JPH01157008A - Superconductive thin film - Google Patents
Superconductive thin filmInfo
- Publication number
- JPH01157008A JPH01157008A JP62314503A JP31450387A JPH01157008A JP H01157008 A JPH01157008 A JP H01157008A JP 62314503 A JP62314503 A JP 62314503A JP 31450387 A JP31450387 A JP 31450387A JP H01157008 A JPH01157008 A JP H01157008A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- substrate
- superconductive
- oxide
- temperature
- 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 25
- 239000000758 substrate Substances 0.000 claims abstract description 19
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 9
- 239000002887 superconductor Substances 0.000 claims description 17
- 239000004020 conductor Substances 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000007704 transition Effects 0.000 abstract description 10
- 239000010408 film Substances 0.000 abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 7
- 239000010453 quartz Substances 0.000 abstract description 4
- 239000004570 mortar (masonry) Substances 0.000 abstract description 3
- 239000008188 pellet Substances 0.000 abstract description 3
- 229910021521 yttrium barium copper oxide Inorganic materials 0.000 abstract description 3
- 238000005289 physical deposition Methods 0.000 abstract 1
- 238000005118 spray pyrolysis Methods 0.000 abstract 1
- 238000004544 sputter deposition Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000000470 constituent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052747 lanthanoid Inorganic materials 0.000 description 3
- 150000002602 lanthanoids Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 239000011882 ultra-fine particle 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
- 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
本発明は高い導電性を有し、高温超電導性を示す新規な
超電導体薄膜に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel superconductor thin film having high electrical conductivity and exhibiting high temperature superconductivity.
従来の技術
最近、ランタニウム（Ｌａ）−バリウム（Ｂａ）−銅（
Ｏｕ）−酸素（０）あるいはイツトリウム（Ｙ ） −
Ｂａ−Ｏｕ−０からなる酸化物導電体が高い超電導転移
点（Ｔｃ）を有するという重要な発見が為された。Ｔｃ
としては構成元素或は化合物組成の制御により３０以上
ＬＯＯＫ（−１７３℃）迄の値が報告されている。特に
、Ｙ−Ｂａ−Ｏｕ−０系（以下ＹＢＯＯと略す）では、
３金属の原子比率が１：２：３の時最も高いＴｃが得ら
れ、電気抵抗がゼロとなる温度（Ｔｏｆｆ と略す）
は、最も再現性のあるデータで、９５にであると言われ
ている。酸素の含有量に関しては、６．９程度であろう
と予想されている。更に、ＹＢＣＯ系でＹをランタニド
系列元素（例えば、Ｌｕ、 Ｙｂ、 Ｔｍ、ｇｒ、 Ｈ
ｏ、 Ｄｙ、 Ｇｄ、 Ｅｕ、 Ｓｍ、 Ｎｄ、 Ｌａ
）で置き換えた化合物が多く合成されており、その犬、
半が９０に以上のＴｃを示している。この様に、高い温
度で超電導を示す酸化物導電体は、Ｏｕ −０を基本元
素として含み、イツトリウムあるいはランタニド元素お
よびアルカリ土類元素により結晶構造及び電子状態をう
まく制御されたものであると言える。Conventional technology Recently, lanthanium (La)-barium (Ba)-copper (
Ou) - oxygen (0) or yttrium (Y) -
An important discovery has been made that oxide conductors consisting of Ba-Ou-0 have a high superconducting transition temperature (Tc). Tc
Values of 30 or more up to LOOK (-173°C) have been reported by controlling the constituent elements or compound composition. In particular, in the Y-Ba-Ou-0 system (hereinafter abbreviated as YBOO),
The highest Tc is obtained when the atomic ratio of the three metals is 1:2:3, and the temperature at which the electrical resistance becomes zero (abbreviated as Toff)
is said to be the most reproducible data, with a value of 95. The oxygen content is expected to be around 6.9. Furthermore, in the YBCO system, Y is replaced by a lanthanide series element (for example, Lu, Yb, Tm, gr, H
o, Dy, Gd, Eu, Sm, Nd, La
) have been synthesized, and the dog,
Half of the samples showed a Tc of 90 or more. In this way, it can be said that oxide conductors that exhibit superconductivity at high temperatures contain Ou-0 as a basic element, and have their crystal structures and electronic states well controlled by yttrium or lanthanide elements and alkaline earth elements. .
また、極最近オプンンスキー氏らは、フッ素を含むＹ−
Ｂａ−Ｃｊｕ−０系酸化物に於て１５０にのＴｏｆｆを
認めている（フィジカル レビュー レターズ；Ｐｈｙ
ｓ、 ｒ（、ｅｖ、Ｌｅｔｔ、 誌、５８巻、２５
９７頁（１９８７年））。更に、他の元素を添加するこ
とにより室温以上での超電導の兆しが見えたとの報告も
ある。更に、江原氏らはＹ−Ｂ ａ−８ｒ−Ｏｕ −０
から成る酸化物に於て、６５°Ｃで抵抗がゼロになる現
象を報告している（ジャーナル オブ アプライド フ
ィツクス；Ｊ。In addition, very recently, Mr. Opunski et al.
Toff of 150 is recognized in Ba-Cju-0 series oxides (Physical Review Letters; Phys.
s, r(, ev, Lett, Magazine, vol. 58, 25
97 pages (1987)). Furthermore, there are reports that signs of superconductivity at temperatures above room temperature can be seen by adding other elements. Furthermore, Mr. Ehara et al. Y-B a-8r-Ou -0
reported that the resistance becomes zero at 65°C in an oxide consisting of (Journal of Applied Fixtures; J.
Ａｐｐｌ、Ｐｈｙｓ０誌、２６巻、１９８７年）。Appl, Phys0 Journal, Volume 26, 1987).
一方、これらの超電導体がエレクトロニクスデバイスと
して用いられるには、薄膜あるいは厚膜の製造が必須で
ある。その様な観点から、酸化物＠雷導体の皮膜化の検
討が行われ、スパッタリング、スクリーン印刷などによ
りある程度の特性を有する薄膜が調製されている。現在
酸化物超電導体の薄膜化で最も問題になっているのは、
基板材料の制約である。確実に再現性および安定性の高
い超電導体薄膜を与える基板材料はチタン酸ストロンチ
ウムのみであると言われている。On the other hand, in order for these superconductors to be used as electronic devices, it is essential to manufacture thin or thick films. From this point of view, studies have been conducted on forming films of oxides@lightning conductors, and thin films with certain characteristics have been prepared by sputtering, screen printing, etc. Currently, the biggest problem in thinning oxide superconductors is
This is a limitation of the substrate material. It is said that strontium titanate is the only substrate material that reliably provides superconductor thin films with high reproducibility and stability.
発明が解決しようとする問題点
以上述べた、超電導体および薄膜の性質に関し、本発明
が解決しようとする問題点は二つある。最近報告されて
いる１００に以上の転移点を有する超電導体は、再現性
に乏しく、安定性が殆ど無いことが第一の問題点である
。事実、ＩＢＭのグループの最近の発表によれば、それ
らのほとんどは測定上の問題点および組成の不均一性な
どを含んでいるといわれている。また、Ｙ−Ｂａ−Ｃｕ
−０系超電導体における元素置換効果の検討が多くの研
究者により行われているが、抵抗がゼロになる温度Ｔｏ
ｆｆ として９５に以上の値が得られたという信頼で
きる報告は一つもないのが現状である。Problems to be Solved by the Invention There are two problems to be solved by the present invention regarding the properties of superconductors and thin films described above. The first problem with recently reported superconductors having a transition point of 100 or more is that they have poor reproducibility and almost no stability. In fact, according to a recent announcement by an IBM group, most of them are said to include measurement problems and compositional non-uniformity. Also, Y-Ba-Cu
Many researchers are investigating the effect of element substitution in −0-based superconductors, but the temperature at which the resistance becomes zero, To
At present, there is no reliable report that a value of 95 or higher has been obtained for ff.
第二の問題点は、超電導薄膜を形成する基板材料の制限
である。入手が簡単で、安定性の高い超電導特性を与え
る基板材料が切望されている。The second problem is the limitation of the substrate material on which the superconducting thin film is formed. There is a need for substrate materials that are easily available and provide highly stable superconducting properties.
本発明は上記従来の問題点に鑑み、超電導転移点の向上
を図り、再現性および安定性に優れた超電導体薄膜の提
供を目的とするものである。In view of the above-mentioned conventional problems, the present invention aims to improve the superconducting transition point and provide a superconducting thin film with excellent reproducibility and stability.
問題点を解決するための手段
本発明は上記目的を達成するもので、その技術的手段は
、基板上に酸化錫薄膜を介してイツトリウム、バリウム
、銅及び酸素からなる酸化物導電体の薄膜を形成したこ
とを特徴とする超電導体薄膜の提供にある。Means for Solving the Problems The present invention achieves the above object, and its technical means is to deposit a thin film of an oxide conductor consisting of yttrium, barium, copper and oxygen on a substrate via a thin film of tin oxide. It is an object of the present invention to provide a superconductor thin film characterized in that it has been formed.
作用
本発明は、酸化錫基板の温度は実験装置の制約上６００
℃迄しか上げられなかったが、５００°Ｃ以上の温度で
スパッリングが行われた場合、得られた薄膜は明確な超
電導特性を示した。特に、６００°Ｃでは、超電導転移
温度が１１５にで、抵抗がゼロとなる温度が約１０１Ｋ
まで上昇していた。また、この皮膜を８００から９２０
°Ｃの間の温度で、酸素気流中で４０時間アニールする
と、ゼロ抵抗温度は１０５Ｋになり、超電導の安定性も
著しく向上した。Operation In the present invention, the temperature of the tin oxide substrate is set at 600°C due to the limitations of the experimental equipment.
When sputtering was carried out at temperatures above 500°C, the resulting thin films showed clear superconducting properties. In particular, at 600°C, the superconducting transition temperature is 115, and the temperature at which resistance becomes zero is approximately 101K.
It had risen to. In addition, this film is 800 to 920
When annealing for 40 hours in an oxygen stream at a temperature between 10°C and 10°C, the zero resistance temperature reached 105K, and the stability of the superconductor was also significantly improved.
本発明は、新規な基板材料を用いることにより、上に述
べた二つの問題点を同時に解決しようとするものである
。本発明者等は、鋭意研究を重ねた結果、構成元素の一
部として錫（Ｓｎ）を一部含むＹ−Ｂａ−Ｃｕ−Ｑ 系
酸化物が上記の問題点が解決することを見いだし、同一
出願人による発明として出願した。即ち、Ｙ−Ｂａ−Ｃ
ｕ−０光導電体のＢａの一部を錫に置き換えた導電体に
おいては、Ｔｃが１１０°Ｃ迄上昇することを初めて明
らかにした。The present invention attempts to simultaneously solve the above two problems by using a new substrate material. As a result of extensive research, the present inventors discovered that Y-Ba-Cu-Q-based oxides containing some tin (Sn) as a constituent element can solve the above problems. The application was filed as an invention by the applicant. That is, Y-Ba-C
It was revealed for the first time that in a conductor in which part of the Ba of the u-0 photoconductor was replaced with tin, Tc increased to 110°C.
更に、この発見に基づき、本発明者らは５ｎＯｚを基板
としてＹ −Ｂ ａ −Ｃｕ −０系の酸化物の薄膜を
形成すると、超電導転移点が１０５に一部で上昇し、安
定な超電導体薄膜が得られることを発見した。Furthermore, based on this discovery, the present inventors formed a thin film of Y-Ba-Cu-0 based oxide using 5nOz as a substrate, and the superconducting transition point partially rose to 105, making it a stable superconductor. It was discovered that a thin film could be obtained.
本発明の超電導体薄膜の基本的な製造方法は次のとおり
である。基板として用いる酸化錫は、通常のスプレーパ
イロリンス法によって、石英板上に形成させたものを用
いた。また、薄膜を形成する酸化物導電体は次のように
して調製された。メノウの乳鉢を用いて、最初に定めら
れた組成比（Ｙ：Ｂａ：Ｏｕの原子比率が１：２：３で
あることを基準にする）のＹ２Ｏ３、ＢａＯおよびＯｕ
Ｏ６るいはＣｕ超微粒子を粉砕し、均一になるまで混合
する。粉砕後、１２０℃以上の温度で十分に乾燥させ、
成型を行う。成型圧力は、５００Ｋｑ ／ ｃｉ以上で
あれば良かった。しかし、焼結体の均−性を考慮して、
一般には２．５ｔ／７の圧力で成型した。作られたベレ
ットの焼成は、通常の管状炉を用いて、空気中で行った
。焼成温度は、８５０から９４５℃の間が適当であった
。焼成後、８００℃に１０時間、４００°Ｃに１０時間
放置してアニールを施した。この様にして得られたＹ−
Ｂａ−Ｏｕ−０の焼結体は、９５にで抵抗がゼロとなる
超電導体であったが、次に、これをターゲットにして高
周波スパッタリングを行う。励起源が１３．６ＭＨｚの
マグネトロン゛スパッタリンーグ装置を用い、酸素を５
から１５％を含むアルゴンガスの濃度を２から１０ Ｐ
ａとし、種々の基板温度でスパッタリングを行った。こ
のようにして、３０から６０分のスパッタリングにより
、３０００から８０００ オングストロームの均一な皮
膜が得られた。The basic method for manufacturing the superconductor thin film of the present invention is as follows. The tin oxide used as the substrate was formed on a quartz plate by the usual spray pyrorinse method. Further, an oxide conductor forming a thin film was prepared as follows. Using an agate mortar, Y2O3, BaO and O of the initially determined composition ratio (based on the atomic ratio of Y:Ba:Ou being 1:2:3) were prepared.
Pulverize O6 or Cu ultrafine particles and mix until homogeneous. After pulverizing, thoroughly dry at a temperature of 120°C or higher,
Perform molding. The molding pressure had to be 500 Kq/ci or more. However, considering the uniformity of the sintered body,
Generally, molding was carried out at a pressure of 2.5t/7. Firing of the produced pellets was carried out in air using a conventional tube furnace. The firing temperature was suitably between 850 and 945°C. After firing, it was annealed by leaving it at 800°C for 10 hours and at 400°C for 10 hours. Y- obtained in this way
The Ba-Ou-0 sintered body was a superconductor whose resistance became zero at 95%, and next, high-frequency sputtering was performed using this as a target. Using a magnetron sputtering device with an excitation source of 13.6 MHz, oxygen was
The concentration of argon gas containing 15% from 2 to 10 P
a, and sputtering was performed at various substrate temperatures. In this way, a uniform film of 3000 to 8000 angstroms was obtained after 30 to 60 minutes of sputtering.
実施例 以上に本発明の実施例を詳細に説明する。Example The embodiments of the present invention will be described in detail above.
〔実施例１〕
試薬として入手したｙ２ｏ３、ＢａＯおよびＯｕＯをメ
ノウの乳鉢で高純度エタノールを滴下しつつ、完全に粉
砕した。この粉末を５０７から１０２の間の重さとして
秤量し、直径１３ｃｒｎの成型治具の甲に充填し加圧し
た。圧力は約２５００Ｋｙ／ｃｒ／ｌで、排気しつつ３
０分間行った。このペレットを白金板の上に置き、管状
炉の中のにセットして熱処理を行った。例えば、４時間
の熱処理の結果、９００°Ｃでは２００８／ｃｍであっ
た。最高の電導度は９００から９４０℃の間の温度で得
られ、５００から７００８／ｃＩｎで４つだ。また、９
４５℃以上の温度では、抵抗が再び上昇する傾向が見ら
れた（例えは９８０°Ｃで約７ Ｑ Ｓ ７ｃｍ ）。[Example 1] y2o3, BaO, and OuO obtained as reagents were completely ground in an agate mortar while dropping high-purity ethanol. This powder was weighed to have a weight between 507 and 102, and was filled into the shell of a molding jig having a diameter of 13 crn and pressurized. The pressure is about 2500Ky/cr/l, and while exhausting
It lasted 0 minutes. The pellets were placed on a platinum plate and placed in a tube furnace for heat treatment. For example, the result of heat treatment for 4 hours was 2008/cm at 900°C. The highest conductivities are obtained at temperatures between 900 and 940° C. and 4 between 500 and 7008/cIn. Also, 9
At temperatures above 45°C, there was a tendency for the resistance to rise again (eg, about 7 Q S 7cm at 980°C).
このようにして作られたＹＢＣＯ酸化物導電体をターゲ
ットにし、酸素を１５％含むアルゴンガスを用い、［’
ｔＦマグネトロンスパッタリングを行った。ガス圧は３
Ｐａで、高周波入力は１５０Ｗに設定した。基板は５ミ
クロン厚の酸化錫を持つ石英基板（面積抵抗７５０）で
、スパッタリング甲の基板温度は５５０℃とした。約２
時間のスパッタリングにより、黒色の、約１ミクロンの
均一膜が形成された。この様にして得られた薄膜の固有
型導度は１２０８／ｃＩｎで、温度−抵抗特性の測定か
ら明確な超電導性が確認された。即ち、室温から１００
Ｋまでは殆ど抵抗の温度変化はないが、１００により抵
抗が急激に降下し、９６〜９７にでゼロ抵抗を示した。Targeting the YBCO oxide conductor made in this way, using argon gas containing 15% oxygen, ['
tF magnetron sputtering was performed. Gas pressure is 3
The high frequency input was set to 150W. The substrate was a 5 micron thick quartz substrate with tin oxide (area resistance 750), and the substrate temperature of the sputtering layer was 550°C. Approximately 2
After time sputtering, a black, uniform film of approximately 1 micron was formed. The intrinsic conductivity of the thin film thus obtained was 1208/cIn, and clear superconductivity was confirmed by measurement of temperature-resistance characteristics. That is, from room temperature to 100
There is almost no change in resistance with temperature up to 100 K, but the resistance drops rapidly at 100 K and shows zero resistance at 96 to 97 K.
これに反し、６００°Ｃでスパッターされた皮膜はＴｃ
が１０５にの急峻な超電導転移を示した、Ｔｏｆｆ
が１００にと著しい上昇を示した。その特性は非常に安
定で、空気中に放置した後でも、繰り返し再現をするこ
とが出来た。In contrast, the film sputtered at 600°C
showed a steep superconducting transition at 105, Toff
showed a remarkable increase to 100. Its properties were extremely stable and could be reproduced repeatedly even after being left in the air.
〔実施例２〕
ＣｕＯの代わりに銅の超微粒子（平均粒径３００オング
ストローム）を用い、Ｙ：Ｂａ：Ｃｕの原子比率がｌ：
２：３となるような組成を用い、実施例１と同様の方法
で粉砕混合、焼結を行った。[Example 2] Ultrafine copper particles (average particle size 300 angstroms) were used instead of CuO, and the atomic ratio of Y:Ba:Cu was l:
Grinding, mixing, and sintering were performed in the same manner as in Example 1 using a composition with a ratio of 2:3.
９５０℃で１０時間焼結して得られた酸化物をターゲッ
トにして、３５０°Ｃの基板温度で１時間スパッターし
た。次に、得られた皮膜を酸素気流中で約１０時間、８
５０°Ｃのアニールを行った。抵抗−温度特性の測定の
結果、Ｔｏｎは１１４Ｋまで上昇し、Ｔｏｒｆは１０４
から１０５にの間であった。また、この特性は、サンプ
ルを湿気に曝さなければ倒産でも再現させることが出来
た。この様な高い転移点をもつセラミックス電導体は、
スパッタリングあるいはアニールの過程でＢａがＳｎに
より部分的に置換された結果化じたものと思われる。た
だし、アニール条件が厳しくなる（９００以上、数１０
時間以上）と、スパッター膜の電導度が急激に低下し、
超電導特性が明確でなくなる傾向が観測された。Using the oxide obtained by sintering at 950°C for 10 hours as a target, sputtering was performed at a substrate temperature of 350°C for 1 hour. Next, the obtained film was heated for about 10 hours in an oxygen stream for 8 hours.
Annealing was performed at 50°C. As a result of measuring resistance-temperature characteristics, Ton rose to 114K and Torf rose to 104K.
It was between 105 and 105. Moreover, this property could be reproduced even in bankruptcies as long as the sample was not exposed to moisture. Ceramic conductors with such a high transition point are
This appears to be the result of Ba being partially replaced by Sn during the sputtering or annealing process. However, the annealing conditions will be stricter (more than 900, several tens of
time), the conductivity of the sputtered film decreases rapidly,
A tendency for superconducting properties to become less clear was observed.
尚、現在知られている高温超電導体、Ｌｎ−Ｂａ−Ｃｕ
−０（Ｌｎはランタニド系列元素）、ではＣｕ−０から
なる電導路を取り巻＜Ｂａ原子の存在が超電導の基本に
なっているので、本発明はそれらの材料にも同様に適用
できることは明らかである。Furthermore, currently known high-temperature superconductors, Ln-Ba-Cu
-0 (Ln is a lanthanide series element), the existence of <Ba atoms surrounding a conductive path made of Cu-0 is the basis of superconductivity, so it is clear that the present invention can be applied to these materials as well. It is.
発明の効果
以上要するに、本発明は、酸化錫を表面に持つ基板上に
Ｙ−Ｂａ−Ｃｕ−０系の高温超電導薄膜を例えば物理蒸
着などにより形成することにより、ＢａがＳｎに部分的
に置換され、超電導転移点が約１０に迄上昇させられた
新規な超電導体薄膜を開示するものである。Effects of the Invention In short, the present invention provides a method in which Ba is partially replaced with Sn by forming a Y-Ba-Cu-0-based high-temperature superconducting thin film on a substrate having tin oxide on the surface, for example, by physical vapor deposition. The present invention discloses a novel superconductor thin film in which the superconducting transition point is raised to about 10.
現在の段階ではこの材料の結晶構造は決定されておらず
、本発明の効果の原因も今後基礎的に解明される必要が
ある。しかしながら、酸化物超電導体の構成元素の一部
としてＳｎを用いることは高温超電導体の製造及び特性
に大きな進歩をもたらすものである。At the current stage, the crystal structure of this material has not been determined, and the cause of the effects of the present invention will need to be fundamentally elucidated in the future. However, the use of Sn as part of the constituent elements of oxide superconductors represents a major advance in the production and properties of high temperature superconductors.
Claims (1)
ウム、バリウム、銅及び酸素から成る酸化物導電体の薄
膜を形成して得られることを特徴とする超電導体薄膜。A superconductor thin film characterized in that it is obtained by forming a thin film of an oxide conductor consisting of yttrium, barium, copper, and oxygen on a tin oxide thin film formed on a substrate as a base.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62314503A JPH01157008A (en) | 1987-12-11 | 1987-12-11 | Superconductive thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62314503A JPH01157008A (en) | 1987-12-11 | 1987-12-11 | Superconductive thin film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01157008A true JPH01157008A (en) | 1989-06-20 |
Family
ID=18054073
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62314503A Pending JPH01157008A (en) | 1987-12-11 | 1987-12-11 | Superconductive thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01157008A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103524131A (en) * | 2013-09-06 | 2014-01-22 | 河南师范大学 | Preparation method of rare-earth element doped YxSm(l-x)BCO superconducting thin film |
-
1987
- 1987-12-11 JP JP62314503A patent/JPH01157008A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103524131A (en) * | 2013-09-06 | 2014-01-22 | 河南师范大学 | Preparation method of rare-earth element doped YxSm(l-x)BCO superconducting thin film |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0356722A1 (en) | Oxide superconductor and method of producing the same | |
| CA1337149C (en) | Devices and systems based on novel superconducting material | |
| KR100268698B1 (en) | Process for making superconducting tl-pb-sr-ca-cu oxide films and devices | |
| US4900710A (en) | Process of depositing an alkali metal layer onto the surface of an oxide superconductor | |
| JPH02212351A (en) | Target material for forming superconducting ceramic film | |
| JPH01157008A (en) | Superconductive thin film | |
| JPH01215712A (en) | Production of thin film of superconductor | |
| EP0299796A2 (en) | Silver additives for ceramic superconductors | |
| US5270292A (en) | Method for the formation of high temperature semiconductors | |
| KR910004862B1 (en) | Target material for forming superconductive film | |
| AU631956B2 (en) | Vanadium-based superconducting metallic oxides | |
| Paulose et al. | Synthesis of YBa2SbO6: a possible new substrate for YBa2Cu3O7-delta thin films | |
| JPH01157009A (en) | Superconductor thin film | |
| JPH01219156A (en) | Manufacture of thin superconductor film | |
| JPH01156463A (en) | Thin superconductor film | |
| JPH10510799A (en) | Improved superconductor | |
| JPH02120233A (en) | Oxide superconducting material | |
| JPH0238359A (en) | Production of superconductor | |
| JPH01157417A (en) | Superconductor | |
| JPH02116623A (en) | Oxide superconducting material | |
| JPH01227480A (en) | Manufacture of superconducting thin-film | |
| JPH01215713A (en) | Production of superconductor | |
| JPH02120226A (en) | Superconducting material of oxide | |
| EP0375134A1 (en) | Bi-Ca-Sr-Cu-O superconducting glass ceramics | |
| Kurian et al. | Percolation Behavior of the Normal-State Resistivity and Superconductivity of the YBa 2 Cu 3 O 7− δ-Ba 2 GdNbO 6 Composite System |