JPH02124718A - Preparation of bi-pb-sr-ca-cu type oxide superconducting film - Google Patents
Preparation of bi-pb-sr-ca-cu type oxide superconducting filmInfo
- Publication number
- JPH02124718A JPH02124718A JP63278383A JP27838388A JPH02124718A JP H02124718 A JPH02124718 A JP H02124718A JP 63278383 A JP63278383 A JP 63278383A JP 27838388 A JP27838388 A JP 27838388A JP H02124718 A JPH02124718 A JP H02124718A
- Authority
- JP
- Japan
- Prior art keywords
- film
- superconducting film
- oxide superconducting
- compds
- air
- 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
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052737 gold Inorganic materials 0.000 claims abstract description 5
- 229910052745 lead Inorganic materials 0.000 claims abstract description 5
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 4
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 229910052709 silver Inorganic materials 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims description 8
- 150000002902 organometallic compounds Chemical class 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910014454 Ca-Cu Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 7
- 125000005609 naphthenate group Chemical group 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 125000002524 organometallic group Chemical group 0.000 abstract 4
- 229910003808 Sr-Cu Inorganic materials 0.000 abstract 1
- 229910052804 chromium Inorganic materials 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 206010011224 Cough Diseases 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- -1 cineral subiris Chemical compound 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005404 magnetometry Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical class [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 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)
- Chemically Coating (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、産業上の利用分野
本発明は、超伝導の特性のあるＢ１−Ｐｂ−３ｒ−Ｃａ
−Ｃｕ系酸化物の薄膜を製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION A. Field of Industrial Application The present invention is directed to B1-Pb-3r-Ca which has superconducting properties.
-Relates to a method of manufacturing a Cu-based oxide thin film.
口、従来の技術
Ｂ１−Ｐｂ−Ｓｒ−Ｃａ−Ｃｕ系酸化物が臨界温度（以
下Ｔｃという）１００に程度で超伝導現象を示すことは
、公知である。BACKGROUND OF THE INVENTION It is known that B1-Pb-Sr-Ca-Cu-based oxides exhibit superconductivity at a critical temperature (hereinafter referred to as Tc) of about 100°C.
この酸化物を膜としＩＣ回路等に利用する試みがなされ
ている。この膜の製造方法としては、ＢｉｚＰｂ、 Ｓ
ｒ、 ＣａおよびＣｕの各酸化物粉末を金属原子比で０
．７．０．３．１．０．１．０および１．８の割合で配
合し、アルコールを混合し、材質がＡ ｌ 、０３、Ｚ
ｒＯ□の成形体の表面に塗布し、乾燥して膜状に定着さ
せたのち、空気中で数百時間８４５〜８６０℃で強熱処
理し、表面を半溶融させて膜とする方法が採られていた
。Attempts have been made to use this oxide as a film in IC circuits and the like. The method for manufacturing this film includes BizPb, S
r, Ca and Cu oxide powders with a metal atomic ratio of 0
．． 7.0.3.1.0.1.0 and 1.8, mixed with alcohol, and the material is Al, 03, Z
The method used is to apply it to the surface of an rO was.
ハ、発明が解決しようとする問題点
前記の方法で膜を製造した場合、その膜には部分的にＴ
ｃが１００に以上の結晶相（以下１１Ｔｃ相という）も
生成するが、多くの場合、Ｔｃが８０に程度の結晶相（
以下ＬＴｃ相という）が生成し、しかも成形体の組成物
と膜の組成物とが反応して意図しない化合物がそれらの
境界で生成したりして、一定の高Ｔｃの膜が必ずしも得
られないという欠点があった。C. Problems to be Solved by the Invention When a film is manufactured by the method described above, the film has a portion of T.
A crystalline phase with c of 100 or more (hereinafter referred to as 11Tc phase) also forms, but in many cases, a crystalline phase with Tc of about 80 (
(hereinafter referred to as LTc phase) is generated, and the composition of the molded body and the composition of the film react and unintended compounds are generated at the boundary between them, making it not necessarily possible to obtain a film with a constant high Tc. There was a drawback.
また強熱処理時間が数百時間にも及び、工業的な製造方
法としては不適当であった。Moreover, the ignition treatment time was several hundred hours, making it unsuitable as an industrial manufacturing method.
二、問題点を解決するための手段
本発明者らは、成形体の材質、膜用に塗布する組成物の
材質、熱処理方法について研究した結果、上記の欠点の
ない方法を見出し本発明を完成するに到った。2. Means for Solving the Problems As a result of research on the material of the molded body, the material of the composition applied to the film, and the heat treatment method, the inventors found a method that does not have the above drawbacks and completed the present invention. I came to the conclusion.
すなわち本発明の要旨は、材質がＡｇ５ＡｕまたはＰｔ
である成形体の表面に、Ｂｉ、、Ｐｂ、 Ｓｒ、、 Ｃ
ａおよびＣｕの金属元素を含む金属有機化合物と溶媒と
の混合溶液を塗布し、乾燥して膜を形成させ、それを加
熱処理して該金属有機化合物を分解させ、さらに空気中
で２０時間以上強熱処理して半溶融させたのち冷却する
ことを特徴とするＢ１−Ｐｂ−Ｓｒ−Ｃａ−Ｃｕ系酸化
物超伝導膜の製造方法にある。That is, the gist of the present invention is that the material is Ag5Au or Pt.
Bi, Pb, Sr, C
A mixed solution of a metal organic compound containing the metal elements a and Cu and a solvent is applied, dried to form a film, heated to decompose the metal organic compound, and further exposed to air for 20 hours or more. A method for producing a B1-Pb-Sr-Ca-Cu-based oxide superconducting film, characterized by performing ignition treatment to semi-melt it and then cooling it.
成形体は、その上に超伝導膜を形成させるもので、その
材質は１ 、０００℃以下で酸化しない金属すなわちＡ
ｇ、 ＡｕおよびＰｔである。その厚さは特に限定しな
いが、経済上数μ厚のものを使用する。面積は超伝導の
大きさで決められる。The molded body has a superconducting film formed thereon, and its material is a metal that does not oxidize at temperatures below 1,000°C, ie A.
g, Au and Pt. Although its thickness is not particularly limited, a thickness of several μm is used for economic reasons. The area is determined by the size of the superconductor.
また、セラミックス、金属等に上記金属をコーティング
したものを用いても、同様の結果が得られる。Similar results can also be obtained by using ceramics, metals, etc. coated with the above metals.
超伝導膜用に使用される旧、Ｐｂ、 Ｓｒ、 Ｃａおよ
びＣｕの金属元素を含む金属有機化合物としては、ナフ
テン酸塩、オクチル酸塩、ステアリン酸塩、アルコキシ
ド、アセチルアセトナート等である。それらの塩は、上
記５金属元素のうち１以上含むものである。これら塩を
配合して上記５金属元素の原子比が下記の範囲となるよ
うにする。Metal-organic compounds containing the metal elements Pb, Sr, Ca, and Cu used for superconducting membranes include naphthenates, octylates, stearates, alkoxides, acetylacetonates, and the like. These salts contain one or more of the above five metal elements. These salts are blended so that the atomic ratio of the five metal elements is within the following range.
Ｂｉ ： ０．６５〜０．７５ Ｐｂ ： ０．２５〜０．５５ Ｓｒ ： ０．９５〜１．０５ Ｃａ ： ０．９５〜１．０５ Ｃｕ ： １．７５〜１．８５ 上記の範囲外ではＴｃが低くなる。Bi: 0.65~0.75 Pb: 0.25-0.55 Sr: 0.95-1.05 Ca: 0.95-1.05 Cu: 1.75-1.85 Outside the above range, Tc becomes low.
溶媒はトルエン、キシレン、シネラルスビリソト、ブタ
ノール、エタノール、イソプロパツール等である。Solvents include toluene, xylene, cineral subiris, butanol, ethanol, isopropanol, and the like.
金属有機化合物と溶媒との混合溶液の濃度は、上記５金
属元素が１．２Ｘ １０−４〜２．３Ｘ ｌ Ｏ−’ｍ
ｏ１／ｇがよい。高濃度にすれば１回の塗布で厚い膜が
できるが、熱処理した際、収縮により大きなりラックが
発生する危険がある。The concentration of the mixed solution of the metal-organic compound and the solvent is such that the above five metal elements are 1.2X 10-4 to 2.3X l O-'m
o1/g is good. If the concentration is high, a thick film can be formed with one application, but there is a risk that a large rack will occur due to shrinkage during heat treatment.
この混合溶液を成形体の表面に塗布するには、筆やハケ
によって塗ってもよく、また液を滴下し、形成体を傾斜
させて拡げてもよい。In order to apply this mixed solution to the surface of the molded body, it may be applied with a brush or a brush, or the liquid may be dropped and spread by tilting the molded body.
乾燥は約１００℃程度で行えばよい。Drying may be performed at about 100°C.
加熱処理は、空気中３００〜６００℃、５〜１５分間行
ない、金属有機化合物を熱分解させ、部分的に遊離した
金属を酸化させる。The heat treatment is performed in air at 300 to 600°C for 5 to 15 minutes to thermally decompose the metal organic compound and oxidize the partially liberated metal.
混合溶液の塗布、乾燥、加熱の工程１回で約０．１〜１
．５μの厚さの膜ができる。膜を厚くしたい場合には、
この工程を繰り返せばよい。Approximately 0.1 to 1 per process of applying mixed solution, drying, and heating
．． A film with a thickness of 5μ is formed. If you want to make the film thicker,
You can repeat this process.
強熱処理は、空気巾約８２０〜８４０℃、２０〜５０時
間行ない、塗布膜を半溶融状態にする。The ignition treatment is carried out at an air width of approximately 820 to 840° C. for 20 to 50 hours to bring the coating film into a semi-molten state.
半溶融状態は金属元素の原子比で異なる。例えばＢｉＯ
，７、ＰｂＯ，３、Ｓｒ１．０、Ｃａ １．０． Ｃ
ｕ１．８の場合、強熱温度は８３０〜８３２℃である。The semi-molten state differs depending on the atomic ratio of the metal elements. For example, BiO
,7, PbO,3, Sr1.0, Ca 1.0. C
In the case of u1.8, the ignition temperature is 830-832°C.
強熱処理後は放冷する。After ignition treatment, allow to cool.
ホ、実施例
金属有機化合物として、ナフテン酸Ｂｉ、ナフテン酸ｐ
ｂ、ナフテン酸Ｓｒ、ナフテン酸Ｃａおよびナフテン酸
Ｃｕ （いずれも日本化学産業株式会社製）を用い、そ
れらに含まれる金属元素比が第１表に示す割合となるよ
うに配合し、トルエンを加えて５種類の混合溶液をつく
った。e. Examples of metal organic compounds include Bi naphthenate and p naphthenate.
b, Sr naphthenate, Ca naphthenate, and Cu naphthenate (all manufactured by Nihon Kagaku Sangyo Co., Ltd.) were mixed so that the metal element ratios contained in them were as shown in Table 1, and toluene was added. Five types of mixed solutions were prepared.
それぞれの混合溶液を、成形体として予め作製しておい
た１０Ｘ１０Ｘ０．５鶴のＡｇ、 Ａｕ、 ＰＬ板上に
ピペットで滴下し、同板を左右に傾斜させて咳液を板全
面に行きわたらせた。ついで約１００℃で乾燥させたの
ち、同表に示す条件で加熱処理した。この混合溶液の滴
下から加熱処理までの操作を１０回繰り返した。Each mixed solution was dropped with a pipette onto a 10x10x0.5 crane Ag, Au, or PL board that had been prepared in advance as a molded body, and the board was tilted from side to side to spread the cough liquid over the entire surface of the board. . After drying at about 100° C., it was heat-treated under the conditions shown in the table. The operation from dropping the mixed solution to heating treatment was repeated 10 times.
引き続き、同表に示す条件のもとて強熱処理して半溶融
させたのち、炉内放冷して、それぞれの超伝導膜をつく
った。Subsequently, the material was ignited under the conditions shown in the table to semi-melt it, and then allowed to cool in the furnace to produce each superconducting film.
得られた各Ｂ１−Ｐｂ−Ｓｒ−Ｃａ−Ｃｕ系酸化物超伝
導膜について、交流帯磁率測定法で得た見掛けの測定値
を、予め測定しておいた板のみの測定値で補正して、超
伝導膜のＴｃを求めた。For each B1-Pb-Sr-Ca-Cu-based oxide superconducting film obtained, the apparent measured value obtained by AC magnetic susceptibility measurement method was corrected with the measured value of only the plate measured in advance. , the Tc of the superconducting film was determined.
ついで、超伝導膜のＸ線回折（Ｃｕ ｋα）を行ない、
ＨＴｃ相（２θ＝４．７°）およびＬＴｃ相（２θ−５
，８°）の各ピーク高さを測定し、そのピーク高さの和
に対するｔｌＴｃ相のピーク高さの比を求めた。Next, we performed X-ray diffraction (Cu kα) of the superconducting film,
HTc phase (2θ=4.7°) and LTc phase (2θ−5
, 8°) was measured, and the ratio of the peak height of the tlTc phase to the sum of the peak heights was determined.
さらに、超伝導膜を裁断して膜厚を測定した。Furthermore, the superconducting film was cut and its thickness was measured.
以上の各Ｔｃ、ピーク高さ比および膜厚の各データは、
第１表に伴記した。The above data on Tc, peak height ratio, and film thickness are as follows:
It is noted in Table 1.
ヘ、発明の効果 本発明の方法によれば、つぎの効果がある。F. Effect of invention According to the method of the present invention, there are the following effects.
（１） ＨＴｃ相が多量に生成する。(1) A large amount of HTc phase is generated.
（２）Ｘ線回折のピーク比が０．２以上になり、Ｔｃが
１００に以上の超伝導膜が安定して得られる。(2) A superconducting film with an X-ray diffraction peak ratio of 0.2 or more and a Tc of 100 or more can be stably obtained.
（３）強熱処理を２０時間まで短縮できるので、大巾に
製造時間を短縮できる。(3) Since the ignition process can be shortened to 20 hours, the manufacturing time can be significantly shortened.
Claims (1)
Ｂｉ、Ｐｂ、Ｓｒ、ＣａおよびＣｕの金属元素を含む金
属有機化合物と溶媒との混合溶液を塗布し、乾燥して膜
を形成させ、それを加熱処理して該金属有機化合物を分
解させ、さらに空気中で２０時間以上強熱処理して半溶
融させたのち冷却することを特徴とするＢｉ−Ｐｂ−Ｓ
ｒ−Ｃａ−Ｃｕ系酸化物超伝導膜の製造方法。On the surface of the molded body whose material is Ag, Au or Pt,
A mixed solution of a metal organic compound containing the metal elements Bi, Pb, Sr, Ca and Cu and a solvent is applied, dried to form a film, heated to decompose the metal organic compound, and further Bi-Pb-S characterized by being ignited in air for 20 hours or more to semi-melt it and then cooling it.
A method for producing an r-Ca-Cu-based oxide superconducting film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63278383A JP2796587B2 (en) | 1988-11-02 | 1988-11-02 | Method for producing Bi-Pb-Sr-Ca-Cu-based oxide superconducting film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63278383A JP2796587B2 (en) | 1988-11-02 | 1988-11-02 | Method for producing Bi-Pb-Sr-Ca-Cu-based oxide superconducting film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02124718A true JPH02124718A (en) | 1990-05-14 |
| JP2796587B2 JP2796587B2 (en) | 1998-09-10 |
Family
ID=17596575
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63278383A Expired - Lifetime JP2796587B2 (en) | 1988-11-02 | 1988-11-02 | Method for producing Bi-Pb-Sr-Ca-Cu-based oxide superconducting film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2796587B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH038722A (en) * | 1989-06-06 | 1991-01-16 | Fujitsu Ltd | Production of superconducting film |
-
1988
- 1988-11-02 JP JP63278383A patent/JP2796587B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH038722A (en) * | 1989-06-06 | 1991-01-16 | Fujitsu Ltd | Production of superconducting film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2796587B2 (en) | 1998-09-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0443847B2 (en) | ||
| US4908348A (en) | Barrier layer arrangement for conductive layers on silicon substrates | |
| US5021399A (en) | Spray pyrolysis process for preparing superconductive films | |
| US4994434A (en) | Method of forming a barrier layer arrangement for conductive layers on silicon substrates | |
| JPH02124718A (en) | Preparation of bi-pb-sr-ca-cu type oxide superconducting film | |
| JPS63279527A (en) | Manufacture of superconductor device | |
| JPH07118012A (en) | Oxide superconductor and its production | |
| AU592943B2 (en) | Formation of superconducting metal oxide film by pyrolysis | |
| JP2627803B2 (en) | Method of forming metal nitride thin film | |
| JPH01313332A (en) | Production of thin oxide superconducting film | |
| JPH02302324A (en) | Method for formation of conductive film and product produced by it | |
| JPH01203258A (en) | Production of oxide superconducting sintered body | |
| JPS63231819A (en) | Manufacture of oxide superconductive material | |
| JPH01138129A (en) | Production of oxide superconductor thin film | |
| JPH02258626A (en) | Coating composition for forming conductive film | |
| JPH04317417A (en) | Method of forming high-temperature superconductor on surface of metallic support | |
| JPH01137523A (en) | Manufacture of oxide superconductive thin film | |
| JPH01212219A (en) | Production of thin oxide superconducting film | |
| JPH0238359A (en) | Production of superconductor | |
| JP4697499B2 (en) | Manufacturing method of oxide film | |
| CA1311164C (en) | Europium, barium, copper oxide film superconductors | |
| JPH0458414A (en) | Manufacture of oxide-based superconducting wire | |
| JPH02102123A (en) | Production of superconductor | |
| EP0310247A2 (en) | Ytterbium, barium, copper oxide film superconductors | |
| JPH05262597A (en) | Production of superconducting film of bi-based oxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |