JPH0297427A - Production of oxide superconducting thin film - Google Patents
Production of oxide superconducting thin filmInfo
- Publication number
- JPH0297427A JPH0297427A JP63248057A JP24805788A JPH0297427A JP H0297427 A JPH0297427 A JP H0297427A JP 63248057 A JP63248057 A JP 63248057A JP 24805788 A JP24805788 A JP 24805788A JP H0297427 A JPH0297427 A JP H0297427A
- Authority
- JP
- Japan
- Prior art keywords
- film
- superconducting thin
- thin film
- oxide superconducting
- substrate
- 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
- 239000010409 thin film Substances 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000010408 film Substances 0.000 claims abstract description 45
- 238000001659 ion-beam spectroscopy Methods 0.000 claims abstract description 5
- 230000003647 oxidation Effects 0.000 claims abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 4
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 abstract description 21
- 239000013078 crystal Substances 0.000 abstract description 17
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002245 particle Substances 0.000 abstract description 5
- 230000005012 migration Effects 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 3
- 238000012544 monitoring process Methods 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000010894 electron beam technology Methods 0.000 abstract 1
- 238000004544 sputter deposition Methods 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- 239000002887 superconductor Substances 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 5
- 229910001882 dioxygen Inorganic materials 0.000 description 5
- 239000000395 magnesium oxide Substances 0.000 description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 5
- -1 oxygen ions Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000002128 reflection high energy electron diffraction Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 230000008685 targeting Effects 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- 229910014454 Ca-Cu Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004343 Calcium peroxide Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000005513 bias potential Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000000097 high energy electron diffraction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は酸化物超伝導薄膜の製造方法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing an oxide superconducting thin film.
（従来の技術）
超伝導薄膜は、ジョセフソン接合による量子磁気干渉素
子や、超伝導ＬＳＩ配線、さらに超伝導能動素子等への
応用上欠かせないものである。近年、１９８２年２月米
国ヒユーストン大学のチュー（Ｃｈｕ）らにより発見さ
れた臨界温度９０に級のＹ系酸化物超伝導体を始めとし
、金属材料研究所の前出らによる臨界温度１１０に級の
Ｂｉ系酸化物超伝導体、さらに米国アーカンサス大学の
チュン（Ｚ、 Ｚ、 Ｃｈｅｎｇ）らによる臨界）温度
１２Ｏに級のＴｌ系酸化物超伝導体と液体窒素温度を越
える臨界温度を持つ酸化物超伝導体が相次いで発見され
た。このことにより従来液体Ｈｅを用いなければならな
かった超伝導応用デバイスが液体窒素で実現できること
になり、特にこれら酸化物超伝導体の薄膜化は液体窒素
温度以上動くジョセフソン接合による量子磁気干渉素子
や、超伝導ＬＳＩ配線、さらに超伝導能動素子等を実現
し、その応用は広く利用され得る。さて、Ｂｉ系超伝導
体薄膜は、従来基本的に次の３つの方法において製造さ
れてきた。(Prior Art) Superconducting thin films are indispensable for applications such as quantum magnetic interference devices using Josephson junctions, superconducting LSI wiring, and superconducting active devices. In recent years, Y-based oxide superconductors with a critical temperature of 90 degrees were discovered in February 1982 by Chu et al. of Hughston University in the United States, and others with a critical temperature of 110 degrees were discovered by the aforementioned researchers of the Institute for Materials Research. Bi-based oxide superconductors, Tl-based oxide superconductors with a critical temperature of 12 O, and oxides with critical temperatures exceeding the liquid nitrogen temperature, developed by Cheng et al. of the University of Arkansas in the United States. Superconductors were discovered one after another. As a result, superconducting applied devices that conventionally had to use liquid He can now be realized using liquid nitrogen, and in particular, the thinning of these oxide superconductors can be used to create quantum magnetic interference devices using Josephson junctions that move above the liquid nitrogen temperature. , superconducting LSI wiring, superconducting active devices, etc., and its applications can be widely used. Now, Bi-based superconductor thin films have conventionally been produced basically by the following three methods.
第一の方法は、例えばアプライドフィジックスレター（
Ａｐｐｌ、 Ｐｈｙｓ、 Ｌｅｔｔ、）巻５３．４２７
頁のようにマグネトロンスパッタ法を用い、Ｂｉ、 Ｓ
ｒ、 Ｃａ、 Ｃｕの組成からなる単一ターゲットを用
いて成膜を行い、この膜を後から酸素中８８０°Ｃ熱処
理を加える事により８３にでゼロ抵抗を示すＣ軸配向膜
が得られている。The first method is, for example, Applied Physics Letter (
Appl, Phys, Lett,) Volume 53.427
Using the magnetron sputtering method as shown in
By forming a film using a single target consisting of R, Ca, and Cu, and then heat-treating this film at 880°C in oxygen, a C-axis oriented film exhibiting zero resistance was obtained in 83. There is.
また第二の方法としては例えばアプライドフィジックス
レター（Ａｐｐｌ、 Ｐｈｙｓ、 Ｌｅｔｔ、）巻５３
．３３７頁のようにパルスレーザ−を用い、第一の方法
と同様単一ターゲットを用いて成膜を行い、後に８７５
°Ｃの酸素中熱処理を行うことで８０にの超伝導薄膜を
得ている。The second method is, for example, Applied Physics Letters (Appl, Phys, Lett,) Vol. 53.
．． As shown on page 337, film formation was performed using a pulsed laser and a single target as in the first method, and later on 875
A superconducting thin film of 80 °C was obtained by heat treatment in oxygen at 80 °C.
さらに第三の方法としては、例えば、アプライドフィジ
ックスレター（Ａｐｐｌ、 Ｐｈｙｓ、 Ｌｅｔｔ、）
巻５３゜６２４頁のようにＢｉ、 Ｓｒ、 Ｃａ、 Ｃ
ｕをそれぞれ独立した蒸着源から同時に蒸発させ、成膜
後８６０°Ｃの酸素中熱処理をおこなうことで、３５に
でゼロ抵抗超伝導膜を得ている。Furthermore, as a third method, for example, Applied Physics Letter (Appl, Phys, Lett,)
As per Volume 53, page 624, Bi, Sr, Ca, C
A zero-resistance superconducting film was obtained in 35 by simultaneously evaporating u from independent vapor deposition sources and performing heat treatment in oxygen at 860°C after film formation.
（発明が解決しようとする課題）
しかし、いずれの場合も従来の超伝導膜製造法では超伝
導膜を作るために８５０°Ｃ以上の高温熱処理が必要な
こと、また、膜はＣ軸配向しているものの表面が荒れて
いること、及び超伝導のオンセットは１１０Ｋに見えて
いるものの、最終的なゼロ抵抗温度が低いこと等の理由
により、デバイス応用を困難にしている。また、ジョセ
フソンジャンクションの均質性を高めるためには単結晶
膜であることが望ましい。(Problem to be solved by the invention) However, in any case, the conventional superconducting film manufacturing method requires high-temperature heat treatment of 850°C or higher to make a superconducting film, and the film is C-axis oriented. The surface of the material is rough, and although the onset of superconductivity appears to be 110 K, the final zero resistance temperature is low, making device application difficult. Further, in order to improve the homogeneity of the Josephson junction, it is desirable to use a single crystal film.
本発明の目的は、このＢｉ系酸化物超伝導薄膜を、基板
」二に単結晶膜として低温で合成する方法を提供する事
にある。An object of the present invention is to provide a method for synthesizing this Bi-based oxide superconducting thin film as a single crystal film on a substrate at a low temperature.
（課題を解決するための手段）
本発明は、ターゲットとしてＢｉ２Ｏ３とＳｒ、、・Ｃ
ａ、・Ｃｕ２・Ｏｘ（ただし０＜ｗ＜５．０＜ｙ＜５．
１＜ｚ＜５．Ｏ＜ｘ）の２種類のターゲットを交互にも
ちいイオンビームスパッタ法により、基板上に酸化物超
伝導薄膜を交互に層状成長させる酸化物超伝導薄膜の製
造方法と、成膜プロセス中に真空中容器内に高周波（Ｒ
Ｆ）を導入すること、ターゲットとして酸化ビスマスの
代りに（Ｂｉ２Ｏ３）１−ｘ（Ｐｂ０入（ただし０＜ｘ
＜０．１）の組成を用いる前記酸化物超伝導薄膜の製造
方法である。(Means for Solving the Problem) The present invention uses Bi2O3 and Sr as targets.
a, ・Cu2・Ox (0<w<5.0<y<5.
1<z<5. A method for producing an oxide superconducting thin film in which oxide superconducting thin films are grown in layers on a substrate by ion beam sputtering using alternately two types of targets (O < High frequency (R
F) as a target instead of bismuth oxide (Bi2O3)1-x (with Pb0 (however, 0<x
<0.1).
本方法では、Ｂｉ系酸化物超伝導体の結晶構造に特有の
Ｃ軸方向に（Ｂｉ−○）２原子層／（Ｓｒ−ＣａＣｕ−
０）ペロブスカイト型層／（Ｂｉ−０）２原子層・・・
の周期構造を人工的に積層成長させるもので、各層膜厚
は（Ｂｉ−０）層５人、（Ｓｒ−Ｃａ−Ｃｕ・Ｏ）層は
Ｂｉ系の８０に相の場合で１０人、１１０に相の場合に
は１３人に設定する。望ましくは基板温度を５００°Ｃ
〜８００°Ｃ１基板上の酸素ガス分圧を２Ｘ１０−４Ｔ
ｏｒｒ以上に保つと、エピタキシャル成長したＢｉ系酸
化物超伝導薄膜が合成される。この時各積層プロセスの
間に１０秒以上の緩和時間を設けることが望ましく、こ
の間に表面のスパッタ粒子のマイグレーションと積層相
の結晶性の改質が起こる。さらに、酸化ビスマス、また
はストロンチウム・カルシウム・銅酸化物は基板上にヘ
テロエピタキシャル成長させる事ができ、エピタキシャ
ル層を初期に約１０〜１００人程度成長させる事により
その後の膜成長プロセスにより単結晶のＢｉ系酸化物超
伝導薄膜が成長する。さらに真空チャンバー内にＲＦを
導入することでスパッタ粒子を活性化し膜の結晶化温度
を下げることができると共に酸素もイオン化されること
により各構成元素の酸化が促進される。さらにＲＦもし
くは酸素イオン源より生成された酸素イオンをＩＯＶ〜
８０■に加速して膜成長面に照射することにより膜成長
面での酸化とマイグレーションが促進され膜の結晶性の
改善と膜表面の平坦性化がよくなる。さらにＢｉの一部
をＰｂで置換することにより超伝導特性が改善され転移
がシャープになる。これらのエピタキシャル膜は酸化マ
グネシウム（ＭｇＯ）単結晶、チタン酸ストロンシウム
（ＳｒＴｉ０３）単結晶、イツトリウム安定化ジルコニ
ア（ＹＳＺ）単結晶、ジルコニア（ＺｒＯ□）単結晶い
ずれの基板上にも合成することができる。In this method, two atomic layers (Bi-○)/(Sr-CaCu-
0) Perovskite type layer/(Bi-0) two atomic layer...
The periodic structure is artificially layered and grown, and the thickness of each layer is 5 layers for the (Bi-0) layer, 10 layers for the (Sr-Ca-Cu・O) layer in the case of Bi-based 80 phase, and 110 layer for the Bi-based layer. In the case of phase 1, it is set to 13 people. Preferably the substrate temperature is 500°C.
~800°C Oxygen gas partial pressure on one substrate 2X10-4T
If the temperature is maintained above orr, an epitaxially grown Bi-based oxide superconducting thin film is synthesized. At this time, it is desirable to provide a relaxation time of 10 seconds or more between each lamination process, during which migration of sputtered particles on the surface and modification of the crystallinity of the laminated phase occur. Furthermore, bismuth oxide or strontium/calcium/copper oxide can be grown heteroepitaxially on the substrate. An oxide superconducting thin film is grown. Furthermore, by introducing RF into the vacuum chamber, sputtered particles can be activated and the crystallization temperature of the film can be lowered, and oxygen is also ionized, thereby promoting oxidation of each constituent element. Furthermore, oxygen ions generated from RF or an oxygen ion source are
By irradiating the film growth surface at an acceleration of 80 cm, oxidation and migration on the film growth surface are promoted, improving the crystallinity of the film and flattening the film surface. Furthermore, by substituting a part of Bi with Pb, the superconducting properties are improved and the transition becomes sharper. These epitaxial films can be synthesized on any of the following substrates: magnesium oxide (MgO) single crystal, strontium titanate (SrTi03) single crystal, yttrium stabilized zirconia (YSZ) single crystal, and zirconia (ZrO□) single crystal. can.
（実施例）
多層周期構造薄膜を製造するために用いたデュアルのイ
オンビームスパッタ装置を第１図に示す。(Example) FIG. 1 shows a dual ion beam sputtering apparatus used to manufacture a multilayer periodic structure thin film.
真空チャンバー１２は２基のカウフマン型イオン源１．
２を装備し、それぞれＢｉ２Ｏ３ターゲット３、Ｓｒ−
Ｃａ−Ｃｕ−０（組成比２：２：３）ターゲット４をス
パッタする。スパッタされた粒子３゛、４′は天板５で
発散視野が制限され、さらに真空チャンバー外部から駆
動されるシャッター６．７及び水晶振動子膜厚計１５に
より膜厚をモニターしながらシャッターの交互開閉によ
り多層周期構造が形成される。９はヒータ、１３はＲＨ
ＥＥＤ用電子銃、１４はＲＨＥＥＤスクリーンである。The vacuum chamber 12 has two Kaufmann type ion sources 1.
2, Bi2O3 target 3, Sr-
A Ca-Cu-0 (composition ratio 2:2:3) target 4 is sputtered. The sputtered particles 3' and 4' have a divergent field of view restricted by the top plate 5, and the shutters are alternately operated while monitoring the film thickness using shutters 6 and 7 driven from outside the vacuum chamber and a crystal oscillator film thickness gauge 15. A multilayer periodic structure is formed by opening and closing. 9 is heater, 13 is RH
An electron gun for EED, 14 is a RHEED screen.
この時チャンバー内の真空度は４Ｘ １０−’ ｔｏｒ
ｒ、基板付近は酸化促進のために酸素ガスを吹き付は局
部的に２Ｘ １Ｏ−３ｔｏｒｒの酸素分圧とした。基板
温度は６２Ｏ°Ｃとし、基板面内の膜厚分布を避けるよ
うに６０ｒｐｐｍの回転を与えている。チャンバー内は
、ニュートラライザでイオン源からでるＡｒ＋を中和し
ている。イオン源１の出力を６００Ｖ、 ３０ｍＡとし
た時にＢ１２Ｏ３の成膜速度は０．２Ａ／ｓｅｃであり
、イオン源２の出力を６００ｖ、４０ｍＡとした時の５
ｒ−Ｃａ−Ｃｕ−０の成膜速度は０．１８人／ｓｅｅで
あった。At this time, the degree of vacuum in the chamber is 4X 10-' tor
r, oxygen gas was locally blown near the substrate to promote oxidation at an oxygen partial pressure of 2×1O−3 torr. The substrate temperature was 620° C., and rotation was applied at 60 rpm to avoid film thickness distribution within the substrate surface. Inside the chamber, a neutralizer neutralizes Ar+ emitted from the ion source. When the output of ion source 1 was set to 600 V and 30 mA, the film formation rate of B12O3 was 0.2 A/sec, and when the output of ion source 2 was set to 600 V and 40 mA, it was 5.
The film formation rate of r-Ca-Cu-0 was 0.18 people/see.
次にＭｇ０（１００）基板を用いた成膜例を示す。基板
温度６３０°Ｃ１基板付近の酸素ガス分圧ｌＸｌ０−２
Ｔｏｒｒの条件で周期長３６Ａの膜を成膜中にＲＨＥＥ
Ｄパターンで確認しながら形成した。まず基板上に５ｒ
２Ｃａ２Ｃｕ３０Ｘ７２成長させ、ＭｇＯの基板方位を
一致させてバッファー層としての５ｒＣａＣｕＯをヘテ
ロエビタギシャル成長させた。この場合の５ｒＣａＣｕ
Ｏ層は３０人である。ヘテロエピタキシャル層成膜後４
分間の緩衝時間の後ＢｉＯをエピタキシャル成長させた
。Next, an example of film formation using an Mg0 (100) substrate will be shown. Substrate temperature 630°C1 Oxygen gas partial pressure near the substrate lXl0-2
RHEE while forming a film with a periodic length of 36A under Torr conditions.
It was formed while checking with the D pattern. First, place 5R on the board.
2Ca2Cu30X72 was grown, and 5rCaCuO was heteroevitably grown as a buffer layer by matching the substrate orientation of MgO. 5rCaCu in this case
There are 30 people in the O layer. After heteroepitaxial layer deposition 4
After a buffer time of 1 minute, the BiO was epitaxially grown.
さらに４分間の緩衝時間を経て交互に１３人の（Ｓｒ−
Ｃａ−Ｃｕ−０）／（Ｂｉ−０）／−・−と成長させた
。ＲＨＥＥＤの回折スポットはストリーク状になり膜表
面の平坦性が良好である事、さらにエピタキシャル成長
が持続している事を確認した。この人工的周期長１８人
を１５回繰り返し総膜厚３００人の時のＸ線回折パター
ンを第２図に示す。このｙｔＱ回折パターンより、設計
値通りに３６人（１８人×２）のＢｉ系超伝導体の１１
０に層がきれいにＣ軸配向してできている事が分かる。After another 4 minutes of buffering time, 13 (Sr-
It was grown as Ca-Cu-0)/(Bi-0)/-.-. The RHEED diffraction spot became streak-like, confirming that the film surface had good flatness and that epitaxial growth continued. Figure 2 shows the X-ray diffraction pattern when this artificial period length of 18 people was repeated 15 times and the total film thickness was 300 people. From this ytQ diffraction pattern, 11
It can be seen that the layer 0 has a neat C-axis orientation.
この膜の電気抵抗は、１１０Ｋにオンセットを持ち１０
７にで超伝導となることが確認された。同様の手段にお
いてＢｉ２Ｏ３をターゲットとし、Ｂ１−０を５人、５
ｒ２Ｃａ１Ｃｕ２Ｏｘをターゲットとして５ｒＣａＣｕ
Ｏを１Ｏ人と設定することによりＢｉ系８０に超伝導相
の膜も容易に作製できた。これらの作製例を第１表に示
す。また、バッファー層としてＢｉＯを用いる事も可能
であり、前述のプロセスを行う事で単結晶膜を合成する
ことができた。The electrical resistance of this film is 10K with an onset of 110K.
7, it was confirmed that it became superconducting. In the same way, targeting Bi2O3, 5 people and 5 people of B1-0
5rCaCu targeting r2Ca1Cu2Ox
By setting O to 10, it was possible to easily fabricate a Bi-based 80 superconducting phase film. Examples of these preparations are shown in Table 1. It is also possible to use BiO as a buffer layer, and a single crystal film could be synthesized by performing the process described above.
第１表
これらのプロセスにおいて、膜特性と基板温度及び基板
付近の酸素ガス分圧基板温度は５００〜８００°Ｃが適
当であり、５００’Ｃ以下では結晶性が悪く超伝導特性
が得られなくなり、８００°Ｃ以上では膜の組成ずれ及
び銅が還元されて非超伝導相が成長してしまう。酸素分
圧は結晶成長させるためには最低でも２Ｘ１０−４ｔｏ
ｒｒ必要である。また真空チャンバー内にＲＦを導入す
ることにより、ＲＦコイル内でスパッタ粒子が活性化さ
れ同時に酸素プラズマが発生する。この環境での上記同
様の成長をおこなうことにより膜の超伝導臨界温度の向
上が確認され、さらにＲＦプラズマにバイアス電位をか
けて酸素イオンをＩＯＶ〜８０Ｖに加速して基板に照射
することにより膜表面の平坦性を改善が見られた。また
加速酸素イオンの発生源として別に酸素イオンガンを真
空チャンバー内に設置することによっても同様の平坦性
を改善効果がみられた。Table 1 In these processes, the appropriate temperature for the film properties, substrate temperature, and oxygen gas partial pressure near the substrate is 500 to 800°C; below 500°C, the crystallinity is poor and superconducting properties cannot be obtained. , at 800° C. or higher, the film composition shifts and copper is reduced, resulting in the growth of a non-superconducting phase. Oxygen partial pressure should be at least 2X10-4to for crystal growth.
rr is necessary. Furthermore, by introducing RF into the vacuum chamber, sputtered particles are activated within the RF coil and at the same time oxygen plasma is generated. By performing the same growth as above in this environment, it was confirmed that the superconducting critical temperature of the film was improved, and by applying a bias potential to the RF plasma to accelerate oxygen ions to IOV~80V and irradiating the substrate, the film Improvement in surface flatness was observed. A similar effect of improving flatness was also seen by installing an oxygen ion gun in the vacuum chamber as a source of accelerated oxygen ions.
次にターゲットとして酸化ビスマスの代りに（Ｂｉ２Ｏ
３）ｌ−ｘ （ｐｂｏ入（０くＸ≦０．１）を用いてエ
ピタキシャル膜を作製した。成膜中の酸素ガス分圧はｌ
Ｘｌ０−２Ｔｏｒｒと固定しである。ｘ＝０．１程度ま
で超伝導特性は改善される（Ｔｃが５〜１５の上昇した
。）が、これ以上では膜中に異相が発生することにより
単結晶膜としての品質が落ちるのであまり実用的でなく
なる。Next, instead of bismuth oxide as a target (Bi2O
3) An epitaxial film was prepared using l-x (pbo input (0x≦0.1).The oxygen gas partial pressure during film formation was l
It is fixed at Xl0-2 Torr. The superconducting properties are improved until x = 0.1 (Tc increases by 5 to 15), but beyond this the quality of the single crystal film deteriorates due to the generation of different phases in the film, so it is not practical. It becomes irrelevant.
以上は酸化マグネシウム（ＭｇＯ）単結晶基板上に合成
されたエピタキシャル膜について述べたが、チタン酸ス
トロンチウム（ＳｒＴｉ０３）単結晶、イツトリウム安
定化ジルコニア（ＹＳＺ）単結晶、ジルコニア（Ｚｒ０
２）単結晶いずれの基板上にも同様に合成することがで
きた。The above has described an epitaxial film synthesized on a magnesium oxide (MgO) single crystal substrate, but strontium titanate (SrTi03) single crystal, yttrium stabilized zirconia (YSZ) single crystal, zirconia (Zr0)
2) Single crystals could be similarly synthesized on any substrate.
（発明の効果）
以上のように本発明を適応することにより、約１０７に
での超伝導を示し、かつ単一相のエピタキシャル膜を低
温で容易に合成され、デバイス等への応用上非常に有効
である。(Effects of the Invention) As described above, by applying the present invention, it is possible to easily synthesize a single-phase epitaxial film that exhibits superconductivity at about 107°C at a low temperature, which is extremely useful for applications to devices, etc. It is valid.
第１図は、本発明を実施したデュアルイオン系によるイ
オンビームスパッタ装置の構造概略図である。第２図は
Ｘ線回折図である。
図において、１，２・・・イオン源、３・・・Ｂｉ２Ｏ
３ターゲット、４・・・５ｒＣａＣｕＯ酸化物ターゲツ
ト、５・・・天板、６゜７・・・シャッター、８・・・
基板ホルダー、９・・・ヒータ、１０・・・ゲートバル
ブ、１１・・・真空排気ポンプ、１２・・・真空チャン
バー、１３・・・反射高エネルギー電子線回折（ＲＨＥ
ＥＤ）用電子銃、１４・・・ＲＨＥＥＤスクリーン、１
５・・・水晶振動子膜厚モニタである。FIG. 1 is a schematic structural diagram of an ion beam sputtering apparatus using a dual ion system in which the present invention is implemented. FIG. 2 is an X-ray diffraction diagram. In the figure, 1, 2... ion source, 3... Bi2O
3 target, 4...5rCaCuO oxide target, 5... top plate, 6° 7... shutter, 8...
Substrate holder, 9... Heater, 10... Gate valve, 11... Vacuum pump, 12... Vacuum chamber, 13... Reflected high energy electron diffraction (RHE)
ED) electron gun, 14...RHEED screen, 1
5...Crystal resonator film thickness monitor.
Claims (3)
ａ＿ｙ・Ｃｕ＿ｚ・Ｏ＿ｘ（ただし０＜ｗ＜５、０＜ｙ
＜５、１＜ｚ＜５、０＜ｘ）の２種類の組成のターゲッ
トを交互にもちいてイオンビームスパッタを行うことに
より、酸化物超伝導薄膜を交互に層状成長させることを
特徴とする酸化物超伝導薄膜の製造方法。(1) Bi_2O_3 and Sr_w・C as targets
a_y・Cu_z・O_x (0<w<5, 0<y
An oxidation method characterized by alternately growing oxide superconducting thin films in layers by performing ion beam sputtering using alternately targets with two types of compositions: <5, 1<z<5, 0<x). Method for manufacturing superconducting thin films.
を導入することを特徴とした特許請求の範囲第１項記載
の酸化物超伝導薄膜の製造方法。(2) Radio frequency (RF) is applied inside the vacuum container during the film formation process.
A method for producing an oxide superconducting thin film according to claim 1, characterized in that the method comprises introducing:
２Ｏ＿３）＿１＿−＿ｘ（ＰｂＯ）＿ｘ（ただし０＜ｘ
≦０．１）を用いることを特徴とした特許請求の範囲第
１項又は第２項記載の酸化物超伝導薄膜の製造方法。(3) Instead of bismuth oxide as a target (Bi_
2O_3)_1_-_x(PbO)_x (0<x
≦0.1), the method for producing an oxide superconducting thin film according to claim 1 or 2, wherein
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63248057A JPH0297427A (en) | 1988-09-30 | 1988-09-30 | Production of oxide superconducting thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63248057A JPH0297427A (en) | 1988-09-30 | 1988-09-30 | Production of oxide superconducting thin film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0297427A true JPH0297427A (en) | 1990-04-10 |
Family
ID=17172561
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63248057A Pending JPH0297427A (en) | 1988-09-30 | 1988-09-30 | Production of oxide superconducting thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0297427A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02149401A (en) * | 1988-11-29 | 1990-06-08 | Fujitsu Ltd | Preparation of superconducting film |
| JPH02233525A (en) * | 1989-03-06 | 1990-09-17 | Kawasaki Heavy Ind Ltd | Production of superconductive film |
| JPH04132280A (en) * | 1990-09-21 | 1992-05-06 | Agency Of Ind Science & Technol | Tunnel barrier deposition method |
| EP0939423A1 (en) * | 1998-02-26 | 1999-09-01 | Eaton Corporation | Ion source having wide output current operating range |
| US9630755B2 (en) | 2001-10-16 | 2017-04-25 | Medinstill Development Llc | Dispenser and method for storing and dispensing sterile product |
| US9668914B2 (en) | 2000-10-23 | 2017-06-06 | Dr. Py Institute Llc | Method for dispensing ophthalmic fluid |
| US9725228B2 (en) | 2000-10-23 | 2017-08-08 | Dr. Py Institute Llc | Fluid dispenser having a one-way valve, pump, variable-volume storage chamber, and a needle penetrable and laser resealable portion |
| US9938128B2 (en) | 2004-12-04 | 2018-04-10 | Medinstill Development Llc | One-way valve and apparatus and method of using the valve |
-
1988
- 1988-09-30 JP JP63248057A patent/JPH0297427A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02149401A (en) * | 1988-11-29 | 1990-06-08 | Fujitsu Ltd | Preparation of superconducting film |
| JPH02233525A (en) * | 1989-03-06 | 1990-09-17 | Kawasaki Heavy Ind Ltd | Production of superconductive film |
| JPH04132280A (en) * | 1990-09-21 | 1992-05-06 | Agency Of Ind Science & Technol | Tunnel barrier deposition method |
| EP0939423A1 (en) * | 1998-02-26 | 1999-09-01 | Eaton Corporation | Ion source having wide output current operating range |
| US9668914B2 (en) | 2000-10-23 | 2017-06-06 | Dr. Py Institute Llc | Method for dispensing ophthalmic fluid |
| US9725228B2 (en) | 2000-10-23 | 2017-08-08 | Dr. Py Institute Llc | Fluid dispenser having a one-way valve, pump, variable-volume storage chamber, and a needle penetrable and laser resealable portion |
| US9630755B2 (en) | 2001-10-16 | 2017-04-25 | Medinstill Development Llc | Dispenser and method for storing and dispensing sterile product |
| US9938128B2 (en) | 2004-12-04 | 2018-04-10 | Medinstill Development Llc | One-way valve and apparatus and method of using the valve |
| US10464801B2 (en) | 2004-12-04 | 2019-11-05 | Medinstill Development Llc | One-way valve and apparatus and method of using the valve |
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