JPH01192720A - Production of superconducting thin film - Google Patents
Production of superconducting thin filmInfo
- Publication number
- JPH01192720A JPH01192720A JP63014387A JP1438788A JPH01192720A JP H01192720 A JPH01192720 A JP H01192720A JP 63014387 A JP63014387 A JP 63014387A JP 1438788 A JP1438788 A JP 1438788A JP H01192720 A JPH01192720 A JP H01192720A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- thin film
- superconducting thin
- film
- electron beam
- 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
- 238000004519 manufacturing process Methods 0.000 title description 2
- 239000000843 powder Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 26
- 229910052802 copper Inorganic materials 0.000 claims abstract description 18
- 229910052788 barium Inorganic materials 0.000 claims abstract description 14
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000004544 sputter deposition Methods 0.000 claims description 11
- 238000007740 vapor deposition Methods 0.000 claims description 11
- 238000010304 firing Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 16
- 239000007788 liquid Substances 0.000 abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 8
- 239000008188 pellet Substances 0.000 abstract description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 abstract description 3
- 238000000313 electron-beam-induced deposition Methods 0.000 abstract 2
- 230000008016 vaporization Effects 0.000 abstract 2
- 238000009834 vaporization Methods 0.000 abstract 2
- 238000001354 calcination Methods 0.000 abstract 1
- 238000001017 electron-beam sputter deposition Methods 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 21
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 13
- 238000010894 electron beam technology Methods 0.000 description 12
- 229910052727 yttrium Inorganic materials 0.000 description 12
- 239000000758 substrate Substances 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 6
- 238000000151 deposition Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052594 sapphire Inorganic materials 0.000 description 2
- 239000010980 sapphire Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- ANYNLKBYFRTNQP-UHFFFAOYSA-N [O].[Ti].[Sr] Chemical compound [O].[Ti].[Sr] ANYNLKBYFRTNQP-UHFFFAOYSA-N 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y02E40/641—
Abstract
Description
【発明の詳細な説明】
・′ 〔概要〕
超伝導薄膜の形成方法、特に電子ビーム（ＥＢ）蒸着、
スパッタ法による超伝導薄膜形成において、蒸着源（ソ
ース）として、ＲＥ、 ｇａｚｃｕ ｓｅｘの焼成粉体
に、ＲＢ＋ Ｂａｒ Ｃｕを粉体で混合させたものを用
いる方法に関し、
ＲＥＩ Ｂａ、Ｃｕ３０ｘを蒸着源として薄膜を形成す
る場合、成膜された薄膜に欠乏するＲＥとＣｕまたはＢ
ａとＣｕとが補償される超伝導薄膜の形成方法を提供す
ることを目的とし、
蒸着法あるいはスパッタ法によりＲＥ、Ｂａ工Ｃｕ３０
７−ｘ系（ただし、ＲＥは希土類元素）の超伝導薄膜を
作成するにおいて、ＲＥ、 Ｂａｒ Ｃｕの酸化物を１
：２：３の比で混合した後に焼成し、かくして得られた
焼成物を粉砕したものにＲＥ２Ｏ３とＣｕを粉体で加え
焼成したソースを用いることを特徴とする超伝導薄膜の
形成方法を含み構成する。[Detailed description of the invention] ・′ [Summary] A method for forming superconducting thin films, particularly electron beam (EB) evaporation,
Regarding the method of using RE, gazcu sex fired powder mixed with powder of RB+ Bar Cu as a vapor deposition source in forming a superconducting thin film by sputtering method, REI Ba, Cu30x as a vapor deposition source. When forming a thin film, RE and Cu or B, which are deficient in the formed thin film,
The purpose of this study is to provide a method for forming a superconducting thin film in which a and Cu are compensated.
In creating a superconducting thin film of the 7-x system (where RE is a rare earth element), RE, Bar Cu oxide,
: A method for forming a superconducting thin film characterized by using a source obtained by mixing the mixture at a ratio of 2:3 and firing the resulting fired product, adding RE2O3 and Cu in the form of powder to the pulverized product, and firing the resulting product. Configure.
本発明は、超伝導薄膜の形成方法、特に電子ビーム（Ｅ
Ｂ）蒸着、スパッタ法による超伝導薄膜形成において、
蒸着源（ソース）として、Ｙ、 Ｂａ２．Ｃｕ３−ＯＸ
の焼成粉体に、’Ｙ、 Ｂａ、 Ｃｕを粉体で混合させ
たものを用いる方法に関する。The present invention relates to a method for forming a superconducting thin film, particularly an electron beam (E)
B) In forming a superconducting thin film by vapor deposition or sputtering,
As a vapor deposition source, Y, Ba2. Cu3-OX
The present invention relates to a method using a powder mixture of Y, Ba, and Cu in the fired powder.
液体窒素温度で超伝導状態を示すＹ−Ｂａ−Ｃｕ−０系
セラミツクスが産業界に与えるインパクトは図り知れな
いものがある。かかるセラミックスをエレクトロニクス
に応用する場合に不可欠な事項は、その薄膜化である。The impact that Y-Ba-Cu-0 ceramics, which exhibit a superconducting state at liquid nitrogen temperatures, has on industry is immeasurable. When applying such ceramics to electronics, it is essential to reduce the thickness of the ceramics.
現在、スパッタ法、 ＥＢ蒸着法。Currently, sputtering method, EB evaporation method.
ＭＢＢ、（分子ビームエピタキシャル）法などによる薄
膜形成が試みられている状態である。Attempts are being made to form thin films using MBB, (molecular beam epitaxial) methods, and the like.
Ｙ−Ｂａ−Ｃｕ−０系薄膜をＥＢ蒸着法、 ＭＢＢ法な
どで成膜する場合、希土類元素（ＲＥ）であるイツトリ
ウム（Ｙ）、バリウム（Ｂａ）および銅（Ｃｕ）を別々
に蒸着させる方法は既に検討されている。しかし、この
方法によると、プロセスが複雑化し、蒸着膜形成後のア
ニールでＹ、 Ｂａ、 Ｃｕの混合が不十分で、結晶化
が完全に進行しない問題がある。そこで、本願の発明者
等はＹＩＢａ、Ｃ勧Ｏｘの焼結体を蒸着源として単一プ
ロセスで薄膜を形成することを試みた。しかし、 Ｙ、
Ｂａ、Ｃｕ３０ｘ （これは超伝導となる）を蒸着
源とした場合に、形成された膜は、ＹとＣｕとが足りな
い状態となることを確認した。When forming a Y-Ba-Cu-0 based thin film using the EB evaporation method, MBB method, etc., there is a method in which the rare earth elements (RE) yttrium (Y), barium (Ba), and copper (Cu) are separately evaporated. is already being considered. However, this method has the problem that the process is complicated, and that Y, Ba, and Cu are insufficiently mixed during annealing after forming the deposited film, and crystallization does not proceed completely. Therefore, the inventors of the present application attempted to form a thin film in a single process using a sintered body of YIBa and COx as a deposition source. However, Y.
It was confirmed that when Ba and Cu30x (which are superconducting) were used as the evaporation source, the formed film was in a state in which Y and Cu were insufficient.
他方、Ｙ−Ｂａ−Ｃｕ−０系Ｗｌ膜をスパッタ法で成膜
する場合に、ＹＩ Ｂａ１Ｃｕ３０ｘのターゲットを用
いると、形成された膜ではＢａとＣｕとが欠乏状態にあ
ることが判明した。そこで、Ｙ、０３１ ＢａＣＯ３＋
ＣｕＯの粉末をターゲットとする成膜方法をとったが
、その場合に得られる膜は液体Ｈｅ温度でしか超伝導に
ならないことが確認された。On the other hand, it has been found that when a Y-Ba-Cu-0 based Wl film is formed by sputtering using a target of YI Ba1Cu30x, the formed film is deficient in Ba and Cu. Therefore, Y, 031 BaCO3+
A film formation method using CuO powder as a target was used, but it was confirmed that the film obtained in that case became superconducting only at the temperature of liquid He.
そこで、本発明は、ＲＢＩ Ｂａ２ＣｕＪＯｘを蒸着源
として薄膜を形成する場合、成膜された薄膜に欠乏する
ＲＥとＣｕまたはＢａとＣｕとが補償される超伝導薄膜
の形成方法を提供することを目的とする。Therefore, an object of the present invention is to provide a method for forming a superconducting thin film that compensates for the lack of RE and Cu or Ba and Cu in the formed thin film when forming a thin film using RBI Ba2CuJOx as a deposition source. shall be.
上記問題点は、蒸着法あるいはスパッタ法によりＲｆ！
ＩＢａｚＣｕ？Ｏフ−ｘ系（ただし、ＲＥは希土類元素
）の超伝導薄膜を作成するにおいて、ＲＬ Ｈａ、 Ｃ
ｕの酸化物を１：１．３の比で混合した後に焼成し、か
くして得られた焼成物を粉砕したものにＲＥＩＯ３とＣ
ｕを粉体で加え焼成したソースを用いることを特徴とす
る超伝導薄膜の形成方法によって解決される。The above problem can be solved by using Rf!
IBazCu? In creating a superconducting thin film of O-x system (RE is a rare earth element), RL Ha, C
After mixing oxides of
This problem is solved by a method for forming a superconducting thin film characterized by using a source prepared by adding u in powder form and firing it.
欠乏するＹとＣｕとを補償しようとする場合、酸化イン
ドリウム（ＹｇＬ０３） 、炭酸バリウム（ＢａＣＯ３
）、酸化第１銅（Ｃｕｂ）の粉体を、ＹＩＢａｚ−ＣＩ
ＪＪ Ｏｘよりも、Ｙ、Ｃｕを補償した量論比で混合し
て、これを蒸着源として成膜したが、この方法によると
液体Ｈｅ温度でしか超伝導とならない、この方法で得た
薄膜の超伝導移転温度が低いのは、結晶化が完全に進行
していないことによるものと解される。When trying to compensate for the deficiency of Y and Cu, indium oxide (YgL03), barium carbonate (BaCO3)
), cuprous oxide (Cub) powder, YIBaz-CI
A film was formed by mixing Y and Cu in a compensated stoichiometric ratio rather than JJ Ox and using this as a deposition source. It is understood that the low superconducting transition temperature is due to the fact that crystallization has not completely progressed.
そこで、本発明の方法においては、次のような蒸着源（
ソース）を用いた成膜を行った。すなわち、ＹＪＬＯ３
、ＣｕＯ、ＢａＣＯ３を混ぜて焼成し、ＹＩ Ｂａ１Ｃ
ｕ３０ｘとなる焼結体を−先ず作ると、この焼結体は、
ＢａＣ０３のＣがほぼ完全に除去されたものであり、液
体窒素温度で超伝導となり、斜方晶ペロブスカイトであ
る。これを粉砕し、これにＹ工０３粉、Ｃｕ粉を加え、
成型し、蒸着源とした。この方法によって得られた膜は
、液体Ｎ２温度で超伝導となった。Therefore, in the method of the present invention, the following evaporation source (
Film formation was performed using a source (source). That is, YJLO3
, CuO, and BaCO3 are mixed and fired to form YI Ba1C.
When a sintered body of u30x is first made, this sintered body becomes
It is BaC03 from which C has been almost completely removed, becomes superconducting at liquid nitrogen temperature, and is an orthorhombic perovskite. Grind this, add Yko03 powder and Cu powder,
It was molded and used as a vapor deposition source. The membrane obtained by this method became superconducting at liquid N2 temperature.
他方、Ｙ−Ｂａ−Ｃｕ−Ｏｘ系薄膜をスパッタ法で成膜
する場合、Ｙ、Ｂａ１Ｃｕ３０ｘのターゲットを用いる
と、膜ではＢａとＣｕが欠乏状態となることが判明した
ので、Ｙ、（）３１ ＢａＣ０ａ １ＣｕＯの粉体を、
ＢａとＣｕが多くなるように混合して、これを圧粉して
ターゲットとする成膜方法をとると、液体Ｈｅ温度でし
か超伝導とならない。On the other hand, when forming a Y-Ba-Cu-Ox based thin film by sputtering, it was found that if a Y, Ba1Cu30x target was used, the film would be deficient in Ba and Cu. BaC0a 1CuO powder,
If a film formation method is adopted in which a large amount of Ba and Cu is mixed and the mixture is pressed into powder and used as a target, superconductivity will occur only at the liquid He temperature.
そこで、本発明では、前記した場合と同様に、Ｙ、０３
、 ＣｕＯ、ＢａＣＯ３粉体を混合し、Ｙ、Ｂａ、Ｃ
ｕ、Ｏｘとなる焼結体を−先ず作る。この焼結体は、液
体窒素温度で超伝導となる。これを粉砕し、それにＢａ
Ｃ０３とＣｕＯ粉を加えて混合し、圧粉してターゲット
とした。この方法によって得られた膜は、液体窒素温度
で超伝導となった。Therefore, in the present invention, as in the case described above, Y, 03
, CuO, BaCO3 powders are mixed, Y, Ba, C
First, a sintered body serving as u and Ox is made. This sintered body becomes superconductive at liquid nitrogen temperature. Crush this and add Ba
C03 and CuO powder were added, mixed, and pressed to form a target. The membrane obtained by this method became superconducting at liquid nitrogen temperatures.
以下、本発明を図示の一実施例により具体的に説明する
。Hereinafter, the present invention will be specifically explained with reference to an illustrated embodiment.
本発明の第１実施例はＥＢ蒸着法に関する。先ず、ＹＩ
Ｂａ ｚｃｕｓ Ｏｘ焼結体（斜方晶ペロブスカイト
、液体Ｎ２温度で超伝導となる）の作成方法は次のステ
ップによる。A first embodiment of the present invention relates to an EB deposition method. First, YI
A method for producing a Bazcus Ox sintered body (orthorhombic perovskite, which becomes superconducting at liquid N2 temperature) is performed in the following steps.
ＹＬ０３ ＋ ２ ＢａＣＯ３＋ ３ ＣｕＯを混合し
、空気中で８５０℃＋ １０ ｈｒ仮焼する。YL03 + 2 BaCO3 + 3 CuO are mixed and calcined in air at 850°C + 10 hr.
次いで、粉砕、混合、圧粉を３００ｋｇｆ／ ｃｍ２で
行い、空気中で９５０℃、 １０ｈｒ焼成する。次に、
０．５”Ｃ／ｍｉｎで冷却して
Ｙ、Ｂａ３Ｃｕ３０ｘ
の焼結体を得る。この焼成において、結晶生成の妨げと
なるＢａＣ０３のＣが十分に除去される。Next, pulverization, mixing, and powder compaction are performed at 300 kgf/cm2, followed by firing in air at 950°C for 10 hours. next,
A sintered body of Y, Ba3Cu30x is obtained by cooling at 0.5''C/min. In this firing, C of BaC03, which obstructs crystal formation, is sufficiently removed.
次に、蒸着源の作成と成膜について説明すると、上記の
方法で得られたＹＩＢａ□Ｃｕ３０ｘの焼結体を粉砕し
、それにＹ２Ｏ３粉（Ｂａに対して４〜６の割合）とＣ
ｕ粉（Ｂａに対して１の割合）とを混合すると、Ｙｓ−
，７ＢａｔＣｕｔＦＯｘ
なる組成の粉体が得られる。Ｙ（４の比率は、電子ビー
ムのパワーに応じて定まるものである。それをベレット
に成型し、 ｏ２中で５００℃、２ｈｒ仮焼する。Next, to explain the creation of a vapor deposition source and film formation, the sintered body of YIBa□Cu30x obtained by the above method is crushed, and Y2O3 powder (4 to 6 ratios to Ba) and carbon are added to it.
When mixed with u powder (ratio of 1 to Ba), Ys-
, 7BatCutFOx is obtained. The ratio of Y(4) is determined depending on the power of the electron beam. It is formed into a pellet and calcined in O2 at 500°C for 2 hours.
次に、このペレットを用い、第１図の装置を用いるＥＢ
蒸着方で成膜するが、第１図において、１１はチャンバ
、１２は基板ホルダー、１３は基板、１４はヒーター、
１５は酸素供給管、１５ａは孔、１６は酸素導入管、１
７は前記したＹ、ｙ〜７ＢａＬＣｕチ０χの蒸着源、１
日はフィラメント、１９はマグネット、２ｏは電子銃、
２１は電子ビーム（ＥＢ） 、２２は排気管を示す。Next, using this pellet, EB using the apparatus shown in FIG.
The film is formed by vapor deposition, and in FIG. 1, 11 is a chamber, 12 is a substrate holder, 13 is a substrate, 14 is a heater,
15 is an oxygen supply pipe, 15a is a hole, 16 is an oxygen introduction pipe, 1
7 is the vapor deposition source of Y, y~7BaLCu 0χ described above, 1
Day is filament, 19 is magnet, 2o is electron gun,
21 is an electron beam (EB), and 22 is an exhaust pipe.
この装置において、蒸着源１７はＥＨ１１によって熔融
、気化され蒸発して、ヒーター１４によって６００℃に
加熱された基板１３上にＹ、Ｂａ、Ｃｕ、Ｂｏｘ膜が成
膜される。基板には、サファイア、 ＭｇＯまたはスト
ロンチウム・チタン酸素（５ｒＴｉＯ３）を用いる。成
膜中十分な酸素（０２）が供給されるよう、導入管１６
から導入される０２は酸素供給管１５の孔１５ａから基
板１３へ向けて噴射される。In this apparatus, the vapor deposition source 17 is melted and vaporized by the EH 11, and Y, Ba, Cu, and Box films are formed on the substrate 13, which is heated to 600° C. by the heater 14. Sapphire, MgO, or strontium titanium oxygen (5rTiO3) is used for the substrate. In order to supply sufficient oxygen (02) during film formation, the introduction pipe 16
02 introduced from the oxygen supply pipe 15 is injected toward the substrate 13 from the hole 15a of the oxygen supply pipe 15.
次いで、膜をつ２中で９００℃、 ２ｈｒ＋４５０ ”
Ｃ。Then, the membrane was heated in a chamber at 900°C for 2 hours + 450 ”
C.
４ｈｒのアニールを行ったところ、膜は液体窒素温度で
超伝導となった。When annealing was performed for 4 hours, the film became superconductive at liquid nitrogen temperature.
本発明の第２実施例であるスパッタ法による成膜のため
のＹ、Ｂａ、、Ｃｕ３０ｘ焼結体の作成においては、前
記した方法によって、 ＹＩＢａＪｕ５０χ焼結体を得
る。In producing a Y, Ba, Cu30x sintered body for film formation by sputtering, which is the second embodiment of the present invention, a YIBaJu50x sintered body is obtained by the method described above.
次に、この焼結体を粉砕し、それにＢａＣＯ３粉（Ｙに
対して２の割合）とＣｕＯ粉（Ｙに対して２の割合）を
加え、Ｙ、 Ｂａｔ Ｃｕの比率を１：４：５にする。Next, this sintered body was crushed, and BaCO3 powder (ratio of 2 to Y) and CuO powder (ratio of 2 to Y) were added to it to make the ratio of Y and Bat Cu 1:4:5. Make it.
この比率はスパッタ装置に応じて適宜変更する。ＢａＣ
０３粉とＣｕＯ粉とを混合し、Ｙ、Ｂａ ｌＣｕ４＝（
Ｏｘ
の組成の粉体とする。This ratio is changed as appropriate depending on the sputtering apparatus. BaC
03 powder and CuO powder were mixed, Y, Ba lCu4=(
The powder has a composition of Ox.
次いで圧粉してターゲットにし、０２中で５００”Ｃ＋
２ｈｒ仮焼する。このターゲットよりスパッタ法で成膜
し、膜をアニール（０２中で９００℃、２ｈｒ＋ ４５
０℃、４ｈｒ）したところ、液体窒素温度で超伝導とな
った。基板には、サファイア＋ ＭｇＯ１ＳｒＴｉ０３
などを用いた。Then, it was compacted into a target and heated to 500”C+ in 02
Calculate for 2 hours. A film was formed using the sputtering method from this target, and the film was annealed (900°C in 02, 2 hr + 45
0° C. for 4 hours), it became superconductive at liquid nitrogen temperature. The substrate is sapphire + MgO1SrTi03
etc. were used.
スパッタ装置は第２図の断面図に示され、図中、３１は
チャンバ、３２は基板ホルダー、３３は基板、３４はＹ
、 Ｂａ３Ｃｕ４−ｇｏｘのターゲット、３５は（Ａｒ
＋ Ｏｚ ）の導入管、３６は排気管、３７はＲＦ電
源を示し、Ａｒ５０％＋０２５０％を導入して１０−
’ Ｔｏｒｒの圧力を保つ。The sputtering apparatus is shown in a sectional view in FIG. 2, in which 31 is a chamber, 32 is a substrate holder, 33 is a substrate, and 34 is a Y
, Ba3Cu4-gox target, 35 is (Ar
36 is the exhaust pipe, 37 is the RF power supply, and 50% + 0250% Ar is introduced, and 10-
' Maintain Torr pressure.
基板３３は図示しないヒーターで６００℃に加熱し、基
板ホルダー３２は固定された構成とする。The substrate 33 is heated to 600° C. by a heater (not shown), and the substrate holder 32 is fixed.
なお、以上ではＹを例として説明したが、本発明の通用
範囲はその場合に限られるものでなく、＋３価の酸化状
態をとるスカンジウム（Ｓｃ） 、ランタン（Ｌａ）
、ネオジウム（Ｎｄ） 、サマリウム（ＳＩｌｌ）ｌガ
ドリニウム（Ｇｄ） 、ジスプロシウム（Ｄｙ）、ホル
ミウム（Ｈｏ） 、エルビウム（Ｅｒ） 、ツリウム（
Ｔｍ） 、ルテチウム（Ｌｕ） 、プロメチウム（Ｐｍ
） 、ユーロピウム（Ｅｕ） 、イソテリビウム（Ｙｂ
）を用いる場合にも及ぶものである。In addition, although Y was explained above as an example, the scope of the present invention is not limited to that case, and scandium (Sc), lanthanum (La), which has a +3 valence oxidation state, etc.
, neodymium (Nd), samarium (SIll), gadolinium (Gd), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (
Tm), lutetium (Lu), promethium (Pm)
), europium (Eu), isoterbium (Yb)
).
以上のように本発明によれば、ＥＢ蒸着またはスパッタ
で欠乏するＹとＣｕまたはＢａとＣｕを補償することに
より、単一プロセスで、液体窒素温度にて超伝導を示す
薄膜の形成が可能となり、この薄膜はＣを含まない良質
の結晶膜であることが確認された。As described above, according to the present invention, by compensating for the depletion of Y and Cu or Ba and Cu during EB evaporation or sputtering, it is possible to form a thin film exhibiting superconductivity at liquid nitrogen temperature in a single process. It was confirmed that this thin film was a high quality crystalline film containing no carbon.
第１図は本発明第１実施例断面図、 第２図は本発明第２実施例断面図 である。 。 図中、 １１はチャンバ、 １２は基板ホルダー、 １３は基板、 １４はヒーター、 １５は酸素供給管、 １５ａは孔、 １６は酸素導入管、 １７は蒸着源（ソース）、 １８はフィラメント、 １９はマグネット、 ２０は電子銃、 ２１は電子ビーム、 ２２は排気管、 ３１はチャンバ１ ３２は基板ホルダー、 ３３は基板、 ３４はターゲット、 ３５は（Ａｒ＋ ０２ ）導入管、 ３６は排気管、 ３７はＲＰｇ源 を示す。 特許出願人 富士通株式会社 代理人弁理士 久木元 彰 FIG. 1 is a sectional view of the first embodiment of the present invention. Figure 2 is a sectional view of the second embodiment of the present invention. It is. . In the figure, 11 is a chamber; 12 is a board holder; 13 is a board; 14 is a heater, 15 is an oxygen supply pipe; 15a is a hole; 16 is an oxygen introduction pipe; 17 is a vapor deposition source (source); 18 is a filament, 19 is a magnet, 20 is an electron gun, 21 is an electron beam, 22 is the exhaust pipe, 31 is chamber 1 32 is a board holder; 33 is a board; 34 is the target, 35 is (Ar+02) introduction pipe, 36 is the exhaust pipe, 37 is the RPg source shows. Patent applicant: Fujitsu Limited Representative Patent Attorney Akira Kukimoto
Claims (1)
ｕ＿３Ｏ＿７＿−＿ｘ（ただし、ＲＥは希土類元素）の
超伝導薄膜を作成するにおいて、 ＲＥ、Ｂａ、Ｃｕの酸化物を１：２：３の比で混合した
後に焼成し、かくして得られた焼成物を粉砕したものに
ＲＥ＿２Ｏ＿３とＣｕを粉体で加え焼成したソースを用
いることを特徴とする超伝導薄膜の形成方法。[Claims] RE_1Ba_2C by vapor deposition method or sputtering method
To create a superconducting thin film of u_3O_7_-_x (where RE is a rare earth element), oxides of RE, Ba, and Cu are mixed in a ratio of 1:2:3 and then fired, and the fired product thus obtained is A method for forming a superconducting thin film characterized by using a source obtained by adding RE_2O_3 and Cu in the form of powder to a pulverized material and firing the mixture.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63014387A JPH01192720A (en) | 1988-01-27 | 1988-01-27 | Production of superconducting thin film |
| EP89101208A EP0326087A3 (en) | 1988-01-27 | 1989-01-24 | Method of fabricating a superconductive film |
| US07/300,889 US4914080A (en) | 1988-01-27 | 1989-01-24 | Method for fabricating superconductive film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63014387A JPH01192720A (en) | 1988-01-27 | 1988-01-27 | Production of superconducting thin film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01192720A true JPH01192720A (en) | 1989-08-02 |
Family
ID=11859648
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63014387A Pending JPH01192720A (en) | 1988-01-27 | 1988-01-27 | Production of superconducting thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01192720A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01264952A (en) * | 1988-04-08 | 1989-10-23 | Kyocera Corp | Production of oxide superconductor |
| JP2000503351A (en) * | 1996-11-01 | 2000-03-21 | テファ デュンシヒトテヒニク ゲーエムベーハー | Equipment for manufacturing thin oxide coatings |
-
1988
- 1988-01-27 JP JP63014387A patent/JPH01192720A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01264952A (en) * | 1988-04-08 | 1989-10-23 | Kyocera Corp | Production of oxide superconductor |
| JP2000503351A (en) * | 1996-11-01 | 2000-03-21 | テファ デュンシヒトテヒニク ゲーエムベーハー | Equipment for manufacturing thin oxide coatings |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Norton | Synthesis and properties of epitaxial electronic oxide thin-film materials | |
| US4900710A (en) | Process of depositing an alkali metal layer onto the surface of an oxide superconductor | |
| JPH01192720A (en) | Production of superconducting thin film | |
| JPS63270450A (en) | Production of thick film oxide super conductor | |
| JP2975608B2 (en) | Insulating composition | |
| JPH02167820A (en) | Method for forming tl-base multiple oxide superconducting thin film | |
| JP3507887B2 (en) | Method for forming epitaxial thin film on surface of single crystal substrate | |
| JP2603688B2 (en) | Superconducting material reforming method | |
| JPH0556283B2 (en) | ||
| JP2765138B2 (en) | Preparation method of high quality oxide superconducting thin film | |
| JP2598055B2 (en) | Oxide superconducting thin film for electronic devices | |
| JPH0816024B2 (en) | Manufacturing method of superconducting material | |
| JP4153651B2 (en) | Seed crystal of oxide superconducting material and manufacturing method of oxide superconducting material using the same | |
| JP2980650B2 (en) | Method for producing rare earth oxide superconductor | |
| JPH04160005A (en) | Production of superconducting oxide | |
| JP2525852B2 (en) | Preparation method of superconducting thin film | |
| KR20090093618A (en) | Method of forming a precursor solution for metal organic deposition and mothod of forming a superconducting thick film using thereof | |
| JP2597579B2 (en) | Superconductor manufacturing method | |
| JPH01278449A (en) | Production of oxide superconductor | |
| JPH01242477A (en) | Formation of protective film on superconductor | |
| JPS63303851A (en) | Sintered body of superconducting ceramic | |
| JPH01164768A (en) | Production of oxide superconductor | |
| JPH06287100A (en) | Formation of thin oxide superconducting film containing rare earth element | |
| JPS63248019A (en) | Manufacture of oxide superconductive thin film | |
| JPH01179722A (en) | Production of oxide superconductor |