JPH0244013A - Method for forming superconducting thin film - Google Patents
Method for forming superconducting thin filmInfo
- Publication number
- JPH0244013A JPH0244013A JP63193964A JP19396488A JPH0244013A JP H0244013 A JPH0244013 A JP H0244013A JP 63193964 A JP63193964 A JP 63193964A JP 19396488 A JP19396488 A JP 19396488A JP H0244013 A JPH0244013 A JP H0244013A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- film
- substrate
- superconducting thin
- superconducting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010409 thin film Substances 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims description 38
- 239000010408 film Substances 0.000 claims abstract description 73
- 239000000758 substrate Substances 0.000 claims abstract description 72
- 238000000137 annealing Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 47
- 238000000151 deposition Methods 0.000 claims description 8
- 239000002887 superconductor Substances 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims 1
- 239000001569 carbon dioxide Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 238000009792 diffusion process Methods 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 5
- 229910009203 Y-Ba-Cu-O Inorganic materials 0.000 abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000004544 sputter deposition Methods 0.000 description 26
- 229910052727 yttrium Inorganic materials 0.000 description 8
- 229910052788 barium Inorganic materials 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- WHOPEPSOPUIRQQ-UHFFFAOYSA-N oxoaluminum Chemical compound O1[Al]O[Al]1 WHOPEPSOPUIRQQ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E40/00—Technologies for an efficient electrical power generation, transmission or distribution
- Y02E40/60—Superconducting electric elements or equipment; Power systems integrating superconducting elements or equipment
Landscapes
- Oxygen, Ozone, And Oxides In General (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Physical Vapour Deposition (AREA)
- Chemical 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】
（イ）技術分野
本発明は、超伝導薄膜を形成するための成膜技術に関し
、更に詳しくは非酸化物系の基板表面に超伝導薄膜を成
膜するに際し、該基板表面上に接合層と下地層を設け、
該下地層上に超伝導ｇ膜を形成させる方法に関するもの
である。Detailed Description of the Invention (a) Technical Field The present invention relates to a film formation technique for forming a superconducting thin film, and more specifically, to a method for forming a superconducting thin film on the surface of a non-oxide substrate. A bonding layer and a base layer are provided on the substrate surface,
The present invention relates to a method of forming a superconducting g film on the underlayer.
（ロ）従来技術
超伝導薄膜の形成法としては、大別してスパッタリング
法、蒸着法ならびにＣＶＤ（Ｃ：ｈｅ履１ｃａｌＶａｐ
ｏｕｒ Ｄｅｐｏｓｉｔｉｏｎ ）法があり、これらの
方法は超伝導薄膜の特性や利用形態等によって使い分け
られている。(b) Conventional technology The methods for forming superconducting thin films can be roughly divided into sputtering, vapor deposition, and CVD (C: 1 calVap).
There are two methods: our deposition method, and these methods are used depending on the characteristics of the superconducting thin film, the mode of use, etc.
特に、酸化物超伝導薄膜の成膜法としては、スパッタリ
ング法（−以下、スパッター法という）によるのがほと
んどである。In particular, the most common method for forming oxide superconducting thin films is the sputtering method (hereinafter referred to as sputtering method).
しかしながら、更に高Ｔｃ（臨界温度）酸化物超伝導材
料に関しては、スパッター法が最適かどうかは不明確で
あり、より新しい薄膜形成技術の開発が望まれている。However, with regard to oxide superconducting materials with even higher Tc (critical temperature), it is unclear whether the sputtering method is optimal or not, and the development of newer thin film forming techniques is desired.
薄膜を形成するには、構成元素が基板表面でマイグレー
トする連動エネルギーを持つ必要があり、この連動エネ
ルギーが小さい場合には、該基板の温度を高めてエネル
ギーを補う必要がある。To form a thin film, the constituent elements need to have interlocking energy to migrate on the substrate surface, and if this interlocking energy is small, it is necessary to increase the temperature of the substrate to compensate for the energy.
一般に基板なくしてＳ膜はあり得す、基板は薄膜形成り
極めて重要であり、基板の材質は勿論のこと、エピタキ
シャル技術では基板表面の清浄さと共に高真空技術が必
要となる。In general, an S film cannot exist without a substrate; the substrate is extremely important for forming a thin film, and in addition to the material of the substrate, epitaxial technology requires high vacuum technology as well as cleanliness of the substrate surface.
通常、スパッター法は比較的簡単な薄膜形成技術であり
、物質を選ばないこと、多元化合物の薄膜形成に有利で
あること、高融点材料の薄膜化も容易であること、膜厚
の制御が比較的容易であること、高速粒子が飛び込むた
めに基板との付着力が強い膜が得られること等の利点が
ある。In general, sputtering is a relatively simple thin film formation technique, it is not selective about materials, it is advantageous for forming thin films of multi-component compounds, it is easy to form thin films of high melting point materials, and it is easy to control film thickness. It has the advantages of being easy to target, and because high-velocity particles fly into it, a film with strong adhesion to the substrate can be obtained.
また、スパッター法では結晶品質の向上が可能であるた
め、マグネトロンスパッター法はもとより、ＥＣＲスパ
ッター法等が鋭意開発されているのが現状である。In addition, since the sputtering method can improve the crystal quality, not only the magnetron sputtering method but also the ECR sputtering method and the like are currently being actively developed.
超伝導薄膜を形成するためには、超伝導になる組成膜を
基板上に成膜しなければならないが、この方法としては
、Ｙ−Ｂａ−Ｃｕ−０系超伝導薄膜の場合、Ｙ、Ｂａ及
びＣｕの金属を各々蒸着するか、又はそれらの合金を蒸
着することによって、基板上にＹ、Ｂａ、及びＣｕを各
々ｌ：２：３の組成（ｍｏｌ比）の薄膜を成膜する。In order to form a superconducting thin film, a composition film that becomes superconducting must be formed on a substrate. A thin film of Y, Ba, and Cu each having a composition (molar ratio) of 1:2:3 is formed on the substrate by vapor-depositing the metals Y, Ba, and Cu, respectively, or by vapor-depositing an alloy thereof.
その後、空気あるいは酸素雰囲気中で所定条件下で加熱
処理してＹ、Ｂａ２ Ｃｕ３ｏ、−ｘｃ７）酸化物超伝
導薄膜を形成させる方法と、これに類似する方法として
、直接蒸着過程で酸素を導入して酸化膜を形成させるこ
とも可能であるが、該方法等はスパッター法による場合
が一般的である。Thereafter, a Y, Ba2 Cu3o, -xc7) oxide superconducting thin film is formed by heat treatment under predetermined conditions in an air or oxygen atmosphere, and a similar method involves introducing oxygen during the direct vapor deposition process. Although it is also possible to form an oxide film using a sputtering method, the method is generally a sputtering method.
また、その他の方法としては、Ｙ、Ｂａ、Ｃｕの各酸化
物を各スパッターして、基板上にｌ：２： ３ （ｍｏ
ｌ比）の組成膜を形成させる方法と、Ｙ、Ｂａ、Ｃｕの
各酸化物を所定比率に合成したターゲットを用いて、１
：２：３（ｍｏｌ比）の組成膜を形成させる方法がある
。In addition, as another method, Y, Ba, and Cu oxides are sputtered onto the substrate in a l:2:3 (mo
Using a method of forming a composition film with a composition ratio of
There is a method of forming a film having a composition of :2:3 (molar ratio).
上記の方法等で形成された組成膜は、通常アモルファス
であるために、１ ： ２ ： ３ （＋ｏｌ比）のＭ
」酸比ｃｙ）Ｙ Ｉ Ｂ ａ２Ｃｕａ ０７− Ｘ（７
）結晶とはなっていないのである。Since the composition film formed by the above method is usually amorphous, it has an M of 1:2:3 (+ol ratio).
” acid ratio cy)Y I B a2Cua 07-
) It has not become a crystal.
従って、１：２：３（ｓｏｌ比）の組成膜を形成させた
基板を６００〜７００℃の温度で空気中あるいは酸素中
でアニール処理してアモルファス状の組成膜を結晶化さ
せ、酸化物超伝導薄膜を形成させるのである。Therefore, a substrate on which a composition film with a 1:2:3 (sol ratio) has been formed is annealed in air or oxygen at a temperature of 600 to 700°C to crystallize the amorphous composition film. This forms a conductive thin film.
即ち、に記の超伝導薄膜の形成法例えばＹ−Ｂａ−Ｃｕ
−０系の酸化物超伝導薄膜の場合には、まずその組成比
を有する組成膜の成膜工程と、該組成膜（アモルファス
状）を結晶化させる工程の２工程からなる。That is, the method for forming a superconducting thin film described in, for example, Y-Ba-Cu
In the case of a -0 series oxide superconducting thin film, there are two steps: first, a step of forming a composition film having the composition ratio, and a step of crystallizing the composition film (amorphous).
また、ノ＾板を約７００℃の温度に保持しておき、そこ
にスパッターによりＹ、Ｂａ、Ｃｕを各々１ ： ２
： ３ （ｍｏｌ比）の組成膜を成膜させて、基板表面
上に順次にＹ、Ｂａ２ Ｃｕ、、０フーＸの結晶を形成
させる方法もある。In addition, the plate was kept at a temperature of about 700°C, and Y, Ba, and Cu were added thereto in a ratio of 1:2 each by sputtering.
There is also a method of forming a film having a composition of: 3 (molar ratio) and sequentially forming crystals of Y, Ba2Cu, 0fuX on the substrate surface.
しかしながら、スパッター法により超伝導薄膜を形成す
る場合には、スパッター後あるいはスパッター中に超伝
導薄膜の組成膜を６００℃以上の温度で加熱処理するた
めに、基板材料からの拡散が大きな問題となっていた。However, when forming a superconducting thin film by the sputtering method, diffusion from the substrate material becomes a major problem because the composition of the superconducting thin film is heat-treated at a temperature of 600°C or higher after or during sputtering. was.
また、超伝導薄膜は一般的に１〜２ルｍ程度の膜厚であ
り、超伝導の組成膜から基板へ拡散すること１例えばこ
れはＺｒＯ，＞、基板で確認されているが、この場合も
超伝導組成膜中のＹ２Ｏ。In addition, superconducting thin films are generally about 1 to 2 μm thick, and diffusion from the superconducting composition film to the substrate 1 For example, this has been confirmed for ZrO,> substrates, but in this case Y2O in the superconducting composition film.
ＣｕＯ及びＢａＯ等の各々の基板中における拡散定数の
違いによって、超伝導薄膜中の膜組成がずれるので、超
伝導体にならなかったり、また超伝導特性が劣化したり
して、問題となっている。Due to the difference in diffusion constant in each substrate such as CuO and BaO, the film composition in the superconducting thin film shifts, resulting in problems such as not becoming a superconductor or deteriorating the superconducting properties. There is.
特に、ｙ、Ｂａ２ Ｃｕ３０．− Ｘ（７）場合、Ｃｕ
Ｏが比較的融点が低く、また他の２成分（Ｙ２０ａ
、 Ｂ ａ Ｏ）に比較して蒸気圧も高いので、ＣｕＯ
が減少しやすく、ＣｕＯが減少するとＹ２Ｂａｌ Ｃｕ
、Ｏなる組成のＴＣが４０に級の結晶粒が生成するため
に、酸化物超伝導Ｅ４膜としての特性（Ｔｃ、臨界磁場
（Ｈｃ）、臨界電流密度（Ｊ ｃ）など）が劣化し、
（ａ） Ｂ伝導組成膜が６００℃以上で熱処理されるこ
とにより、該組成膜の構成成分が基板中に選択的に拡散
して行くので、組成ずれを起こす。In particular, y, Ba2 Cu30. − If X(7), then Cu
O has a relatively low melting point, and the other two components (Y20a
, B a O), its vapor pressure is higher than that of CuO.
tends to decrease, and when CuO decreases, Y2Bal Cu
Because crystal grains with a composition of TC of 40 are generated, the properties as an oxide superconducting E4 film (Tc, critical magnetic field (Hc), critical current density (Jc), etc.) deteriorate, (a) When the B-conducting composition film is heat-treated at 600° C. or higher, the constituent components of the composition film selectively diffuse into the substrate, causing a composition shift.
（ｂ） １１１伝導組成膜中に６００℃以上の熱処理に
よって基板からの基板材料の拡散が起こり、超伝導薄膜
にならない組成となってしまう。(b) Diffusion of the substrate material from the substrate occurs in the 111 conductive composition film due to heat treatment at 600° C. or higher, resulting in a composition that does not become a superconducting thin film.
（ｃ）超伝導組成膜が酸化物系であって、基板の材質が
非酸化物系の場合には、該基板と組成膜間の結合力が弱
く、剥離し易い。(c) If the superconducting composition film is an oxide-based material and the substrate material is a non-oxide material, the bonding force between the substrate and the composition film is weak and peeling occurs easily.
などの欠点があった。There were drawbacks such as.
（ハ）発明の開示
本発明は、非酸化物系の基板上に超伝導８１１１を成膜
するに際し、該非酸化物系基板と超伝導薄膜との接合力
を高め、かつ両者間の相互の拡散反応を防止するために
、まず該非酸化物基板表面に該非酸化物基板を構成する
元素の酸化物からなる接合層を形成し、該接合層上に超
伝導組成膜と相互に拡散反応しない酸化物からなる下地
層を成膜し、該下地層上に超伝導薄膜を形成させること
によって、超伝導ｓ膜を非酸化物系基板に高い密着力で
接合させると共に１両者間の相互拡散反応を防止し、高
特性の超伝導薄膜を安定して形成する方法を提供するも
のである。(C) Disclosure of the Invention The present invention aims to increase the bonding force between the non-oxide substrate and the superconducting thin film when forming a superconducting film 8111 on a non-oxide substrate, and to increase the mutual diffusion between the two. In order to prevent the reaction, first a bonding layer made of oxides of the elements constituting the non-oxide substrate is formed on the surface of the non-oxide substrate, and an oxide that does not diffuse and react with the superconducting composition film is formed on the bonding layer. By forming a superconducting thin film on the base layer, the superconducting S film can be bonded to the non-oxide substrate with high adhesion, and interdiffusion reactions between the two can be prevented. The present invention provides a method for stably forming superconducting thin films with high characteristics.
即ち、第１の発明は、
非酸化物基板に該非酸化物基板を構成する少なくとも一
種の元素を含有する酸化物からなる接合層を成膜し、該
接合層上に７二一リング処理時に超伝導組成薄膜と相互
に反応しない酸化物からなる下地層を成膜し、該下地層
上に超伝導体となる組成で各成分元素を含む薄層からな
る超伝導組成薄膜をｒ＆膜することによって多層成膜体
を形成し、該多層成膜体を７二−リング処理することを
特徴とする超伝導薄膜の形成方法であり、第２の発明は
、
成膜装置内で所定温度に加熱された非酸化物基板表面に
、該非酸化物基板を構成する少なくとも一種の元素を含
有する酸化物からなる接合層を成膜し、該接合層上に該
非酸化物基板を加熱した状態においても超伝導薄膜と相
互に反応しない酸化物からなる下地層を成膜し、該下地
層上に超伝導体となる組成で各成分元素を薄層状に被着
せしめて、超伝導薄膜を成膜することを特徴とする超伝
導薄膜の形成方法である。That is, the first invention is to form a bonding layer made of an oxide containing at least one element constituting the non-oxide substrate on a non-oxide substrate, and to deposit a bonding layer on the bonding layer during the 7-21 ring treatment. By forming a base layer made of an oxide that does not react with the conductive composition thin film, and depositing a superconducting composition thin film consisting of a thin layer containing each component element with a composition that becomes a superconductor on the base layer. A second invention is a method for forming a superconducting thin film, which is characterized in that a multilayer film is formed and the multilayer film is subjected to a 7-ring treatment, and the second invention is a method for forming a superconducting thin film, which is heated to a predetermined temperature in a film forming apparatus. A bonding layer made of an oxide containing at least one element constituting the non-oxide substrate is formed on the surface of the non-oxide substrate, and the bonding layer has superconductivity even when the non-oxide substrate is heated. A superconducting thin film is formed by forming a base layer made of an oxide that does not interact with the thin film, and depositing each component element in a thin layer on the base layer with a composition that becomes a superconductor. This is a unique method for forming superconducting thin films.
上記第１の発明は、非酸化物基板表面に超伝導のアモル
ファス状の組成膜を形成させた後、アニーリング処理し
て結晶化させ、超伝導薄膜を成膜する２工程からなる成
膜方法において、該非酸化物基板表面に該非酸化物基板
を構成する元素の酸化物からなる接合層を形成させて接
合力を高め、更に該接合層上に７二一リング処理時に超
伝導薄膜と相互拡散反応を起こさないような物質で下地
層を形成しておき、この下地層の上に超伝導組成膜を形
成した後、この多層成膜体を７二−リング処理して超伝
導薄膜を成膜する方法である。The first invention provides a film formation method comprising two steps of forming a superconducting amorphous composition film on the surface of a non-oxide substrate and then annealing and crystallizing it to form a superconducting thin film. , a bonding layer made of oxides of the elements constituting the non-oxide substrate is formed on the surface of the non-oxide substrate to increase the bonding strength, and a mutual diffusion reaction occurs between the bonding layer and the superconducting thin film during the 721 ring treatment. A base layer is formed with a material that does not cause oxidation, and a superconducting composition film is formed on this base layer, and then a superconducting thin film is formed by subjecting this multilayered film to a 72-ring treatment. It's a method.
例えば、Ｙ−Ｂａ−Ｃｕ−０系の酸化物超伝導薄膜を非
酸化物基板表面に成膜する場合について説明すれば、該
非酸化物基板表面に直接Ｙ−Ｂａ−Ｃｕ−０系の酸化物
超伝導薄膜を成膜すると、接合力が弱いので剥離してし
まったり、該基板と酸化物ａ電導薄膜との間で相互拡散
反応を起こし、超伝導Ｓ膜にならなかったり、特性の悪
い薄膜しか形成できない。For example, to explain the case where a Y-Ba-Cu-0 based oxide superconducting thin film is formed on the surface of a non-oxide substrate, a Y-Ba-Cu-0 based oxide superconducting thin film is formed directly on the surface of the non-oxide substrate. When a superconducting thin film is formed, it may peel off due to weak bonding strength, or a mutual diffusion reaction may occur between the substrate and the oxide a conductive thin film, resulting in a thin film with poor characteristics. can only be formed.
例えば、ＳｆＣ基板表面にスパッター法で、Ｙ−Ｂａ−
Ｃｕ−Ｑ系組成膜を成膜しても、６００℃で５時間アニ
ーリング処理することによって。For example, Y-Ba-
Even when a Cu-Q based composition film is formed, annealing treatment is performed at 600° C. for 5 hours.
密着力が弱く極めて剥離し易い超伝導Ｒ膜しか形成でき
ないし、またＡＩＮ基板上にスパッター法によりＡｎ、
０３を形成させ（接合層）、その上に同様にスパッター
法で超伝導組成膜を成膜しても、６００℃で５時間の７
二−リング処理によりＡｎ２０３接合層からの拡散反応
が一部に起こり、超伝導９Ｍが形成させれても特性が悪
く、品質の安定した超伝導薄膜を形成することはできな
い。Only superconducting R films with weak adhesion and extremely easy to peel can be formed, and An,
Even if 03 is formed (bonding layer) and a superconducting composition film is similarly formed on it by the sputtering method, it will take 7 hours at 600°C for 5 hours.
Due to the two-ring treatment, a diffusion reaction from the An203 bonding layer occurs partially, and even if superconducting 9M is formed, the properties are poor and a superconducting thin film with stable quality cannot be formed.
この対策として、鋭意研究の結果開発された技術が本発
明法であって、Ｓｉ３Ｎ４．ＡＬ；ＬＮ。As a countermeasure to this problem, a technique developed as a result of intensive research is the method of the present invention. AL; LN.
ＳｉＣ，ＴｉＣ，ＴｉＮ、ＢＮ、Ｓｉ等からなる群から
選ばれる少なくとも一種の非酸化物からなる基板の表面
に、Ｓｉ、Ｔｉ、Ａｉ、Ｂ等の該非酸化物基板を構成す
る少なくとも一種の元素を含む酸化物からなる接合層を
成膜し、該接合層上にアニーリング処理時に超伝導組成
９ｉ膜と相互に拡故反応しない元素であるＭ ｇ 、
Ｔ ａ 、 Ｎ ｉ 、 Ｗ 。At least one element constituting the non-oxide substrate such as Si, Ti, Ai, B, etc. is added to the surface of a substrate made of at least one non-oxide selected from the group consisting of SiC, TiC, TiN, BN, Si, etc. A bonding layer made of an oxide containing Mg, which is an element that does not undergo a diffusion reaction with the superconducting composition 9i film during annealing treatment, is formed on the bonding layer.
Ta, Ni, W.
Ｃａ及びＴｉからなる群から選ばれる少なくとも一種の
元素の酸化物からなる薄層状の下ｔ＃！層を成膜し、該
下地層Ｅに超伝導組成薄膜を成膜することによって多層
成膜体を形成し、該多層成膜体を所定条件で７二−リン
グ処理することによって、超伝導特性の高い薄膜を高密
着力で接合成膜することができるのである。A thin layer of lower t#! made of an oxide of at least one element selected from the group consisting of Ca and Ti! A superconducting composition thin film is formed on the base layer E to form a multilayer film, and the multilayer film is subjected to a 7-ring treatment under predetermined conditions to obtain superconducting properties. It is possible to bond thin films with high adhesion strength.
例えばＡ交Ｎ基板表面にＡ交２０３の接合層を形成させ
、該Ａｌｚ０３接合層ＥにＴｉｅ、下地層を形成させ、
該下地層−Ｆに所定比率のＹ−Ｂａ−Ｃｕ−０系の超伝
導組成膜を成膜して多層成膜体を形成して、この多層成
膜体を６００℃で５時間アニーリング処理することによ
り、Ｔｃが９０に級の高品質なＹ＋ Ｂａ２ Ｃｕ３０
ｔ −Ｘ（７）超伝導薄膜を安定して形成することがで
きるのである。For example, forming a bonding layer of A203 on the surface of the A203 substrate, forming a tie and a base layer on the Alz03 bonding layer E,
A Y-Ba-Cu-0 based superconducting composition film of a predetermined ratio is formed on the base layer -F to form a multilayer film body, and this multilayer film body is annealed at 600° C. for 5 hours. As a result, high quality Y+ Ba2 Cu30 with a Tc of 90
A t −X(7) superconducting thin film can be stably formed.
次に、−上記第２の発明について説明する。Next, - the above-mentioned second invention will be explained.
成膜装置内で基板をあらかじめ７００℃程度の温度に保
持させておき、そこでスパッターによりＹ、Ｂａ、Ｃｕ
を各”ｌ：２：３（ｍｏｌ比）の組成膜を成膜させ、基
板表面に順次にＹＩＢａ２Ｃｕ３０．−ｘの結晶を形成
させる方法においても１本発明法の如き接合層及び下地
層を形成させない場合には、非酸化物基板と超伝導組成
薄膜間で相互に拡散反応を起こし、超伝導薄膜とならな
かったり、また形成されたとしても特性が悪く、品質不
安定なものしか形成されないのみならず、基板との接合
力が弱いために剥離してしまうのである。The substrate is kept at a temperature of about 700°C in advance in the film forming apparatus, and then Y, Ba, and Cu are deposited by sputtering.
In the method of forming a film with a composition of 1:2:3 (molar ratio) and sequentially forming YIBa2Cu30.-x crystals on the substrate surface, it is also possible to form a bonding layer and an underlayer as in the method of the present invention. If this is not done, a mutual diffusion reaction will occur between the non-oxide substrate and the superconducting composition thin film, and a superconducting thin film may not be formed, or even if it is formed, it will only have poor characteristics and unstable quality. Instead, it peels off because the bonding force with the substrate is weak.
これに対して１本発明のように５ｉ３Ｎ４Ａ旦Ｎ、Ｓｉ
Ｃ，ＴｉＣ，ＴｉＮ、ＢＮ２ Ｓｔ等からなる群から選
ばれる少なくとも一種の非酸化物からなる基板の表面に
、Ｓ ｉ 、 Ｔ ｉ 、 Ａ文、Ｂ等の該非酸化物基
板を構成する少なくとも一種の元素を含む酸化物からな
る接合層を成膜し、該接合層上に該非酸化物基板を加熱
した状態においても超伝導薄膜と相互拡散反応を実質的
に起こさない元素であるＭ ｇ 、 Ｔ ａ 、 Ｎ
ｉ 、 Ｗ 、 Ｃａ及びＴｉからなる群から選ばれる
少なくとも一種の元素の酸化物からなる＃層状の下ｉ１
！！層を成膜させ、この基板と接合層と下地層を約７０
０℃の温度に保持させておき、該下地層上にスパッター
法によりＹ、Ｂａ、Ｃｕを各所定比率の組成膜に成膜さ
せて、下地層上に順次にＹＩ Ｂａ、、Ｃｕ３ ｏ、−
Ｘの結晶を形成させることによって、Ｔｃ：９０に級の
高品質なＹ、ＢａｚＣｕ３０７− ｘ超伝導薄膜を高密
着力で接合して形成させることができるのである。On the other hand, as in the present invention, 5i3N4AdanN, Si
On the surface of a substrate made of at least one non-oxide selected from the group consisting of C, TiC, TiN, BN2 St, etc., at least one of the non-oxide substrate such as Si, Ti, A, B, etc. A bonding layer made of an oxide containing the elements is formed, and M g and T a are elements that do not substantially cause an interdiffusion reaction with the superconducting thin film even when the non-oxide substrate is heated on the bonding layer. , N
#Layered lower i1 made of an oxide of at least one element selected from the group consisting of i, W, Ca, and Ti
! ! This substrate, bonding layer and underlayer are approximately 70% thick.
The temperature was maintained at 0° C., and Y, Ba, and Cu were formed into a film with a predetermined ratio of Y, Ba, and Cu on the underlayer by sputtering, and YI Ba, Cu3 o, - was sequentially formed on the underlayer.
By forming a crystal of X, a high-quality Y, BazCu307-x superconducting thin film of Tc: 90 grade can be bonded with high adhesion.
上記の通り、従来の非酸化物基板表面に超伝導薄膜を成
膜する方法では、基板と超伝導薄膜間の接合力が弱く、
剥離してしまったり、相互拡散反応が起こり、高特性の
超伝導薄膜を形成しにくかったが、非酸化物基板表面に
接合力の強い酸化物からなる接合層を形成させ、更に接
合層上に超伝導ｇｉ膜と相互拡散反応を実質的に起こさ
ない物質によって下地層を形成させておき、この下地層
上に超伝導薄膜を形成させる本発明法によれば。As mentioned above, in the conventional method of forming a superconducting thin film on the surface of a non-oxide substrate, the bonding force between the substrate and the superconducting thin film is weak.
Although it was difficult to form a superconducting thin film with high properties due to peeling and interdiffusion reactions, we formed a bonding layer made of an oxide with strong bonding strength on the surface of a non-oxide substrate, and then added a bonding layer on top of the bonding layer. According to the method of the present invention, a base layer is formed of a substance that does not substantially cause an interdiffusion reaction with the superconducting GI film, and a superconducting thin film is formed on the base layer.
安定して高品質の超伝導薄膜を剥離等の懸念もなく形成
することができるのである。A stable, high-quality superconducting thin film can be formed without concerns about peeling or the like.
本発明法（上記した第１及び第２の発明）は、Ｙ−Ｂａ
−Ｃｕ−０系の超伝導薄膜の形成に限定されるものでは
なく、酸化物超伝導薄膜は勿論のこと、スパッタリング
法や薄着法あるいはＣＶＤ法等で形成される超伝導薄膜
の成膜法にも適応できる。The method of the present invention (the first and second inventions described above) uses Y-Ba
-It is not limited to the formation of Cu-0-based superconducting thin films, but can also be applied to oxide superconducting thin films as well as superconducting thin films formed by sputtering, thin deposition, CVD, etc. can also be adapted.
以下、実施例によって本発明の詳細な説明する。Hereinafter, the present invention will be explained in detail with reference to Examples.
（ニ）実施例
実施例ｌ
ＳｉＣ基板表面にスパッター装置により４Ｘ１ ０−
３ ｔｏｒｒ（ｍｓ−Ｈｇ） 、 Ａｒ ：０
２ ＝３ ： １ 。(D) Example Example 1 A 4X1 0-
3 torr (ms-Hg), Ar: 0
2 = 3: 1.
出力４００Ｗの条件で、Ｓｔメタ−ットによってスパッ
タリングし、５ｉ０２膜を１ｇｍ成膜した後（接合層）
、上記と同条件でＭｇターゲットを用いてこの５ｉ０２
接合層上にＭｇＯ膜を膜厚１ルｍ成膜した（下地層）。After forming 1gm of 5i02 film by sputtering with St metal under the condition of output 400W (bonding layer)
, this 5i02 using Mg target under the same conditions as above.
An MgO film with a thickness of 1 m was formed on the bonding layer (base layer).
次に、このＭｇＯ下地層ヒにＹ−Ｂａ−Ｃｕ−Ｏ系ター
ゲットにより上記と同条件でスパッタリングし、Ｙ、Ｂ
ａ２ Ｃｕ３０７− ｘの超伝導組成薄膜を膜厚２ｇｍ
成膜した。Next, this MgO underlayer was sputtered using a Y-Ba-Cu-O target under the same conditions as above, and Y, B
a2 Superconducting thin film of Cu307-x with a thickness of 2 gm
A film was formed.
この多層ｒ＆膜体を空気中６００℃で５時間アニーリン
グ処理を行なった。This multilayer R& film body was annealed in air at 600° C. for 5 hours.
得られた超伝導薄膜の特性を四端子法で測定した結果、
Ｔｃは８２にであり、剥離現象は全く認められなかった
。As a result of measuring the properties of the obtained superconducting thin film using the four-terminal method,
Tc was 82, and no peeling phenomenon was observed.
実施例２
Ｔ ｉ Ｃ基板表面にスパッター装置により４×１Ｏ−
３ｔｏｒｒ（＊ｍ−Ｈｇ）、Ａｒ：０２ ＝３： ｌ
。Example 2 4×1O− was deposited on the surface of the TiC substrate using a sputtering device.
3torr (*m-Hg), Ar: 02 = 3: l
.
出力４０ＱＷの条件で、Ｔｉターゲットを用いてスパッ
タリングし、ＴｉＯ２膜（接合層）を、１８！厚１ルｍ
成膜した。Sputtering was performed using a Ti target under the condition of an output of 40 QW to form a TiO2 film (bonding layer) at 18! Thickness 1 lm
A film was formed.
次に、このＴｉＯ２接合層上にＢａＯターゲットを用い
てＢａ０ｆｉ膜を成膜し、この上にＹ−Ｂａ−Ｃｕ−０
系ターゲツトによって上記と同条件でスパッタリング処
理し、ＹＩ Ｂａ２ Ｃｕ３０７−ｘの超伝導組成膜を
膜厚２ルｍ形成した。Next, a Ba0fi film is formed on this TiO2 bonding layer using a BaO target, and on this Y-Ba-Cu-0
A sputtering process was carried out under the same conditions as above using a target of the above-mentioned type, and a superconducting composition film of YI Ba2 Cu307-x was formed to a thickness of 2 μm.
この多層膜体を空気中６００℃で５時間アニーング処理
を行なった。This multilayer film body was annealed in air at 600° C. for 5 hours.
得られた超伝導薄膜の特性を四端子法で測定した結果、
Ｔｃ ： ７５にであり、剥離現象は全く認められなか
った。As a result of measuring the properties of the obtained superconducting thin film using the four-terminal method,
Tc: 75, and no peeling phenomenon was observed.
実施例３
Ａ交Ｎ基板表面にスパッター装置により４ｘ１０−”ｔ
ｏｒｒ（ｓ＋ｇｒ−Ｈｇ） 、Ａｒ：０２ ＝３：
１ 。Example 3 4x10-”t was deposited on the surface of the A/N substrate using a sputtering device.
orr(s+gr-Hg), Ar:02=3:
1.
出力４００Ｗの条件で、Ａｎターゲットによってスパッ
タリングし、Ａｌ２Ｏ２膜（接合層）をＩＪＬｍ成膜し
た後、上記と同条件でＭｇＯターゲットを用いてＭｇＯ
膜（下地層）を膜厚ｌ濤ｍ成膜した。After forming an Al2O2 film (bonding layer) in IJLm by sputtering with an An target under the conditions of an output of 400 W, MgO was formed using an MgO target under the same conditions as above.
A film (base layer) was formed to a thickness of 1 m.
次に、こ（７）ＭｇＯ下地層上にＹ−Ｂａ−Ｃｕ−Ｏ系
ターゲットを用いて上記と同条件でスパッタリングし、
Ｙ、Ｂａ２ Ｃｕ３ ｏ、−ｘ超電導組成膜を膜厚２Ｉ
Ｌｍ成膜した。Next, (7) sputtering is performed on the MgO underlayer using a Y-Ba-Cu-O based target under the same conditions as above,
Y, Ba2 Cu3 o, -x superconducting composition film with a thickness of 2I
Lm film was formed.
この多層膜体を空気中８５０℃で２時間アニーリング処
理した。This multilayer film body was annealed in air at 850° C. for 2 hours.
得られた超伝導薄膜の特性を四端子法で測定した結果、
Ｔｃ ： ８０にであり、剥離現象は全く認められなか
った。As a result of measuring the properties of the obtained superconducting thin film using the four-terminal method,
Tc: 80, and no peeling phenomenon was observed.
実施例４
ＳｉＮ基板表面にスパッター装置により４×１０”
３ ｔｏｒｒ（ｗｍ−Ｈｇ） 、Ａｒ：０２ ＝
３： １ 。Example 4 4×10” on the surface of the SiN substrate using a sputtering device
3 torr(wm-Hg), Ar:02=
3:1.
出力４００Ｗの条件で、Ｓｔメタ−ットを用いてスパッ
タリングし、５ｉ０２膜（接合層）をｔ４ｍ成膜した後
、上記と同条件で５ｒＴｉＯａターゲツトを用いてＳ
ｒ Ｔ ｉＯａ膜（下地層）を膜厚ｌｐＬｍ成膜した。After forming a 5i02 film (bonding layer) for 4 m by sputtering using a St metal under the conditions of an output of 400 W, S was sputtered using a 5rTiOa target under the same conditions as above.
An r TiOa film (base layer) was formed to a thickness of lpLm.
次に、コ（’） Ｓ ｒ Ｔ Ｉ Ｏ３下地層上にＹ−
Ｂａ−Ｃｕ−０系ターゲツトを用いて上記と同条件でス
パッタリングし、Ｙｌ Ｂａ２ Ｃｕａ ｏ、−ｘ超伝
導組１ｊｌＥ膜を膜厚２ｇｍに形成した。Next, Y-
Sputtering was performed using a Ba-Cu-0 target under the same conditions as above to form a Yl Ba2 Cuao, -x superconducting 1jlE film with a thickness of 2 gm.
この多層４体を空気中８００℃で３時間アニーング処理
した。These four multilayer bodies were annealed in air at 800° C. for 3 hours.
得られた超伝導薄膜の特性を四端子法で測定した結果、
Ｔｃ：８０にであり、剥離現象は全く認められなかった
。As a result of measuring the properties of the obtained superconducting thin film using the four-terminal method,
Tc: 80, and no peeling phenomenon was observed.
（ホ）発明の効果
ヒ述したように、従来の方法では非酸化物基板表面に超
伝導組成膜を形成すると、両者間の接合力が弱いので、
剥離してしまったり、アニーリング処理時に該非酸化物
基板と超伝導組成膜との間で相互拡散反応を起こし、超
伝導ＦＪｊ膜にならなかったり、特性の悪い薄膜しか形
成できなかったが、本発明法即ち非酸化物基板表面に該
非酸化物基板を構成する元素の酸化物からなる接合層を
形成し、該接合層上にアニーリング処理時に超伝導組成
膜と相互に拡散反応しない元素の酸化物からなる下地層
を形成し、該下地層上に超伝導薄膜を成膜することによ
って、Ｉｔｉｌｌ現象の全く認められない高特性の超伝
導ＦＭ膜を安定して形成することができる利点がある。(e) Effects of the invention As mentioned above, when a superconducting composition film is formed on the surface of a non-oxide substrate using the conventional method, the bonding force between the two is weak.
In some cases, the non-oxide substrate peels off, a mutual diffusion reaction occurs between the non-oxide substrate and the superconducting composition film during annealing treatment, and a superconducting FJj film is not formed, or only a thin film with poor characteristics is formed. In other words, a bonding layer made of an oxide of an element constituting the non-oxide substrate is formed on the surface of a non-oxide substrate, and a bonding layer made of an oxide of an element that does not undergo a mutual diffusion reaction with the superconducting composition film during annealing treatment is formed on the bonding layer. By forming a base layer and depositing a superconducting thin film on the base layer, there is an advantage that a superconducting FM film with high characteristics without any Itill phenomenon can be stably formed.
特 許 出 願 人 同和鉱業株式会社り、 −ＪPatent applicant: Dowa Mining Co., Ltd. -J
Claims (2)
なくとも一種の元素を含有する酸化物からなる接合層を
成膜し、該接合層上にアニーリング処理時に超伝導組成
薄膜と相互に反応しない酸化物からなる下地層を成膜し
、該下地層上に超伝導体となる組成で各成分元素を含む
薄層からなる超伝導組成薄膜を成膜することによって多
層成膜体を形成し、該多層成膜体をアニーリング処理す
ることを特徴とする超伝導薄膜の形成方法。(1) A bonding layer made of an oxide containing at least one element constituting the non-oxide substrate is formed on the surface of the non-oxide substrate, and reacts with the superconducting composition thin film during annealing treatment on the bonding layer. A multi-layered film is formed by forming a base layer made of an oxide that does not contain carbon dioxide, and then depositing a superconducting composition thin film consisting of a thin layer containing each component element with a composition that becomes a superconductor on the base layer. A method for forming a superconducting thin film, which comprises subjecting the multilayered film to an annealing treatment.
構成する少なくとも一種の元素を含有する酸化物からな
る接合層を成膜し、該接合層上に該非酸化物基板を加熱
した状態においても超伝導薄膜と相互に反応しない酸化
物からなる下地層を成膜し、該下地層上に超伝導体とな
る組成で各成分元素を薄層状に被着せしめて超伝導薄膜
を成膜することを特徴とする超伝導薄膜の形成方法。(2) A state in which a bonding layer made of an oxide containing at least one element constituting the non-oxide substrate is formed on the surface of the heated non-oxide substrate, and the non-oxide substrate is heated on the bonding layer. Also, a base layer made of an oxide that does not react with the superconducting thin film is formed, and each component element is deposited in a thin layer on top of the base layer with a composition that becomes a superconductor to form a superconducting thin film. A method for forming a superconducting thin film characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63193964A JP2821885B2 (en) | 1988-08-03 | 1988-08-03 | Superconducting thin film forming method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63193964A JP2821885B2 (en) | 1988-08-03 | 1988-08-03 | Superconducting thin film forming method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0244013A true JPH0244013A (en) | 1990-02-14 |
| JP2821885B2 JP2821885B2 (en) | 1998-11-05 |
Family
ID=16316695
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63193964A Expired - Fee Related JP2821885B2 (en) | 1988-08-03 | 1988-08-03 | Superconducting thin film forming method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2821885B2 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63292518A (en) * | 1987-05-26 | 1988-11-29 | Sumitomo Electric Ind Ltd | Compound ceramic superconductor |
| JPS6452328A (en) * | 1987-08-22 | 1989-02-28 | Sumitomo Electric Industries | Superconductive material |
| JPH01316469A (en) * | 1987-12-24 | 1989-12-21 | Asea Brown Boveri Ag | Superconductor and its production |
-
1988
- 1988-08-03 JP JP63193964A patent/JP2821885B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63292518A (en) * | 1987-05-26 | 1988-11-29 | Sumitomo Electric Ind Ltd | Compound ceramic superconductor |
| JPS6452328A (en) * | 1987-08-22 | 1989-02-28 | Sumitomo Electric Industries | Superconductive material |
| JPH01316469A (en) * | 1987-12-24 | 1989-12-21 | Asea Brown Boveri Ag | Superconductor and its production |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2821885B2 (en) | 1998-11-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH03150218A (en) | Production of superconductive thin film | |
| CA2037481C (en) | Method of preparing oxide superconducting film | |
| JPH0354116A (en) | Compound oxide superconducting thin film and production thereof | |
| JPH04300292A (en) | Film forming method for multicomponent oxide film superconducting film | |
| JPH0244013A (en) | Method for forming superconducting thin film | |
| JPH01305580A (en) | Monocrystalline wafer material for forming superconductive ceramic thin film for manufacturing semiconductor element | |
| US5416062A (en) | Thin film superconductor with an interlayer on a silicon substrate | |
| JPS63239742A (en) | Manufacturing method of thin film superconductor | |
| JPH0218974A (en) | Supeconducting device and its manufacture | |
| JP2590142B2 (en) | Superconductor | |
| JPH0244012A (en) | Method for forming superconducting thin film | |
| JPH0281625A (en) | Laminated substrate for oxide based superconductive thin film | |
| JP3068917B2 (en) | Superconducting device | |
| JP2616986B2 (en) | Manufacturing method of Tl based superconductor laminated film | |
| JP3485601B2 (en) | Manufacturing method of superconducting composite thin film | |
| JPH0244782A (en) | Superconducting element and its manufacturing method | |
| JPH07226115A (en) | Yttrium-based oxide superconducting material and method for producing the same | |
| JP2913653B2 (en) | Oxide superconducting thin film structure | |
| JPH02194184A (en) | Production of oxide superconducting thin film | |
| JPH0244781A (en) | Superconductive element and manufacture thereof | |
| JPS63306678A (en) | Josephson element | |
| JPH01105416A (en) | Manufacture of thin film superconductor | |
| JPS63279515A (en) | Superconductor structure | |
| JPH01246371A (en) | Manufacture of oxide superconducting film | |
| JPH01170060A (en) | Semiconductor substrate having superconductor layer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |