JPH01138129A - Production of oxide superconductor thin film - Google Patents
Production of oxide superconductor thin filmInfo
- Publication number
- JPH01138129A JPH01138129A JP29577887A JP29577887A JPH01138129A JP H01138129 A JPH01138129 A JP H01138129A JP 29577887 A JP29577887 A JP 29577887A JP 29577887 A JP29577887 A JP 29577887A JP H01138129 A JPH01138129 A JP H01138129A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- superconductor thin
- oxide superconductor
- producing
- alkoxide
- 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 33
- 239000002887 superconductor Substances 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- -1 yttrium alkoxide Chemical class 0.000 claims abstract description 20
- 238000011282 treatment Methods 0.000 claims abstract description 14
- 239000010408 film Substances 0.000 claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 10
- 238000000137 annealing Methods 0.000 claims abstract description 9
- 229910052788 barium Inorganic materials 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 6
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 229960005235 piperonyl butoxide Drugs 0.000 claims description 4
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 3
- LJDSTRZHPWMDPG-UHFFFAOYSA-N 2-(butylamino)ethanol Chemical compound CCCCNCCO LJDSTRZHPWMDPG-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- IWSZDQRGNFLMJS-UHFFFAOYSA-N 2-(dibutylamino)ethanol Chemical compound CCCCN(CCO)CCCC IWSZDQRGNFLMJS-UHFFFAOYSA-N 0.000 claims description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical group CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 2
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 2
- 229960002887 deanol Drugs 0.000 claims description 2
- 239000012972 dimethylethanolamine Substances 0.000 claims description 2
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 claims description 2
- 238000001879 gelation Methods 0.000 claims description 2
- 229940102253 isopropanolamine Drugs 0.000 claims description 2
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical group [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 claims description 2
- IKNCGYCHMGNBCP-UHFFFAOYSA-N propan-1-olate Chemical compound CCC[O-] IKNCGYCHMGNBCP-UHFFFAOYSA-N 0.000 claims description 2
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 claims description 2
- KODLUXHSIZOKTG-UHFFFAOYSA-N 1-aminobutan-2-ol Chemical compound CCC(O)CN KODLUXHSIZOKTG-UHFFFAOYSA-N 0.000 claims 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims 1
- 150000004703 alkoxides Chemical class 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 238000003980 solgel method Methods 0.000 abstract description 4
- 229910009203 Y-Ba-Cu-O Inorganic materials 0.000 abstract 1
- 239000007789 gas Substances 0.000 abstract 1
- 108010025899 gelatin film Proteins 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- RRBXHIYJTGFUDF-UHFFFAOYSA-N 1-amino-2,3-dimethylbutan-2-ol Chemical compound CC(C)C(C)(O)CN RRBXHIYJTGFUDF-UHFFFAOYSA-N 0.000 description 1
- KYUPIHBUKDNZKE-UHFFFAOYSA-N 1-amino-3-methylbutan-2-ol Chemical compound CC(C)C(O)CN KYUPIHBUKDNZKE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- AYNQPTYHFBBKFC-UHFFFAOYSA-N copper;methanolate Chemical compound [Cu+2].[O-]C.[O-]C AYNQPTYHFBBKFC-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1254—Sol or sol-gel processing
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1279—Process of deposition of the inorganic material performed under reactive atmosphere, e.g. oxidising or reducing atmospheres
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Metallurgy (AREA)
- Ceramic Engineering (AREA)
- Dispersion Chemistry (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Chemically Coating (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、超伝導性複合酸化物（Ｙ−Ｂａ−Ｃｕ−０系
複合酸化物）薄膜の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing a superconducting composite oxide (Y-Ba-Cu-0 based composite oxide) thin film.
従来の技術
Ｙ −［３ａ −Ｃｕ −０系の超伝導性複合酸化物薄
膜の製造方法としては従来から（１）プラズマスプレー
デポジット法、（２）スクリーン印刷法、（３）スパッ
タ法、（４）イオンビーム蒸着法および（５）金属塩分
解法等が知られているが、（１）と（２）の方法による
と膜厚は１００μ肩以上となって薄膜化は困難であり、
（３）と（４）の方法によると膜組成の変動が大きいば
かりでなく、面積の大きい薄膜を得ることは実際上不可
能であり、また（５）の方法は簡易な方法であるが、出
発原料の精製が難しいために膜に不純物が混入しやすい
だけでなく、薄膜の微細構造を制御することが困難であ
る、等の問題がある。Conventional techniques Conventional methods for producing Y-[3a-Cu-0-based superconducting composite oxide thin films include (1) plasma spray deposition, (2) screen printing, (3) sputtering, and (4) ) Ion beam evaporation method and (5) metal salt decomposition method are known, but methods (1) and (2) result in a film thickness of more than 100 μm, making it difficult to thin the film.
Methods (3) and (4) not only cause large fluctuations in film composition, but also make it practically impossible to obtain a thin film with a large area, and method (5) is a simple method, but There are problems such as difficulty in purifying the starting material, which not only makes it easy for impurities to be mixed into the film, but also makes it difficult to control the fine structure of the thin film.
一方、Ｙ−Ｂａ−Ｃｕ−０系以外の超伝導性複合酸化物
薄膜の製造方法としては、金属アルコキシドを出発原料
とするゾル−ゲル法が知られており、該製法によれば、
被コーテイング基体の形状を問わずに面積の大きい薄膜
の製造が可能である。均一組成の薄膜が簡易な装置で製
造可能である。原料の精製が容易で、薄膜の微細構造の
制御が可能である、等の利点が得られる。On the other hand, a sol-gel method using a metal alkoxide as a starting material is known as a method for producing superconducting composite oxide thin films other than Y-Ba-Cu-0, and according to this method,
It is possible to produce a thin film with a large area regardless of the shape of the substrate to be coated. Thin films with uniform composition can be produced using simple equipment. Advantages such as ease of refining the raw material and control of the fine structure of the thin film can be obtained.
しかしながら、銅アルコキシドはアルコール類やアセト
ン等のゾル−ゲル法で常用されている溶媒を含む一般的
な有機溶媒に溶解しないために、該方法をＹ−Ｂａ−Ｃ
ｕ−０系の超伝導性複合酸化物薄膜の製造に適用する技
術は朱だ１こ開発されていない。However, since copper alkoxide does not dissolve in general organic solvents, including alcohols and acetone, which are commonly used in sol-gel methods, this method
No technology has been developed that can be applied to the production of u-0-based superconducting composite oxide thin films.
発明が解決しようとする問題点
本発明は、銅アルコキシドの有機溶媒への可溶化を図る
ことによって、上記の製造上の利点を有するゾル−ゲル
法のＹ−Ｂａ−Ｃｕ−０系超伝導性複合酸化物薄膜の製
造への適用を可能にするためになされたものである。Problems to be Solved by the Invention The present invention aims to solubilize copper alkoxide in an organic solvent to produce a Y-Ba-Cu-0 based superconductor produced by the sol-gel method, which has the above-mentioned manufacturing advantages. This was done to enable application to the production of composite oxide thin films.
問題点を解決するための手段
即ち本発明は、イツトリウムアルコキシド、バリウムア
ルコキシドおよび銅アルコキシドをアルカノールアミン
含有有機溶媒に溶解させた溶液を基体上に塗布し、該塗
布膜をゲル化させ、該ゲル化膜を前焼成処理に付した後
、酸素雰囲気下での焼鈍処理後、炉中冷却することを特
徴とする酸化物超伝導体薄膜の製造方法に関する。A means for solving the problem, that is, the present invention, is to apply a solution in which yttrium alkoxide, barium alkoxide, and copper alkoxide are dissolved in an alkanolamine-containing organic solvent onto a substrate, to gel the coating film, and to form a gel. The present invention relates to a method for producing an oxide superconductor thin film, which comprises subjecting the film to a pre-calcination treatment, followed by annealing in an oxygen atmosphere, and then cooling in a furnace.
本発明に使用するイツトリウム、バリウムまたは銅のア
ルコキシドとしてはメトキシド、エトキシド、ノルマル
プロポキシド、イソプロポキシド、ノルマルブトキシド
、イソブトキシド、セカンダリ−ブトキシドおよびター
シャリ−ブトキシドが例示され、これらは所望により２
Ｆ１以上併用してもよい。Examples of yttrium, barium or copper alkoxides used in the present invention include methoxide, ethoxide, normal propoxide, isopropoxide, normal butoxide, isobutoxide, secondary butoxide and tertiary butoxide, which may optionally be
F1 or higher may be used in combination.
このような金属アルコキシドは公知の方法、例えばこれ
らの金属の塩化物とりチウムアルコキシドとの交換反応
等によって調製することができる。Such metal alkoxides can be prepared by known methods such as exchange reaction of chlorides of these metals with tium alkoxides.
本発明に使用するアルカノールアミンとしては、モノエ
タノールアミン、ジェタノールアミン、トリエタノール
アミン、メチルモノエタノールアミン、エヂルモノエタ
ノールアミン、イソプロピルモノエタノールアミン、ノ
ルマルブヂルモノエタノールアミン、ジメチルエタノー
ルアミン、ジメチルエタノールアミン、メチルイソプロ
ピルエタノールアミン、ノルマルブチルジェタノールア
ミン、ジブチルエタノールアミン、トリイソプロパノー
ルアミンおよびイソプロパノールアミン等が例示され、
これらは所望により２種以上併用してもよい。The alkanolamines used in the present invention include monoethanolamine, jetanolamine, triethanolamine, methylmonoethanolamine, edylmonoethanolamine, isopropylmonoethanolamine, n-butylmonoethanolamine, dimethylethanolamine, and dimethylethanol. Examples include amine, methylisopropylethanolamine, n-butyljetanolamine, dibutylethanolamine, triisopropanolamine and isopropanolamine,
Two or more of these may be used in combination if desired.
この種のアルカノールアミンの有機溶媒への配合量は特
に限定的ではないが、通常は１〜２０％である。The amount of this type of alkanolamine added to the organic solvent is not particularly limited, but is usually 1 to 20%.
アルカノールアミンを配合する有機溶媒としてはメタノ
ール、エタノール、ノルマルプロパツール、ノルマルブ
タノール、イソブタノール、セカンダリ−ブタノールお
よびターシャリ−ブタノール等の低級アルコールが好適
であるが、その他の溶媒、例えばベンゼン、トルエン、
キシレン、およびエヂレングリコール等のグリコール類
等を適宜使用してもよい。Lower alcohols such as methanol, ethanol, normal propatool, normal butanol, isobutanol, secondary butanol, and tertiary butanol are suitable as the organic solvent in which the alkanolamine is blended, but other solvents such as benzene, toluene,
Glycols such as xylene and ethylene glycol may be used as appropriate.
上Ｓ己のイツトリウムアルコキシド、バリウムアルコキ
シドおよび銅アルコキシドを所定の割合、例えば、イツ
トリウム１モルあたりバリウム１．５〜２．５モル、銅
２．５〜３．５モルの割合でアルカノールアミン含有有
機溶媒に溶解させた溶液を基体上に塗布する。The alkanolamine-containing organic yttrium alkoxide, barium alkoxide, and copper alkoxide of the above are mixed in a predetermined ratio, for example, 1.5 to 2.5 moles of barium and 2.5 to 3.5 moles of copper per mole of yttrium. A solution dissolved in a solvent is applied onto a substrate.
彼コーティング基体の材質は特に限定的ではないが、基
体上に形成される超伝導性複合酸化物との反応性が極め
て低く、熱膨張係数や格子定数が複合酸化物の値と類似
する材質、例えばジルコニア、マグネシア、ヂタン酸ス
トロンチウム、または高純度アルミナ等が好ましい。The material of the coating substrate is not particularly limited, but materials that have extremely low reactivity with the superconducting composite oxide formed on the substrate and whose coefficient of thermal expansion and lattice constant are similar to those of the composite oxide; For example, zirconia, magnesia, strontium ditanate, high purity alumina, etc. are preferred.
上記のイツトリウムアルコキシド等の金属アルコキシド
溶液を基体上に塗布する方法も特に限定的ではなく、該
溶液を基体上に滴下する簡易な方法を使用してもよいが
、通常は基体を該溶液中に浸漬した後、ゆっくりと引き
上げるデイツプコーティング法、またはスピンコーティ
ング法等を使用する。The method of applying a metal alkoxide solution such as the above-mentioned yttrium alkoxide onto a substrate is not particularly limited, and a simple method of dropping the solution onto the substrate may be used, but usually the substrate is placed in the solution. A dip coating method or a spin coating method, in which the material is dipped in water and then slowly pulled up, is used.
基体上の塗布膜は次いでゲル化処理に付される。The coating film on the substrate is then subjected to a gelling treatment.
ゲル化は通常、ホットプレート等の加熱手段を用いて約
８０〜３００℃で約１〜１０分間加熱することによって
行なうが、これに限定されない。Gelation is usually carried out by heating at about 80 to 300° C. for about 1 to 10 minutes using a heating means such as a hot plate, but is not limited thereto.
ゲル化膜は次いで前焼成処理に付される。前焼成処理は
通常、空気中または好ましくは酸素気流中において、４
５０〜９５０℃で１〜２０分間行なう。The gelled film is then subjected to a pre-baking treatment. The pre-calcination treatment is usually carried out in air or preferably in a stream of oxygen.
It is carried out at 50-950°C for 1-20 minutes.
この前焼成処理までの工程を複数回繰り返すことによっ
て、最終的に得られる薄膜の厚さを適宜調整することが
可能となる。By repeating the steps up to this pre-baking treatment multiple times, it becomes possible to adjust the thickness of the finally obtained thin film as appropriate.
前焼成処理に付した薄膜を最後に酸素雰囲気下での焼鈍
処理およびその後の炉中冷却により、Ｙ−Ｄａ−Ｃｕ−
０系の超伝導性複合酸化物薄膜が得られる。焼鈍処理は
通常、４５０〜９５０℃で１０〜８０時間行ない、処理
後の薄膜は炉内において徐冷しなければならない。The thin film subjected to the pre-baking treatment is finally annealed in an oxygen atmosphere and then cooled in a furnace to form Y-Da-Cu-
A 0-based superconducting composite oxide thin film is obtained. The annealing treatment is usually carried out at 450 to 950° C. for 10 to 80 hours, and the thin film after treatment must be slowly cooled in a furnace.
本発明方法によって得られる薄膜の組成は金属アルコキ
シドの配合割合等によって左右されるが、例えば次の組
成が挙げられる：
ＹＢａｔＣｕ３０’ （ｘ＝６．５〜７．０）以下、
本発明を実施例によって説明する。The composition of the thin film obtained by the method of the present invention depends on the blending ratio of metal alkoxide, etc., but examples include the following composition: YBatCu30' (x = 6.5 to 7.0) and below,
The present invention will be explained by examples.
実施例１
撹拌機と滴下漏斗を備えた反応容器内に金属バリウム０
．８２９とメタノール１０Ｑｉｅを入れ、窒素気流中で
２時間還流した後、イツトリウムブトキシドの０．４４
ｍｏｌ／１２キシレン溶液（北興化学社市販品） ６
＊Ｑとトリエタノールアミン５村を添加し、さらに２
時間還流した。Example 1 Metallic barium 0 in a reaction vessel equipped with a stirrer and a dropping funnel
．． 829 and 10 Qie of methanol were added and refluxed for 2 hours in a nitrogen stream.
mol/12 xylene solution (commercial product from Hokuko Kagakusha) 6
*Add Q and 5 molecules of triethanolamine, and add 2 more
Refluxed for an hour.
反応混合物を室温まで冷却した後、銅メトキシド１．１
９を添加し、撹拌を約２時間続行して得られた濃青色透
明溶液をジルコニア基板（２１ｘｍＸ２ ＋ ｊｆｉＸ
１ ａｍ：日本特殊陶業社製）上に４．ｌ！ｉ（約０
゜２ 麓Ｉ２）滴下し、これをホットプレート上におい
て、約２００℃で数分間の熱処理に付すことによって基
板上に形成されたゲル化膜を空気中において８００°Ｃ
で５分間の前焼成処理に付した。After cooling the reaction mixture to room temperature, copper methoxide 1.1
9 was added, stirring was continued for about 2 hours, and the resulting dark blue transparent solution was transferred to a zirconia substrate (21xmX2 + jfiX
1 am: manufactured by Nippon Tokushu Togyo Co., Ltd.) 4. l! i (approximately 0
゜2 Foot I2) The gelled film formed on the substrate was heated at 800°C in the air by placing it dropwise on a hot plate and subjecting it to heat treatment at approximately 200°C for several minutes.
The sample was pre-baked for 5 minutes.
上記のゲル化形成工程と前焼成処理工程を５回繰り返す
ことによって得られた薄膜を酸素気流中における８００
℃で８０時間の焼鈍処理に付した後、徐冷することによ
って調製された薄膜（厚さ約０゜５μｍ）は、Ｘ線回折
によればＹＩ３ａｔＣｕ３０ｘ（ｘ＝ ６ 、５〜７．
０）の組成を有しており、その抵抗値（室温で約５Ω）
は冷却に伴って９８Ｋから部域し、５ＧＫ付近でゼロと
なった。The thin film obtained by repeating the above gel formation process and pre-baking process 5 times was heated to 800°C in an oxygen stream.
The thin film (approximately 0.5 μm thick) prepared by annealing for 80 hours at 0.degree.
0), and its resistance value (approximately 5Ω at room temperature)
The temperature ranged from 98K with cooling and reached zero around 5GK.
発明の効果
本発明による超伝導性複合酸化物薄膜の製造方法によれ
ば、微細構造が制御された均一組成の超伝導性複合酸化
物薄膜を簡易な装置を用いて容易に製造することができ
るばかりでなく、該薄膜の厚さ、表面積および形態等を
自由に設計することが可能である。Effects of the Invention According to the method for producing a superconducting composite oxide thin film according to the present invention, a superconducting composite oxide thin film with a uniform composition and a controlled microstructure can be easily produced using a simple device. In addition, the thickness, surface area, shape, etc. of the thin film can be freely designed.
従って本発明は、低抵抗で高磁力が要求される広範囲の
分野、例えばジョセフソン素子、プリント配線回路、磁
気シールド、被覆磁気コイル等の分野において有効に利
用できる技術である。Therefore, the present invention is a technology that can be effectively used in a wide range of fields that require low resistance and high magnetic force, such as fields such as Josephson elements, printed wiring circuits, magnetic shields, and coated magnetic coils.
Claims (1)
および銅アルコキシドをアルカノールアミン含有有機溶
媒に溶解させた溶液を基体上に塗布し、該塗布膜をゲル
化させ、該ゲル化膜を前焼成処理に付した後、酸素雰囲
気下での焼鈍処理後、炉中冷却することを特徴とする酸
化物超伝導体薄膜の製造方法。 ２、ゲル化と前焼成処理を複数回繰り返した後、酸素雰
囲気下での焼鈍処理を行なう第１項記載の酸化物超伝導
体薄膜の製造方法。 ３、イットリウム、バリウムまたは銅のアルコキシドが
メトキシド、エトキシド、ノルマルプロポキシド、イソ
プロポキシド、ノルマルブトキシド、イソブトキシド、
セカンダリーブトキシドまたはターシャリーブトキシド
である第１項記載の酸化物超伝導体薄膜の製造方法。 ４、アルカノールアミンが、モノエタノールアミン、ジ
エタノールアミン、トリエタノールアミン、エチルモノ
エタノールアミン、ノルマルブチルモノエタノールアミ
ン、ジメチルエタノールアミン、ジエチルエタノールア
ミン、ノルマルブチルエタノールアミン、ジブチルエタ
ノールアミン、トリイソプロパノールアミンおよびイソ
プロパノールアミンから成る群から選択される１種もし
くはそれ以上のアルカノールアミンである第１項記載の
酸化物超伝導体薄膜の製造方法。 ５、アルカノールアミンの含有量が１〜２０％である第
１項記載の酸化物超伝導体薄膜の製造方法。 ６、前焼成処理を空気中または酸素気流中において４５
０〜９５０℃で１〜２０分間行ない、酸素雰囲気下での
焼鈍処理を４５０〜９５０℃で１０〜８０時間行なう第
１項記載の酸化物超伝導体薄膜の製造方法。 ７、薄膜の組成がＹＢａ＿２Ｃｕ＿３Ｏ＿ｘ（ｘ＝６．
５〜７．０）である第１項記載の酸化物超伝導体薄膜の
製造方法。[Claims] 1. A solution in which yttrium alkoxide, barium alkoxide, and copper alkoxide are dissolved in an alkanolamine-containing organic solvent is applied onto a substrate, the applied film is gelled, and the gelled film is pre-baked. 1. A method for producing an oxide superconductor thin film, the method comprising: annealing in an oxygen atmosphere; and cooling in a furnace. 2. The method for producing an oxide superconductor thin film according to item 1, wherein the gelation and pre-baking treatments are repeated multiple times, followed by annealing in an oxygen atmosphere. 3. Yttrium, barium or copper alkoxide is methoxide, ethoxide, normal propoxide, isopropoxide, normal butoxide, isobutoxide,
2. The method for producing an oxide superconductor thin film according to item 1, which is a secondary butoxide or a tertiary butoxide. 4. Alkanolamines include monoethanolamine, diethanolamine, triethanolamine, ethyl monoethanolamine, n-butyl monoethanolamine, dimethylethanolamine, diethylethanolamine, n-butylethanolamine, dibutylethanolamine, triisopropanolamine, and isopropanolamine. 2. The method for producing an oxide superconductor thin film according to claim 1, wherein the oxide superconductor thin film is one or more alkanolamines selected from the group consisting of: 5. The method for producing an oxide superconductor thin film according to item 1, wherein the alkanolamine content is 1 to 20%. 6. Pre-calcining treatment in air or oxygen stream for 45 minutes
2. The method for producing an oxide superconductor thin film according to item 1, wherein the annealing treatment is performed at 0 to 950°C for 1 to 20 minutes, and the annealing treatment is performed at 450 to 950°C for 10 to 80 hours. 7. The composition of the thin film is YBa_2Cu_3O_x (x=6.
5-7.0) The method for producing an oxide superconductor thin film according to item 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29577887A JPH01138129A (en) | 1987-11-24 | 1987-11-24 | Production of oxide superconductor thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29577887A JPH01138129A (en) | 1987-11-24 | 1987-11-24 | Production of oxide superconductor thin film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01138129A true JPH01138129A (en) | 1989-05-31 |
Family
ID=17825034
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29577887A Pending JPH01138129A (en) | 1987-11-24 | 1987-11-24 | Production of oxide superconductor thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01138129A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5231074A (en) * | 1990-04-17 | 1993-07-27 | Massachusetts Institute Of Technology | Preparation of highly textured oxide superconducting films from mod precursor solutions |
| US5504226A (en) * | 1991-11-28 | 1996-04-02 | Kyocera Corporation | Copper oxide superconductor, a process for its production, and a copper complex used therein |
| US6788247B2 (en) | 2001-02-21 | 2004-09-07 | Mitsubishi Denki Kabushiki Kaisha | Distance/velocity measuring method and radar signal processing device |
-
1987
- 1987-11-24 JP JP29577887A patent/JPH01138129A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5231074A (en) * | 1990-04-17 | 1993-07-27 | Massachusetts Institute Of Technology | Preparation of highly textured oxide superconducting films from mod precursor solutions |
| US5504226A (en) * | 1991-11-28 | 1996-04-02 | Kyocera Corporation | Copper oxide superconductor, a process for its production, and a copper complex used therein |
| US5578553A (en) * | 1991-11-28 | 1996-11-26 | Kyocera Corporation | 1-2-4 copper oxide superconductor, a process for its production, and a copper used therein |
| US6788247B2 (en) | 2001-02-21 | 2004-09-07 | Mitsubishi Denki Kabushiki Kaisha | Distance/velocity measuring method and radar signal processing device |
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