JPH02179880A - Production of thin oxide ceramic superconducting film - Google Patents
Production of thin oxide ceramic superconducting filmInfo
- Publication number
- JPH02179880A JPH02179880A JP33505788A JP33505788A JPH02179880A JP H02179880 A JPH02179880 A JP H02179880A JP 33505788 A JP33505788 A JP 33505788A JP 33505788 A JP33505788 A JP 33505788A JP H02179880 A JPH02179880 A JP H02179880A
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- oxide ceramic
- oxygen plasma
- superconducting
- thin film
- 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
- 239000011224 oxide ceramic Substances 0.000 title claims abstract description 23
- 229910052574 oxide ceramic Inorganic materials 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000000758 substrate Substances 0.000 claims abstract description 40
- 239000001301 oxygen Substances 0.000 claims abstract description 27
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 150000002739 metals Chemical class 0.000 claims abstract description 4
- 239000010409 thin film Substances 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 239000012159 carrier gas Substances 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 238000005507 spraying Methods 0.000 abstract description 6
- 238000000151 deposition Methods 0.000 abstract description 3
- 239000003595 mist Substances 0.000 abstract 3
- 239000007858 starting material Substances 0.000 abstract 2
- 239000002245 particle Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 7
- 229910001882 dioxygen Inorganic materials 0.000 description 7
- 239000010419 fine particle Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000010408 film Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910014454 Ca-Cu Inorganic materials 0.000 description 1
- 241000238366 Cephalopoda Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
この発明は各種超電導機器や超電導素子、例えば超電導
量子干渉計（ＳＱＵＩＤ）やジョセフソン素子、その他
用電導線等として使用される超電導薄膜を製造する方法
に関し、特に酸化物セラミック系の超電導材料からなる
薄膜を形成する方法に関するものである。[Detailed Description of the Invention] Industrial Application Field This invention relates to a method for manufacturing superconducting thin films used as various superconducting devices and superconducting elements, such as superconducting quantum interferometers (SQUID), Josephson devices, and other conductive wires. In particular, the present invention relates to a method for forming a thin film made of an oxide ceramic superconducting material.
従来の技術
各種超電導材料のうちでも、Ｙ系複合酸化物やＢｉ系複
合酸化物のような酸化物セラミック系超電導材料は、臨
界温度（Ｔｃ）が高い高温超電導物質として近年注目を
浴びている。BACKGROUND OF THE INVENTION Among various superconducting materials, oxide ceramic superconducting materials such as Y-based composite oxides and Bi-based composite oxides have attracted attention in recent years as high-temperature superconducting materials with high critical temperatures (Tc).
従来の酸化物セラミック系超電導材料の製造方法として
は、超電導酸化物を構成する原料金属（例えばＹ等）を
含む塩の水溶液を超音波噴霧器等により噴霧化し、その
霧状の液滴を１００〜５００℃に加熱した基板上に供給
して塩を堆積させ、その塩が堆積した基板を空気あるい
は酸素気流中で９００〜１０００℃に加熱（アニール）
することによって酸化物セラミック系超電導物質を合成
する方法（例えば８．にａｗａｉ ｅｔ ａｌ、、 Ｊ
ＪＡＰ ２６ （１９８７） Ｌ １７４０−Ｌ １７
４２） 、あるいは原料金属を含む塩の水溶液を超音波
ｑ４霧器により噴霧して９００〜１０００℃に加熱され
た抵抗加熱炉中に導入し、その炉内で酸化物セラミック
系超電導物質の微粒子を合成し、その後その微粒子を集
めて成形し、焼結する方法（例えばＴ、 Ｔ、にｏｄａ
ｓ ｅｔ ａｌ、、Δｐｐ１． Ｐｈｙｓ、 Ｌｅｔｔ
。A conventional method for manufacturing oxide ceramic superconducting materials involves atomizing an aqueous solution of a salt containing a raw material metal (for example, Y, etc.) constituting the superconducting oxide using an ultrasonic atomizer, and producing atomized droplets of 100 to 100 ml. Salt is deposited by supplying it onto a substrate heated to 500℃, and the substrate on which the salt is deposited is heated to 900 to 1000℃ in air or oxygen stream (annealing).
A method for synthesizing oxide ceramic superconducting materials by
JAP 26 (1987) L 1740-L 17
42) Alternatively, an aqueous solution of a salt containing raw material metal is atomized by an ultrasonic Q4 atomizer and introduced into a resistance heating furnace heated to 900 to 1000°C, and fine particles of an oxide ceramic superconducting material are formed in the furnace. A method of synthesizing, then collecting, molding, and sintering the fine particles (for example, T, T, oda
s et al, Δpp1. Phys, Lett
.
５２ （１９８８） １６２２； あるいはＮ、 Ｔ
ｏｈｇｅ ｅｔ ａｔ。52 (1988) 1622; or N, T
ohge et at.
ＪＪＡＰ ２７ （１９８８） Ｌ １０８６）などが
知られている。JJAP 27 (1988) L 1086) are known.
発明が解決しようとする課題
前述のような従来の酸化物セラミック系超電導材料の製
造方法のうち、曲者の方法では噴霧による原料の堆積後
、アニーリングを行なうことによってはじめて酸化物セ
ラミック系超電導物質を生成することかでき、また後者
の方法では高温炉内への噴霧により超電導微粒子を生成
させた後に微粒子の成形や焼結を施す必要があり、いず
れの方法も多数のプロセスを必要とし、そのためコスト
上昇をＪＥかざるを得ない問題があった。Problems to be Solved by the Invention Among the conventional methods for manufacturing oxide ceramic superconducting materials as described above, the method of the author is to deposit raw materials by spraying and then annealing to produce the oxide ceramic superconducting materials. In addition, in the latter method, it is necessary to form superconducting fine particles by spraying them into a high-temperature furnace, and then mold and sinter the fine particles. Both methods require numerous processes, and are therefore costly. There was a problem that forced JE to increase the price.
この発明は以上の事情を前頭としてなされたもので、極
めて簡単なプロセスで酸化物セラミック系超電導薄膜を
形成することができる、低コストで量産化可能な酸化物
セラミック系超電導簿膜の製造方法を提供することを目
的とするものである。This invention was made with the above circumstances in mind, and it provides a method for manufacturing an oxide ceramic superconducting thin film that can be mass-produced at low cost and that can form an oxide ceramic superconducting thin film using an extremely simple process. The purpose is to provide
問題点を解決するための手段
この発明の酸化物セラミック系超電導薄膜の製造方法は
、酸化物セラミック系超電導材料を構成する金属を含む
塩の水溶液を噴霧化し、得られた霧状の液滴を酸素プラ
ズマ中に供給して、その酸素プラズマ中もしくは酸素プ
ラズマ近傍に配置された基板上に酸化物セラミック系、
Ｖｌｌｌ電導薄膜を生成させることを特徴とするもので
ある。Means for Solving the Problems The method for producing an oxide ceramic superconducting thin film of the present invention involves atomizing an aqueous solution of a salt containing a metal constituting the oxide ceramic superconducting material, and atomizing the resulting atomized droplets. An oxide ceramic system is supplied into an oxygen plasma and placed on a substrate placed in or near the oxygen plasma.
This method is characterized by producing a Vllll conductive thin film.
作 用
酸素プラズマはその酸化性が極めて強く、そのため酸素
プラズマ中に供給された原料金［水溶液の噴霧液滴は、
ただちに酸化されて酸化物、すなわち超電導物質となる
とともに、その酸素プラズマ中に配置された高温の基板
上に堆積され、基板上に酸化物セラミック系の超電導薄
膜が生成される。Oxidation plasma has extremely strong oxidizing properties, and therefore the raw material supplied into the oxygen plasma [atomized droplets of aqueous solution]
It is immediately oxidized to become an oxide, that is, a superconducting material, and is deposited on a high-temperature substrate placed in the oxygen plasma, producing an oxide ceramic superconducting thin film on the substrate.
ここで、原料金属塩水溶液の噴霧液滴は、基板上に到達
する以前の段階で酸素プラズマによって酸化されて超電
導物質微粒子となり、その超電導物質微粒子の状態で基
板上に到達することも、あるいは基板上に到達した債に
酸化が完了して基板上で超電導物質となることもある。Here, the sprayed droplets of the raw metal salt aqueous solution may be oxidized by oxygen plasma and become superconducting material fine particles before reaching the substrate, and may reach the substrate in the state of superconducting material fine particles, or may reach the substrate in the form of superconducting material fine particles. The bond that reaches the top may complete oxidation and become a superconducting material on the substrate.
いずれにしても原料金属塩の酸化による超電導物質の生
成と基板上への堆積による薄膜生成とが一工程で連続的
もしくは同時的になされることになる。In any case, the production of a superconducting material by oxidation of a raw metal salt and the production of a thin film by deposition on a substrate are performed continuously or simultaneously in one step.
実施例
第１図にこの発明の方法を実施するための装置の一例を
概略的に示す。Embodiment FIG. 1 schematically shows an example of an apparatus for carrying out the method of the present invention.
第１図において、原料金属を含む塩の水溶液１は噴霧器
２に導入されて、超音波噴霧あるいは高速気流噴霧等に
より噴霧されて０，３〜２，０顯程度の霧状の液滴とな
り、第１キヤリヤガス３によって石英等からなる反応管
４の上部に導入される。In FIG. 1, an aqueous salt solution 1 containing a raw metal is introduced into a sprayer 2, and is atomized by ultrasonic spraying or high-speed air spraying to form mist-like droplets of about 0.3 to 2.0 mm. The first carrier gas 3 is introduced into the upper part of a reaction tube 4 made of quartz or the like.
またその反応管４の上部には別に第２キヤリヤガス５も
導入される。ここで第１キｒリヤガス３と第２キセリヤ
ガス５とのうち、いずれか一方または双方には、酸素プ
ラズマを生成させるための酸素ガスを含んでいるものと
する。A second carrier gas 5 is also separately introduced into the upper part of the reaction tube 4. Here, it is assumed that either one or both of the first quenching gas 3 and the second quenching gas 5 contains oxygen gas for generating oxygen plasma.
一方反応管４の側方に配設されたマイクロ波発振器６に
より発振されたマイクロ波（例えば周波数２４５０ Ｈ
Ｉ３）は、導波管７を介して反応管４内を通り、さらに
反対側に配置されたマイクロ波プランジｔ８により反射
ゼしめられて再び反応管４内へ戻る。このようなマイク
ロ波によって前述の第１キヤリヤガス３もしくは第２キ
ｒリヤガス５に含まれる酸素ガスがプラズマ化し、反応
管４内に酸素プラズマ９が発生せしめられる。なおこの
酸素プラズマ発生領域内下部には基板１０が配置されて
おり、また反応管内は真空ポンプ１１により減圧されて
いる。On the other hand, microwaves (for example, frequency 2450
I3) passes through the reaction tube 4 via the waveguide 7, is further reflected by the microwave plunge t8 disposed on the opposite side, and returns to the reaction tube 4 again. The oxygen gas contained in the first carrier gas 3 or the second carrier gas 5 is turned into plasma by such microwaves, and oxygen plasma 9 is generated in the reaction tube 4. Note that a substrate 10 is placed in the lower part of this oxygen plasma generation region, and the pressure inside the reaction tube is reduced by a vacuum pump 11.
前述のようにして反応管４内に導入された原料金属の塩
の水溶液の噴霧液滴は、酸素プラズマ９によって急速に
酸化され、原料金属の酸化物が基板１０上に析出される
。すなわち酸化物セラミック系の超電導薄膜が基板１０
上に生成される。The spray droplets of the aqueous solution of the raw metal salt introduced into the reaction tube 4 as described above are rapidly oxidized by the oxygen plasma 9, and the oxide of the raw metal is deposited on the substrate 10. That is, the oxide ceramic superconducting thin film is the substrate 10.
generated above.
なおここでは酸素プラズマ９はマイクロ波によって発生
させるものとしたが、それに限るものではなく、高周波
プラズマブＴ生装置等も利用できることはもちろんであ
る。Here, the oxygen plasma 9 is generated using microwaves, but the present invention is not limited to this, and it goes without saying that a high-frequency plasma generator or the like can also be used.
また第１図中の例では基板１０は酸素プラズマ領域内に
配置して、酸素プラズマ９によって基板自体も加熱する
ものとしたが、場合によっては基板１０は別の加熱源、
例えば抵抗加熱ヒータ等によって加熱するようにしても
良く、この場合は基板ｉｏｔ、を酸素プラズマ領域の直
下に配置しておくことができる。なお基板１０の温度は
８００〜１２００℃程度になるように制御することが好
ましい。Further, in the example shown in FIG. 1, the substrate 10 is placed in an oxygen plasma region, and the substrate itself is heated by the oxygen plasma 9, but in some cases, the substrate 10 may be heated by another heating source,
For example, heating may be performed using a resistance heater or the like, and in this case, the substrate iot can be placed directly below the oxygen plasma region. Note that the temperature of the substrate 10 is preferably controlled to be about 800 to 1200°C.
なおこの発明において製造する対象となる超電４薄膜は
、要は酸化物セラミック系のものであれば良く、例えば
Ｙ−Ｂａ−Ｃｕ−０系酸化物（具体的にはＹＢａ２ Ｃ
ｕ３０７など）、アルイハ８ ｉ −８ｒ−Ｃａ−Ｃｕ
−０系酸化物（具体的にはＢ ｚ Ｓｒ＋ Ｃａｔ Ｃ
Ｃｌ２０Ｘ 、あるイハＢ ｉ４ （Ｓｒ＋−ｘＣａｘ
）ｓ Ｃｕ４０ｙなど）、さらにはＴｆ−Ｂａ−Ｃａ
−Ｃｕ−０系酸化物（具体的にはＴ＆ Ｂａ Ｃａ
Ｃｕ Ｏ；ｎ２ ２ ｎ−
１ｎ ４＋２ｎ−１，２または３）などを製造す
ることができる。Note that the superconductor 4 thin film to be manufactured in this invention may be of an oxide ceramic type, for example, Y-Ba-Cu-0 type oxide (specifically, YBa2C
u307 etc.), Al-Iha8i-8r-Ca-Cu
-0 series oxide (specifically B z Sr+ Cat C
Cl20X, certain IhaB i4 (Sr+-xCax
)s Cu40y, etc.), and even Tf-Ba-Ca
-Cu-0 based oxide (specifically T & Ba Ca
CuO; n2 2 n-
1n 4+2n-1, 2 or 3), etc. can be produced.
また基板の材料は特に限定されないが、例えば石英板、
サファイヤ、シリコン、酸化マグネシウム、チタン酸ス
トロンチウムなどを用いることができる。Further, the material of the substrate is not particularly limited, but for example, quartz plate,
Sapphire, silicon, magnesium oxide, strontium titanate, etc. can be used.
以下にこの発明の製造方法の具体的な実施例を記す。Specific examples of the manufacturing method of the present invention will be described below.
［実施例１１
第１図に示すような装置を用いて、Ｙ−Ｂａ−Ｃｕ−０
系酸化物からなる超電導′ａ膜を次のように形成した。[Example 11 Using the apparatus shown in FIG. 1, Y-Ba-Cu-0
A superconducting 'a' film made of a series oxide was formed as follows.
原料金属の塩の水溶液としては、硝酸イツトリウム０．
１ｎｏｌ／１、硝酸バリウム０．２１１１０１／Ｊ、硝
酸銅０．３ｎ＋ｏｌ／ｆの混合塩水溶液を用い、また第
１キヤリヤガスとしては酸素ガス３００成／市、第２キ
ヤリヤガスとしては酸素ガス２００厩／ ｍａｎを用い
た。噴霧器としては超音波噴霧器を用い、その超音波出
力は２５ｗとした。また酸素プラズマ光土用のマイクロ
波出力は４００Ｗとし、系内圧力は４５Ｔｏｒｒとした
。基板としては酸化マグネシウムを用いて、その基板を
酸素プラズマ中に配置して、プラズマのみにより基板を
加熱するようにした。As the aqueous solution of the raw metal salt, yttrium nitrate 0.
A mixed salt aqueous solution of 1nol/1, barium nitrate 0.211101/J, and copper nitrate 0.3n+ol/f was used, and the first carrier gas was oxygen gas 300ml/man, and the second carrier gas was oxygen gas 200ml/man. was used. An ultrasonic atomizer was used as the atomizer, and its ultrasonic output was 25W. Further, the microwave output for the oxygen plasma light soil was set to 400 W, and the system internal pressure was set to 45 Torr. Magnesium oxide was used as the substrate, and the substrate was placed in oxygen plasma so that the substrate was heated only by the plasma.
なお基板温度は約８８０ ”Ｃであった。Note that the substrate temperature was approximately 880''C.
上記の条件により３時間の処理を行なったところ、基板
上に厚さ１．２伽のＹＢａ２Ｃｕ２Ｏ７薄膜が生成され
た。そのｖＪ膜の超電導臨界温度を調べたところ、Ｔｃ
（Ｏｎ）は７９．０に、 Ｔｃ （Ｅｎｄ）は７４．５
にであった。When the treatment was carried out for 3 hours under the above conditions, a YBa2Cu2O7 thin film with a thickness of 1.2 cm was formed on the substrate. When we investigated the superconducting critical temperature of the vJ film, we found that Tc
(On) is 79.0, Tc (End) is 74.5
It was.
［実施例２１
第１図に示すような装置を用いて、Ｙ−Ｂａ−Ｃｕ−０
系酸化物からなる超電導薄膜を次のように形成した。[Example 21 Using the apparatus shown in FIG. 1, Y-Ba-Cu-0
A superconducting thin film made of a system oxide was formed as follows.
原料金属の塩の水溶液としては、硝酸イツトリウム０．
３ ｎｏｌ／１７、硝酸バリウム０．６ｎｏｌ／６、硝
酸銅０．９１１１０１／ｉ’の混合塩水溶液を用い、ま
た第１キＰリヤガスとしてはアルゴンガス１００ｍ ／
１ｉｈ、第２キヤリヤガスとしては酸素ガス４５０ａｅ
／市を用いた。噴霧器としては超音波噴霧器を用い、
その超音波出力は２５ｗとした。また酸素プラズマ発生
用のマイクロ波出力は４００Ｗとし、系内圧力は７５Ｔ
ｏｒｒとした。基板としては酸化マグネシウムを用い、
その基板をプラズマ直下に配置して、抵抗加熱するよう
にした。なお基板温度は約８７５°Ｃである。As the aqueous solution of the raw metal salt, yttrium nitrate 0.
A mixed salt aqueous solution of 3 nol/17, barium nitrate 0.6 nol/6, and copper nitrate 0.911101/i' was used, and argon gas 100 m/i' was used as the first primary gas.
1ih, oxygen gas 450ae as the second carrier gas
/ City was used. An ultrasonic atomizer is used as the atomizer,
The ultrasonic output was 25W. In addition, the microwave output for oxygen plasma generation was 400W, and the system pressure was 75T.
It was set as orr. Magnesium oxide is used as the substrate,
The substrate was placed directly under the plasma and resistively heated. Note that the substrate temperature was approximately 875°C.
上記の条件により５時間の処理を行なったところ、基板
上に厚さ３．２伽のＹＢａ２ＣＩＪ３０７ 薄膜が生成
された。その薄膜の超電導臨界温度を調べたところ、Ｔ
ｃ（Ｏｎ）は７９．０に、 Ｔｃ （Ｅｎｄ）は７４．
５にであった。When the treatment was carried out for 5 hours under the above conditions, a YBa2CIJ307 thin film with a thickness of 3.2 cm was formed on the substrate. When we investigated the superconducting critical temperature of the thin film, we found that T
c (On) is 79.0, Tc (End) is 74.
It was on 5th.
し実施例３］
第１図に示すような装置を用いて、Ｂ１−８ｒ−Ｃａ−
Ｑｕ−Ｑ系酸化物からなる超電導薄膜を次のように形成
した。Example 3] B1-8r-Ca-
A superconducting thin film made of Qu-Q based oxide was formed as follows.
原料金属の塩の水溶液としては硝酸ビスマス０．１１ｏ
ｌ／ｌ、酢酸ストロンチウム０．１１ｏｌ／ｉ）、硝酸
カルシウム０． Ｉ ｎ＋ｏｌ／ ｌ 、酢酸銅１．８
ｍｏｌ／βの混合塩水溶液を用い、また第１キヤリＡ
７ガスとしては酸素ガス３００ｄ／ｍｉ、第２キヤリヤ
ガスとしては酸素ガス２００威／ ｍｉｎを用いた。噴
霧器としては超音波噴霧器を用い、その超音波出力は２
５Ｗとした。また酸素プラズマ発生用のマイクロ波出力
は４００ｗとした。基板としては酸化マグネシウムを用
い、その基板をプラズマ直下に配置して、高周波加熱す
るようにした。なお基板温度は約９２５℃である。Bismuth nitrate 0.11o as an aqueous solution of raw metal salt
l/l, strontium acetate 0.11 ol/i), calcium nitrate 0. I n+ol/l, copper acetate 1.8
Using a mixed salt aqueous solution of mol/β, and using the first carrier A
As the 7 gas, oxygen gas was used at 300 d/min, and as the second carrier gas, oxygen gas was used at 200 d/min. An ultrasonic atomizer is used as the atomizer, and its ultrasonic output is 2
It was set to 5W. Further, the microwave output for generating oxygen plasma was set to 400W. Magnesium oxide was used as the substrate, and the substrate was placed directly under the plasma and heated with high frequency. Note that the substrate temperature was approximately 925°C.
上記の条件によって６時間処理を行な・ったところ、基
板上に厚さ５．８踊の
８ ｉ４ （Ｓｒ＋−ｘＣａｘ ）１３ Ｃｕ４０ｙ
（２＜ｙ＜３）の薄膜が生成された。その薄膜の超電
導臨界温度を調べたところＴｃ（Ｏｎ）は８０．５ｋ、
ＴＣ（Ｅｎｄ）は７６．３にであった。After processing for 6 hours under the above conditions, 8 i4 (Sr+-xCax)13 Cu40y with a thickness of 5.8 mm was deposited on the substrate.
A thin film of (2<y<3) was produced. When we investigated the superconducting critical temperature of the thin film, Tc (On) was 80.5k.
TC (End) was 76.3.
発明の効果
この発明の超電導薄膜の製造方法によれば、酸化物セラ
ミック系の超電導薄膜を基板上に形成するにあたり、原
料金属を含む塩の水溶液を噴霧し、その霧状の液滴を酸
素プラズマ中に供給して基板上に堆積させることにより
、原料金属を含む塩の酸化による超電導酸化物の生成と
基板上への″ａｌｌ！生成とが一工程で同時的もしくは
連続的になされるため、超電導７ａ膜生成のための処理
工程を従来よりも格段に少なくして、その製造コストを
従来よりも格段に低くすることができ、また全処理が気
相でおこなわれるため量産化も容易に行なうことができ
る。さらにこの発明の製造方法においては、原料金属を
含む塩の水溶液の霧状の液滴が、極めて酸化性の張り酸
素プラズマによって酸化されて超電導酸化物が生成され
るため、未酸化の金属が薄膜中に含まれるおそれが少な
く、そのため′ＥＡ電導特性の優れた薄膜を得ることが
できる。Effects of the Invention According to the method for producing a superconducting thin film of the present invention, when forming an oxide ceramic superconducting thin film on a substrate, an aqueous solution of a salt containing a raw material metal is sprayed, and the atomized droplets are exposed to oxygen plasma. By supplying the superconducting oxide to the substrate and depositing it on the substrate, the generation of superconducting oxide by oxidation of the salt containing the raw material metal and the generation of "all!" on the substrate are performed simultaneously or continuously in one step. The number of processing steps required to generate the superconducting 7a film can be significantly reduced compared to conventional methods, making the manufacturing cost much lower than conventional methods, and mass production is also easy because all processing is performed in the gas phase. Furthermore, in the manufacturing method of the present invention, the atomized droplets of the aqueous salt solution containing the raw material metal are oxidized by highly oxidizing oxygen plasma to produce superconducting oxide. There is little risk of metals being included in the thin film, and therefore a thin film with excellent EA conductivity properties can be obtained.
第１図はこの発明の製造方法を実施する装置の一例を概
略的に示す略解図である。
１・・・原料金属を含む塩の水溶液、 ２・・・噴霧器
、３・・・第１キヤリヤガス、 ４・・・反応管、 ５
・・・第２キヤリヤガス、 ９・・・ＭＩ素プラズマ、
１ｏ・・・基板。FIG. 1 is a schematic diagram schematically showing an example of an apparatus for carrying out the manufacturing method of the present invention. DESCRIPTION OF SYMBOLS 1... Aqueous salt solution containing raw material metal, 2... Sprayer, 3... First carrier gas, 4... Reaction tube, 5
...Second carrier gas, 9...MI elementary plasma,
1o...Substrate.
Claims (1)
の水溶液を噴霧化し、得られた霧状の液滴を酸素プラズ
マ中に供給して、その酸素プラズマ中もしくは酸素プラ
ズマ近傍に配置された基板上に酸化物セラミック系超電
導薄膜を生成させることを特徴とする酸化物セラミック
系超電導薄膜の製造方法。Aqueous solutions of salts containing metals constituting oxide ceramic superconducting materials are atomized, and the resulting atomized droplets are supplied into oxygen plasma, and onto a substrate placed in or near the oxygen plasma. 1. A method for producing an oxide ceramic superconducting thin film, the method comprising: producing an oxide ceramic superconducting thin film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33505788A JPH02179880A (en) | 1988-12-29 | 1988-12-29 | Production of thin oxide ceramic superconducting film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33505788A JPH02179880A (en) | 1988-12-29 | 1988-12-29 | Production of thin oxide ceramic superconducting film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02179880A true JPH02179880A (en) | 1990-07-12 |
| JPH0349985B2 JPH0349985B2 (en) | 1991-07-31 |
Family
ID=18284269
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33505788A Granted JPH02179880A (en) | 1988-12-29 | 1988-12-29 | Production of thin oxide ceramic superconducting film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02179880A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7018676B2 (en) * | 2000-03-29 | 2006-03-28 | Seiko Epson Corporation | Method and device for manufacturing ceramics, semiconductor device and piezoelectric device |
-
1988
- 1988-12-29 JP JP33505788A patent/JPH02179880A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7018676B2 (en) * | 2000-03-29 | 2006-03-28 | Seiko Epson Corporation | Method and device for manufacturing ceramics, semiconductor device and piezoelectric device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0349985B2 (en) | 1991-07-31 |
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