-Patent Citations (2)
| Title |
|---|
| Ｊｐｎ．Ｊ．Ａｐｐｌ．Ｐｈｙｓ，２７（１２）（１９８８）Ｐ．Ｌ２３２１−２３ |
| Ｊｐｎ．Ｊ．Ａｐｐｌ．Ｐｈｙｓ，２７（５）（１９８８）Ｐ．Ｌ８４９−５１ |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02229717A (en) | 1990-09-12 |
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