JPH01212219A - Production of thin oxide superconducting film - Google Patents
Production of thin oxide superconducting filmInfo
- Publication number
- JPH01212219A JPH01212219A JP63048963A JP4896388A JPH01212219A JP H01212219 A JPH01212219 A JP H01212219A JP 63048963 A JP63048963 A JP 63048963A JP 4896388 A JP4896388 A JP 4896388A JP H01212219 A JPH01212219 A JP H01212219A
- Authority
- JP
- Japan
- Prior art keywords
- oxygen
- thin film
- temperature
- atmosphere
- substrate
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000010409 thin film Substances 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000012298 atmosphere Substances 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 239000010408 film Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 239000010949 copper Substances 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 6
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- 238000010304 firing Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- 229910052797 bismuth Inorganic materials 0.000 claims 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract 1
- 238000000137 annealing Methods 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 229910052726 zirconium Inorganic materials 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 230000006399 behavior Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 241000779819 Syncarpia glomulifera Species 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- -1 organic acid salts Chemical class 0.000 description 2
- 239000001739 pinus spp. Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229940036248 turpentine Drugs 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000013522 chelant Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- LMHHRCOWPQNFTF-UHFFFAOYSA-N s-propan-2-yl azepane-1-carbothioate Chemical compound CC(C)SC(=O)N1CCCCCC1 LMHHRCOWPQNFTF-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E40/00—Technologies for an efficient electrical power generation, transmission or distribution
- Y02E40/60—Superconducting electric elements or equipment; Power systems integrating superconducting elements or equipment
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、酸化物超伝導薄膜の製造方法に関し、更に詳
しくは、液体窒素の沸点である７７Ｋを超える臨界温度
（ゼロ抵抗温度）を持つ酸化物超伝導薄膜の製造方法に
関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing an oxide superconducting thin film, and more specifically, to a method for producing an oxide superconducting thin film, and more specifically, an oxide superconducting thin film having a critical temperature (zero resistance temperature) exceeding 77 K, which is the boiling point of liquid nitrogen. This invention relates to a method for manufacturing a superconducting thin film.
発明の背景
高い臨界温度を示す酸化物伝導材料については、室温近
くで超伝導現象を示す材料の創製の対する研究と同時に
、実用化を０指した応用研究が活発に行なわれている。BACKGROUND OF THE INVENTION Concerning oxide conductive materials exhibiting a high critical temperature, research is being actively conducted on the creation of materials exhibiting superconductivity near room temperature, as well as applied research aimed at practical application.
高温超伝導材料の利用形態として、焼結体と薄膜が考え
られ、中でも超伝導薄膜は、エレクトロニクスデバイス
などへの応用が期待されている。High-temperature superconducting materials can be used in sintered bodies and thin films, and superconducting thin films are particularly expected to be used in electronic devices.
酸化物超伝導薄膜は、従来スパッタ法、蒸着法、スクリ
ーン印刷法などで形成されている。酸化物薄膜の形成方
法としては、液相熱分解法も知られており、この方法は
、装置が簡単であり、大面積。Oxide superconducting thin films are conventionally formed by sputtering, vapor deposition, screen printing, and the like. Liquid phase pyrolysis is also known as a method for forming oxide thin films, and this method requires simple equipment and can be applied over a large area.
複雑な形状のものに均一に成膜することができるなど利
点を持ち、超伝導薄膜合成法として非常に有望である。This method has the advantage of being able to form a uniform film on objects with complex shapes, making it a very promising method for synthesizing superconducting thin films.
液相熱分解法を採用した酸化物超伝導薄膜の形成は、熊
谷らにより、Ｃｈｅｍｉｓｔｒｙ Ｌｅｔｔｅｒｓ。The formation of oxide superconducting thin films using liquid phase pyrolysis is described in Chemistry Letters by Kumagai et al.
１６４５−１６４６ （１９８７）に報告されているが
、得られた酸化物超伝導薄膜の臨界温度（ゼロ抵抗温度
）は液体窒素の沸点より低い。1645-1646 (1987), the critical temperature (zero resistance temperature) of the obtained oxide superconducting thin film is lower than the boiling point of liquid nitrogen.
発明の目的
本発明の目的は、液体窒素の沸点７７Ｋを越える臨界温
度（ゼロ抵抗温度）を持ち、しかも臨界電流密度が大き
い高温酸化物超伝導薄膜を有利に製造できる方法を提供
することにある。OBJECTS OF THE INVENTION An object of the present invention is to provide a method that can advantageously produce a high-temperature oxide superconducting thin film that has a critical temperature (zero resistance temperature) exceeding the boiling point of liquid nitrogen, 77 K, and a high critical current density. .
発明の構成
上記目、的は、希土類金属、バリウムおよび／またはス
トロンチウム、並びに銅の各金属塩を含む溶液を、基材
に塗布し、酸素含有雰囲気中、８５０〜９３０℃の温度
で熱処理し、次いで酸素雰囲気中徐冷することを特徴と
する酸化物超伝導薄膜の製造方法により達成される。Structure of the Invention The above object is to apply a solution containing metal salts of rare earth metals, barium and/or strontium, and copper to a base material, and heat-treat the solution at a temperature of 850 to 930°C in an oxygen-containing atmosphere. This is achieved by a method for producing an oxide superconducting thin film, which is characterized in that it is then slowly cooled in an oxygen atmosphere.
本発明の好ましい態様では、金属塩溶液を塗布した基材
を、熱処理前に、４００〜６００℃の温度で焼成する。In a preferred embodiment of the invention, the substrate coated with the metal salt solution is fired at a temperature of 400 to 600° C. before heat treatment.
希土類金属としては、イツトリウム、ランタノイド元素
、およびこれらの混合物などが例示できる。Examples of rare earth metals include yttrium, lanthanide elements, and mixtures thereof.
希土類金属、バリウムおよび／またはストロンチウム、
並びに銅の金属塩としては、有機酸塩（たとえば、ナフ
テン酸塩、カプリル酸塩、ステアリン酸塩）、キレート
錯体（たとえば、アセチルアセトン錯塩）、アルコキシ
ド（たとえば、メチレート、エチラート、イソプロピレ
ート）が好ましく用いられる。rare earth metals, barium and/or strontium,
In addition, as the copper metal salt, organic acid salts (e.g., naphthenate, caprylate, stearate), chelate complexes (e.g., acetylacetone complex salt), and alkoxides (e.g., methylate, ethylate, isopropylate) are preferably used. It will be done.
溶液中の各金属塩の濃度は、得られる超伝導酸化物の組
成に合わせて調整される。一般に、全金属成分濃度は、
６．５重量％以下に調整されるが、この範囲に限定され
ることはない。The concentration of each metal salt in the solution is adjusted according to the composition of the superconducting oxide to be obtained. Generally, the total metal component concentration is
The content is adjusted to 6.5% by weight or less, but is not limited to this range.
溶媒としては、アルコール（たとえば、エタノール、イ
ソプロパツール）、芳香族化合物（たとえば、ベンゼン
、トルエン、キシレン）、シクロヘキサン、ターペン、
灯油、酢酸ブチル、クロロホルム、エーテル、ケトンな
どが例示できる。Solvents include alcohols (e.g. ethanol, isopropanol), aromatic compounds (e.g. benzene, toluene, xylene), cyclohexane, turpentine,
Examples include kerosene, butyl acetate, chloroform, ether, and ketone.
基材の種類は問わないが、イツトリウム安定化ジルコニ
ア（ＹＳＺ）が好ましい。The type of base material does not matter, but yttrium stabilized zirconia (YSZ) is preferred.
本発明の製造方法では、基材を上記のような金属塩溶液
を基材に塗布する。好ましくは、溶液を塗布した基材を
、酸素含有雰囲気（たとえば、空気、酸素／不活性ガス
混合物）または不活性気体（窒素、ヘリウム、アルゴン
など）中、４００〜６００℃の温度で焼成する。この焼
成の初期段階を不活性気体中で行うと、より臨界電流密
度の大きい酸化物超伝導薄膜が得られる。In the manufacturing method of the present invention, a metal salt solution as described above is applied to the base material. Preferably, the substrate coated with the solution is fired at a temperature of 400-600<0>C in an oxygen-containing atmosphere (eg air, oxygen/inert gas mixture) or inert gas (nitrogen, helium, argon, etc.). If this initial stage of firing is performed in an inert gas, an oxide superconducting thin film with a higher critical current density can be obtained.
−回の塗布および焼成によって所望の膜厚が得られない
場合には、塗布および焼成の工程を２回またはそれ以上
繰り返して、所定の厚さの薄膜を得ることができる。塗
膜の厚さは、１．５μ度を越えるのが好ましい。- If the desired film thickness cannot be obtained by coating and baking twice, the coating and baking steps can be repeated two or more times to obtain a thin film of a predetermined thickness. The thickness of the coating film is preferably greater than 1.5 micro degrees.
焼成後、金属酸化物薄膜が塗布された基材を、酸素含有
雰囲気、特に純酸素気流中、８５０〜９３０℃、好まし
くは８７０〜９２０℃の温度で熱処理する。熱処理時間
は、通常３〜３０時間である。好ましくは、酸素含有雰
囲気中で焼成を行った場合には４．５〜８．５時間であ
り、不活性気体雰囲気中′で初期焼成を行った場合には
１２〜３０時間である。After firing, the substrate coated with the metal oxide thin film is heat treated in an oxygen-containing atmosphere, in particular in a stream of pure oxygen, at a temperature of 850-930°C, preferably 870-920°C. The heat treatment time is usually 3 to 30 hours. Preferably, the time is 4.5 to 8.5 hours when the firing is performed in an oxygen-containing atmosphere, and 12 to 30 hours when the initial firing is performed in an inert gas atmosphere.
熱処理後、基材を、酸素気流中、４００℃以下の温度に
徐冷する。After the heat treatment, the substrate is slowly cooled to a temperature of 400° C. or lower in an oxygen stream.
本発明の製造方法によれば、窒素の沸点７７に以上の臨
界温度（ゼロ抵抗温度）を持つ酸化物超伝導薄膜を再現
性よく、かつ効率的に得ることができる。According to the manufacturing method of the present invention, an oxide superconducting thin film having a critical temperature (zero resistance temperature) equal to or higher than the boiling point of nitrogen, 77, can be obtained efficiently and reproducibly.
寒貴桝 以下に実施例を示し、本発明をより詳しく説明する。Kankimasu EXAMPLES The present invention will be explained in more detail with reference to Examples below.
実施例１〜３および比較例１〜３
［薄膜合成］
酸化物超伝導薄膜の合成は、溶液調製一基板への塗布→
熱処理の手順で行った。Examples 1 to 3 and Comparative Examples 1 to 3 [Thin film synthesis] Synthesis of oxide superconducting thin films consists of solution preparation, coating on a substrate →
This was done using a heat treatment procedure.
出発原料としてイツトリウム、バリウムおよび銅それぞ
れのナフテン酸金属塩を用いた。原子比がＹ ：Ｂａ：
Ｃｕ＝ １ ：２ ：３となるように金属塩を混合し、
これをターペンで希釈して金属成分濃度６重量％の溶液
を調製した。Naphthenic acid metal salts of yttrium, barium, and copper were used as starting materials. Atomic ratio is Y:Ba:
Mix metal salts so that Cu=1:2:3,
This was diluted with turpentine to prepare a solution having a metal component concentration of 6% by weight.
この溶液をデイプコーティング法によりＹＳＺ基板に塗
布（引き上げ速度８ 、７ ａｍ／分）した後、大気中
５００℃で焼成した。所定の膜厚になるまで塗布−焼成
を繰り返し、さらに、酸素気流中、８００℃（比較例１
）、９００°Ｃ（実施例１〜３および比較例２）または
９５０°Ｃ（比較例３）で所定時間熱処理した後、２０
０℃まで炉冷することにより、超伝導薄膜を合成した。This solution was applied to a YSZ substrate by a deep coating method (pulling speed: 8, 7 am/min), and then baked at 500° C. in the air. The coating and baking process was repeated until a predetermined film thickness was obtained, and then the film was heated at 800°C in an oxygen stream (Comparative Example 1).
), 900°C (Examples 1 to 3 and Comparative Example 2) or 950°C (Comparative Example 3) for a predetermined period of time, then 20
A superconducting thin film was synthesized by furnace cooling to 0°C.
各実施例における膜厚（表面膜差計により測定）および
熱処理時間を第１表に示す。Table 1 shows the film thickness (measured using a surface film difference meter) and heat treatment time in each example.
［測定コ
得られた薄膜試料を液体窒素を冷媒として冷却し、電気
抵抗の温度依存性および臨界温度を求めた。[Measurement] The obtained thin film sample was cooled using liquid nitrogen as a coolant, and the temperature dependence of electrical resistance and critical temperature were determined.
抵抗測定は、端子を銀ペーストで接着し、直流４端子法
により行ったー。温度はＣＡ熱電対により測定した。The resistance was measured using the DC 4-terminal method with the terminals glued together with silver paste. Temperature was measured with a CA thermocouple.
臨界温度以上での抵抗の温度依存性については、温度が
下がるにつれて電気抵抗が上がる「半導体的挙動」、電
気抵抗が下がる「金属的挙動」、および温度によって電
気抵抗が変わらない「はぼ−定の挙動」に分類される。Regarding the temperature dependence of resistance above the critical temperature, there are ``semiconductor-like behavior'' in which the electrical resistance increases as the temperature decreases, ``metallic behavior'' in which the electrical resistance decreases, and ``virtually constant behavior'' in which the electrical resistance does not change with temperature. behavior.
超伝導に転移する臨界温度としては、温度を下げていく
と抵抗がこれらの挙動からはずれて急激に下がり始める
オンセット温度Ｔ ｏｎｓｅｔと、抵抗が完全にゼロに
なるゼロ抵抗温度Ｔ ｚｅｒｏを第１表に示した。The critical temperatures for transition to superconductivity are the onset temperature T onset, at which the resistance deviates from these behaviors and begins to drop rapidly as the temperature is lowered, and the zero resistance temperature T zero, at which the resistance becomes completely zero. Shown in the table.
この表の結果より明らかなように、抵抗の温度依存性と
臨界温度の間には強い相関関係が存在する。すなわち７
７に以上のゼロ抵抗温度を示すのは抵抗が金属的かある
いは一定の挙動を示す場合のみである。この場合の抵抗
変化を、２７３Ｋにおける抵抗値Ｒ７９，との比Ｒ／Ｒ
ｔ、ａとして第１図に示す。図中、○は実施例１の結果
を、口は実施例２の結果を、△は実施例３の結果を示す
。As is clear from the results in this table, there is a strong correlation between the temperature dependence of resistance and the critical temperature. i.e. 7
A zero resistance temperature of 7 or above is exhibited only when the resistance is metallic or exhibits a certain behavior. The resistance change in this case is expressed as the ratio R/R of the resistance value R79 at 273K.
It is shown in FIG. 1 as t and a. In the figure, ◯ indicates the results of Example 1, ◯ indicates the results of Example 2, and △ indicates the results of Example 3.
実施例４
初期焼成を窒素雰囲気中で行い、熱処理を９００℃で１
６．５時間行う以外は実施例１と同様の方法で、酸化物
超伝導薄膜を形成した。０℃での抵抗率および臨界電流
密度を第２表に示す。Example 4 Initial firing was performed in a nitrogen atmosphere, and heat treatment was performed at 900°C for 1 time.
An oxide superconducting thin film was formed in the same manner as in Example 1, except that the heating was carried out for 6.5 hours. The resistivity and critical current density at 0°C are shown in Table 2.
第２表
発明の効果
本発明の製造方法によれば、臨界温度（ゼロ抵抗温度）
が液体窒素の沸点をこえる酸化物超伝導薄膜が得られる
。Table 2 Effects of the invention According to the manufacturing method of the invention, critical temperature (zero resistance temperature)
An oxide superconducting thin film whose temperature exceeds the boiling point of liquid nitrogen can be obtained.
また、本発明においては、薄膜形成の過程を２つの過程
、すなわち比較的低温での焼成過程（原料の熱分解過程
）と比較的高温での熱処理（結晶化・結晶成長過程）と
に別けて行っている。それ故、薄膜形成において薄膜の
ひび割れが無く、基材と酸化物薄膜との密着性に優れた
製品を得ることができる。Furthermore, in the present invention, the process of thin film formation is divided into two processes: a firing process at a relatively low temperature (thermal decomposition process of raw materials) and a heat treatment at a relatively high temperature (crystallization/crystal growth process). Is going. Therefore, it is possible to obtain a product with no cracks in the thin film during thin film formation and excellent adhesion between the base material and the oxide thin film.
更に、比較的低温での焼成の初期過程を不活性気体雰囲
気中で行うと、酸化物薄膜の臨界電流密度が向上する。Furthermore, if the initial stage of firing at a relatively low temperature is performed in an inert gas atmosphere, the critical current density of the oxide thin film is improved.
第１図は、実施例１〜３で得られた酸化物超伝導薄膜の
抵抗変化を示すグラフである。FIG. 1 is a graph showing the resistance changes of the oxide superconducting thin films obtained in Examples 1 to 3.
Claims (1)
およびストロンチウムから成る群から選ばれた少なくと
も１種の金属元素、並びに銅の各金属塩を含む溶液を、
基材に塗布し、酸素含有雰囲気中、８５０〜９３０℃の
温度で熱処理し、次いで酸素雰囲気中徐冷することを特
徴とする酸化物超伝導薄膜の製造方法。 ２、金属塩溶液を塗布した基材を、酸素含有雰囲気中、
４００〜６００℃の温度で焼成した後、熱処理する特許
請求の範囲第１項記載の酸化物超伝導薄膜の製造方法。 ３、金属塩溶液を塗布した基材を、ます不活性気体雰囲
気中、次いで酸素含有雰囲気中、４００〜６００℃の温
度で焼成した後、熱処理する特許請求の範囲第１項記載
の酸化物超伝導薄膜の製造方法。 ４、希土類金属が、イットリウムである特許請求の範囲
第１項記載の製造方法。 ５、溶液の塗布および４００〜６００℃での焼成を、１
．５μｍを越える膜厚になるまで繰り返し行う特許請求
の範囲第２〜４項のいずれかに記載の製造方法。 ６、８５０〜９３０℃での熱処理を３〜３０時間行う特
許請求の範囲第１項記載の製造方法。 ７、熱処理を純酸素気流中で行う特許請求の範囲第１項
または第６項記載の製造方法。[Claims] 1. A solution containing a rare earth metal or at least one metal element selected from the group consisting of bismuth, barium, calcium, and strontium, and each metal salt of copper,
1. A method for producing an oxide superconducting thin film, which comprises coating on a substrate, heat-treating in an oxygen-containing atmosphere at a temperature of 850 to 930°C, and then slowly cooling in an oxygen atmosphere. 2. The base material coated with the metal salt solution is placed in an oxygen-containing atmosphere.
The method for producing an oxide superconducting thin film according to claim 1, wherein the oxide superconducting thin film is heat-treated after firing at a temperature of 400 to 600°C. 3. The base material coated with the metal salt solution is fired at a temperature of 400 to 600°C in an inert gas atmosphere, then in an oxygen-containing atmosphere, and then heat treated. Method for manufacturing conductive thin film. 4. The manufacturing method according to claim 1, wherein the rare earth metal is yttrium. 5. Applying the solution and baking at 400-600°C, 1.
．． The manufacturing method according to any one of claims 2 to 4, wherein the process is repeated until the film thickness exceeds 5 μm. 6. The manufacturing method according to claim 1, wherein heat treatment is performed at 850 to 930°C for 3 to 30 hours. 7. The manufacturing method according to claim 1 or 6, wherein the heat treatment is performed in a pure oxygen stream.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63048963A JPH01212219A (en) | 1987-10-15 | 1988-03-02 | Production of thin oxide superconducting film |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62-262204 | 1987-10-15 | ||
| JP26220487 | 1987-10-15 | ||
| JP63048963A JPH01212219A (en) | 1987-10-15 | 1988-03-02 | Production of thin oxide superconducting film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01212219A true JPH01212219A (en) | 1989-08-25 |
Family
ID=26389310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63048963A Pending JPH01212219A (en) | 1987-10-15 | 1988-03-02 | Production of thin oxide superconducting film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01212219A (en) |
-
1988
- 1988-03-02 JP JP63048963A patent/JPH01212219A/en active Pending
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