JPH01226783A - Production of superconducting film of bi-sr-ca-cu-o system by screen printing - Google Patents
Production of superconducting film of bi-sr-ca-cu-o system by screen printingInfo
- Publication number
- JPH01226783A JPH01226783A JP63052351A JP5235188A JPH01226783A JP H01226783 A JPH01226783 A JP H01226783A JP 63052351 A JP63052351 A JP 63052351A JP 5235188 A JP5235188 A JP 5235188A JP H01226783 A JPH01226783 A JP H01226783A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- substrate
- screen printing
- superconducting film
- sintering
- 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
- 238000007650 screen-printing Methods 0.000 title claims abstract description 15
- 229910015901 Bi-Sr-Ca-Cu-O Inorganic materials 0.000 title claims abstract 4
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000000843 powder Substances 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 23
- 238000005245 sintering Methods 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 229910052594 sapphire Inorganic materials 0.000 claims abstract description 4
- 239000010980 sapphire Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 16
- 239000011812 mixed powder Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910014454 Ca-Cu Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims 2
- 229910002076 stabilized zirconia Inorganic materials 0.000 claims 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 abstract description 6
- 229910002370 SrTiO3 Inorganic materials 0.000 abstract description 6
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 abstract description 5
- 229910052712 strontium Inorganic materials 0.000 abstract description 3
- 229910052797 bismuth Inorganic materials 0.000 abstract description 2
- 229910052791 calcium Inorganic materials 0.000 abstract description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 abstract 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract 2
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract 1
- 235000010216 calcium carbonate Nutrition 0.000 abstract 1
- 229910052802 copper Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 238000004898 kneading Methods 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 229910000018 strontium carbonate Inorganic materials 0.000 abstract 1
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000010408 film Substances 0.000 description 21
- 239000000463 material Substances 0.000 description 10
- 239000002131 composite material Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000010453 quartz Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 230000005668 Josephson effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 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
- C23C18/1229—Composition of the substrate
- C23C18/1245—Inorganic substrates other than metallic
-
- 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
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はスクリーン印刷及びその後の焼結によりＢｉ−
８ｒ−Ｃａ−Ｃｕ−０系高温超伝導膜を製造する方法に
関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention provides a method for producing Bi-
The present invention relates to a method for manufacturing an 8r-Ca-Cu-0-based high-temperature superconducting film.
（従来の技術及び解決しようとする課題）超伝導体は、
電気抵抗率ゼロ、ジョセフソン効果、完全反磁性等々の
性質を有することから、多量の電力損失があるコイル導
線、ジョセフソン接合素子、磁気シールド材料などの用
途がある。(Conventional technology and problems to be solved) Superconductors are
Because it has properties such as zero electrical resistivity, the Josephson effect, and perfect diamagnetism, it is used in coil conductors, Josephson junction elements, magnetic shielding materials, etc., which have a large amount of power loss.
超伝導膜の形成法としては、真空蒸着、スパッタリング
、スクリーン印刷等の物理的方法と、ＣＶＤ、スプレー
パイロリシス等の化学的方法があるが、要求される膜の
厚さや緻密さ、原料の入手の容易さ等に応じて選ばれる
ものである。Methods for forming superconducting films include physical methods such as vacuum evaporation, sputtering, and screen printing, and chemical methods such as CVD and spray pyrolysis. The method is selected depending on the ease of use, etc.
これらの方法のうち、ジョセフソン素子等のデイバイス
への応用には、真空蒸着法と並び、緻密な膜の形成が可
能であると共に他種膜との連続成膜も可能な真空チャン
バーを利用する方法である真空蒸着法、スパッタリング
法が有効である。また、１０μｍ程度或いはそれ以上の
厚膜の作製には、スクリーン印刷法が有用である。Among these methods, when applied to devices such as Josephson elements, a vacuum chamber is used, which allows the formation of dense films as well as continuous film formation with other types of films, as well as vacuum evaporation methods. Vacuum deposition method and sputtering method are effective methods. Further, a screen printing method is useful for producing a thick film of about 10 μm or more.
高温超伝導膜の形成では、バルクに共通な問題として、
組成と結晶性の制御の問題や安定性の問題があり、膜に
特有な問題として基板との相互作用の問題がある。また
、従来の超伝導物質は概ねＹ等の希土類金属を含む系で
あるので、資源並びにコスト上の問題もあるが、最近、
希土類を含まないＢ ｉ −Ｓ ｒ −Ｃａ −Ｃｕ
−０系物質が超伝導性を有することが報告されている。In the formation of high-temperature superconducting films, there are common problems in bulk.
There are problems in controlling the composition and crystallinity, as well as stability issues, and a problem specific to films is the interaction with the substrate. In addition, since conventional superconducting materials are generally systems containing rare earth metals such as Y, there are resource and cost issues, but recently,
B i -S r -Ca -Cu that does not contain rare earth elements
It has been reported that -0-based materials have superconductivity.
本発明は、高温超伝導膜の製造に関する上述の問題を解
決し、希土類金属を含まないＢｉ−Ｓｒ−Ｃａ−Ｃｕ−
０系を超伝導物質として用い、スクリーン印刷を利用し
て、その組成のコントロールが容易で、安定性のよい膜
を経済的且つ生産性よく製造する方法を提供することを
目的とするものである。The present invention solves the above-mentioned problems regarding the production of high-temperature superconducting films, and provides rare earth metal-free Bi-Sr-Ca-Cu-
The purpose of the present invention is to provide a method for economically and productively manufacturing a film with good stability and easy control of the composition by using 0 series as a superconducting material and using screen printing. .
（課題を解決するための手段）
前記目的を達成するため、本発明者らは、スクリーン印
刷法により超伝導膜を製造する場合、基板との相互作用
が影響することに鑑みて、種々の材質の基板を使用して
Ｂｉ −５ｒ−Ｃａ−Ｃｕ−０系膜との関連について研
究した結果、ＹＳＺ、Ｓ ｒ Ｔ １０３、ＭｇＯなど
の基板を使用した場合に超伝導性の薄膜が得られる可能
性があることが判明した。(Means for Solving the Problems) In order to achieve the above object, the present inventors developed a method using various materials in view of the influence of interaction with a substrate when manufacturing a superconducting film by a screen printing method. As a result of research on the relationship with Bi-5r-Ca-Cu-0 based films using substrates of It turned out that there is a sex.
そこで、スクリーン印刷後の焼結条件と超伝導性との関
連について更に研究を重ねたところ、Ｔｃ（ゼロ抵抗温
度）が６５に以上の高温超伝導薄膜が得られることを見
い出したものである。Therefore, after further research into the relationship between sintering conditions after screen printing and superconductivity, it was discovered that a high-temperature superconducting thin film with a Tc (zero resistance temperature) of 65 or higher could be obtained.
すなわち、本発明は、Ｂｉ −５ｒ−Ｃａ−Ｃｕ−０系
複合酸化物粉又は各金属成分の単一化合物の混合粉を有
機媒体を用いて混練してペーストとし、このペーストを
、ＹＳＺ 、ＳｒＴｉＯ３、ＭｇＯ、アルミナ及びサフ
ァイアのうちの１種からなる基板上にスクリーン印刷し
た後、乾燥し、８００〜９００℃の温度で焼結すること
により、超伝導膜を得ることを特徴とするスクリーン印
刷によるＢｉ−８ｒ−Ｃａ−Ｃｕ−０系超伝導膜の製造
方法を要旨とするものである。That is, in the present invention, Bi-5r-Ca-Cu-0 based composite oxide powder or mixed powder of a single compound of each metal component is kneaded using an organic medium to form a paste, and this paste is mixed with YSZ, SrTiO3 , MgO, alumina, and sapphire, and then drying and sintering at a temperature of 800 to 900°C to obtain a superconducting film. The gist of this paper is a method for manufacturing a Bi-8r-Ca-Cu-0 based superconducting film.
以下に本発明を更に詳細に説明する。The present invention will be explained in more detail below.
ペーストに用いる原料粉末は、Ｂｉ−８ｒ−Ｃａ−Ｃｕ
−０系複合酸化物粉であっても、或いは各金属成分の単
一化合物（酸化物、炭酸塩）の混合粉末であってもよい
。いずれの場合でも、金属成分の組成比（Ｂｉ ： Ｓ
ｒ ： Ｃａ ： Ｃｕ）が原子割合で所定の比率にな
るように調整する必要がある。例えば、Ｂｉ： Ｓｒ：
Ｃａ： Ｃｕが原子割合で１：１：（０，５〜１）：
（１，５〜２）とするのが望ましい。The raw material powder used for the paste is Bi-8r-Ca-Cu
It may be a -0 type composite oxide powder or a mixed powder of a single compound (oxide, carbonate) of each metal component. In either case, the composition ratio of the metal components (Bi:S
r:Ca:Cu) must be adjusted to a predetermined atomic ratio. For example, Bi: Sr:
Ca: Cu in atomic ratio 1:1:(0,5-1):
It is desirable to set it as (1,5-2).
そのためには、Ｂｉ、０３．５ｒＣＯ，、ＣａＣＯ，及
びＣｕＯの各粉末を所定の割合で混合し、その混合粉の
ままで供するか、或いはこの混合粉を８００’ＣＸ１２
ｈｒの仮焼により複合化合物（複合酸化物）とすること
ができる。特に、混合粉を利用できるので、組成比のコ
ントロールが一層容易である。To do this, it is necessary to mix Bi, 03.5rCO, CaCO, and CuO powders in a predetermined ratio and serve the mixed powder as is, or to use the 800'CX12
A composite compound (composite oxide) can be obtained by calcining for hr. In particular, since a mixed powder can be used, it is easier to control the composition ratio.
これらをペースト状にするための有機媒体としては、適
宜のものを使用できるが、沸点が１５０〜２００℃で乾
燥し易く、成る程度粘性があり、印刷し易いものがよく
、例えば、オクチルアルコール、プロピレングリコール
、ヘプチルアルコールなどを使用する。Any suitable organic medium can be used to make these pastes, but those with a boiling point of 150 to 200°C, easy to dry, have a certain degree of viscosity, and are easy to print on are preferred, such as octyl alcohol, Use propylene glycol, heptyl alcohol, etc.
基板（サブストレート）として如何なる材料のものを用
いるかは、超伝導膜を得るうえで重要である。What kind of material is used as the substrate is important in obtaining a superconducting film.
すなわち、石英では焼結条件の如何に拘わらず超伝導性
そのものが得られず、また、ＹＳｚ、ＳｒＴｉＯ３、Ｍ
ｇＯ、アルミナやサファイアを使用しても、焼結条件を
適切に選定しなければ超伝導性が得られないことが判明
した。In other words, superconductivity itself cannot be obtained with quartz regardless of the sintering conditions, and YSz, SrTiO3, M
It has been found that even if gO, alumina, or sapphire is used, superconductivity cannot be obtained unless the sintering conditions are appropriately selected.
スクリーン印刷に際しては、上記の如＜Ｂｉ−５ｒ−Ｃ
ａ−Ｃｕ−０系複合酸化物粉又は混合粉をペースト状に
して、通常使用されているスクリーン印刷機により上記
材質の基板上に適当な厚さで印刷する。When screen printing, as described above, <Bi-5r-C
The a-Cu-0 based composite oxide powder or mixed powder is made into a paste and printed to an appropriate thickness on a substrate made of the above material using a commonly used screen printer.
スクリーン印刷後、乾燥し、焼結するが、焼結は８ｏＯ
〜９００℃、好ましくは８４０〜８５０℃の温度で行う
。混合組成がＢ ｉ、 Ｓ ｒ、 Ｃａ１，２Ｃｕ。After screen printing, dry and sinter, but the sintering is 8oO
It is carried out at a temperature of -900°C, preferably 840-850°C. The mixed composition is B i, S r, Ca1,2Cu.
〜４の原料粉を用いた場合、８４０℃未満では、基板材
料との相互反応は少なくなるものの、Ｂｉ−５ｒ−Ｃａ
−Ｃｕ−Ｏｘ系粉末の焼結速度も遅い。When using the raw material powder of
The sintering speed of the -Cu-Ox powder is also slow.
８５０℃を超えると、Ｂｉ−Ｓｒ−Ｃａ−Ｃｕ−Ｏｘ系
粉末が部分的に溶融を誘発し、溶融部が基板と密接に接
触して膜の結晶構造及び配向性に影響を及ぼす。７なお
、乾燥は大気中又は真空雰囲気中で行う。また焼結時間
は加熱温度に応じて決めればよく、１０分〜１０時間の
範囲を目安とする１例えば、８００℃のときは１０時間
、８４０〜８５０℃のときは１時間、９００℃のときは
１０分加熱する。When the temperature exceeds 850° C., the Bi-Sr-Ca-Cu-Ox powder partially induces melting, and the melted portion comes into close contact with the substrate, affecting the crystal structure and orientation of the film. 7. Note that drying is performed in the air or in a vacuum atmosphere. In addition, the sintering time can be determined according to the heating temperature, and should be in the range of 10 minutes to 10 hours.1For example, 10 hours at 800°C, 1 hour at 840-850°C, and 1 hour at 900°C. Heat for 10 minutes.
次に本発明の実施例を示す。Next, examples of the present invention will be shown.
（実施例）
Ｂｉ２Ｏ，，５ｒＣＯ１、ＣａＣ０，及びＣｕＯの各粉
末の所定量を混合したものを８００℃Ｘ１２ｈｒで仮焼
し、Ｂ ｉ、 Ｓ ｒ、 Ｃａ１Ｃｕ２０Ｘ（粉末Ａ）
と、Ｂｉ。(Example) A mixture of predetermined amounts of each powder of Bi2O, 5rCO1, CaC0, and CuO was calcined at 800°C for 12 hours to produce Bi, Sr, Ca1Cu20X (powder A).
And Bi.
Ｓｒ、Ｃａ、Ｃｕ２Ｏｘ（粉末Ｂ）の２種類のセラミッ
ク粉を準備した。また、Ｂｉ： Ｓｒ： Ｃａ： Ｃｕ
が１：１：１：２の原子割合となるように前記原料酸化
物及び炭酸塩を単に混合した混合粉末（粉末Ｃ）も準備
した。Two types of ceramic powders were prepared: Sr, Ca, and Cu2Ox (powder B). Also, Bi: Sr: Ca: Cu
A mixed powder (powder C) was also prepared by simply mixing the raw material oxide and carbonate in an atomic ratio of 1:1:1:2.
これらの粉末１ｇをオクチルアルコール０．５ｍＱと共
にめのう乳鉢中で混練してペースト状にし、各種材質（
石英、アルミナ、ＹＳＺ（２，５％Ｙで安定化したジル
コニア）、ＳｒＴｉＯ３単結晶）の基板上に１５０メツ
シユスクリーンにて印刷した。1 g of these powders was kneaded with 0.5 mQ of octyl alcohol in an agate mortar to form a paste, and various materials (
Printing was performed using a 150 mesh screen on substrates of quartz, alumina, YSZ (zirconia stabilized with 2.5% Y, SrTiO3 single crystal).
１２０℃、真空中で３時間乾燥した後、これらの印刷膜
を所定の温度（８３０〜９００℃）で１時間焼結した。After drying in vacuum at 120°C for 3 hours, these printed films were sintered at a predetermined temperature (830-900°C) for 1 hour.
なお、膜厚は焼結後で１ｏ±２μｍとなるように決定し
た。The film thickness was determined to be 10±2 μm after sintering.
得られた膜について、室温での電気抵抗率（ρｒｔ）と
、電気抵抗の温度依存性を調べた。それらの結果を第１
図及び第２図に示す。Regarding the obtained film, the electrical resistivity (ρrt) at room temperature and the temperature dependence of the electrical resistance were investigated. those results first
As shown in Fig. and Fig. 2.
基板として石英を用いた場合は上記の条件では伝導性が
得られなかった。When quartz was used as the substrate, conductivity could not be obtained under the above conditions.
一方、基板としてＳｒＴｉＯ３を用いた場合、焼結温度
が８４０℃のとき、１１にで電気抵抗ゼロとなった。し
かし、焼結温度が８５０℃では、室温での電気抵抗率が
低いにも拘わらず、超伝導性にならなかった（第１図）
。On the other hand, when SrTiO3 was used as the substrate, the electrical resistance became zero at 11 when the sintering temperature was 840°C. However, at a sintering temperature of 850°C, superconductivity did not occur despite the low electrical resistivity at room temperature (Figure 1).
.
また、基板としてＹＳＺを用いた場合、焼結温度が８４
０℃で超伝導性が得られ、２２にで抵抗ゼロとなり、更
に８５０℃に高めるとＴ ｃ （ゼロ）が改善され、
６３Ｋ（測定電流密度０．６４Ａ／ｃｍ” ）、６５Ｋ
（測定電流密度０ 、０７ Ａ／Ｃｍ”）で電気抵抗ゼ
ロとなり、粉末Ｂを用いるとＴｃ（ゼロ）が６８Ｋ（０
，６４Ａ／ｃｍ”）が得られた（第２図）。Furthermore, when YSZ is used as the substrate, the sintering temperature is 84
Superconductivity is obtained at 0°C, resistance becomes zero at 22°C, and T c (zero) is improved when the temperature is further increased to 850°C.
63K (measured current density 0.64A/cm"), 65K
(measured current density 0,07 A/Cm"), the electrical resistance becomes zero, and when powder B is used, Tc (zero) becomes 68K (0
, 64 A/cm") was obtained (Fig. 2).
すなわち、上記の条件では、基板材料として、石英やア
ルミナよりもＳ ｒ Ｔ ｉ Ｏ３の方が好ましく、更
にはＹＳＺの方が好ましい。しかし、基板がＹＳＺの場
合でも、焼結温度が８６０℃以上になると、Ｔｃは低下
し始める。更に焼結温度が９００℃の場合、得られた膜
は半導体であった。That is, under the above conditions, S r T i O3 is more preferable than quartz or alumina, and YSZ is more preferable as the substrate material. However, even when the substrate is YSZ, when the sintering temperature reaches 860° C. or higher, Tc starts to decrease. Further, when the sintering temperature was 900°C, the obtained film was a semiconductor.
また、粉末Ｃ（混合物粉）を用い、ＹＳＺの基板の場合
も、焼結温度８５０℃で超伝導性が得られたが、Ｔｃ（
ゼロ）は１１Ｋ（測定電流密度０．０７Ａ／ｃｍ”）で
あり、焼結原料粉を用いた場合の６３によりもかなり低
い。In addition, superconductivity was obtained at a sintering temperature of 850°C using Powder C (mixture powder) and a YSZ substrate, but Tc (
zero) is 11 K (measured current density 0.07 A/cm''), which is considerably lower than 63 when using sintered raw material powder.
（発明の効果）
以上詳述したように、本発明によれば、スクリーン印刷
に使用する基板の材質と印刷後の焼結条件を規制するの
で、Ｂｉ−８ｒ−Ｃａ−Ｃｕ−０系超伝導膜を得ること
ができ、Ｔ ｃ （ゼロ）が１２０に程度まで達成可能
である。(Effects of the Invention) As detailed above, according to the present invention, since the material of the substrate used for screen printing and the sintering conditions after printing are regulated, Bi-8r-Ca-Cu-0 based superconducting Membranes can be obtained and T c (zero) as low as 120 can be achieved.
第１＠及び第２図は基板上のスクリーン印刷・焼結膜に
おける電気抵抗の温度依存性を示す図であって、第１図
はＳｒＴｉＯ３基板の場合、第２図はＹＳＺ基板の場合
を示している。
特許出願人 新技術開発事業団
代理人弁理士 中 村 尚Figures 1@ and 2 are diagrams showing the temperature dependence of electrical resistance in screen-printed and sintered films on substrates. Figure 1 shows the case of a SrTiO3 substrate, and Figure 2 shows the case of a YSZ substrate. There is. Patent applicant Takashi Nakamura, patent attorney, New Technology Development Corporation
Claims (5)
各金属成分の単一化合物の混合粉を有機媒体を用いて混
練してペーストとし、このペーストを、イットリア（Ｙ
）安定化ジルコニア（ＹＳＺ）、ＳｒＴｉＯ＿３、Ｍｇ
Ｏ、アルミナ及びサファイアのうちの１種からなる基板
上にスクリーン印刷した後、乾燥し、８００〜９００℃
の温度で焼結することにより、超伝導膜を得ることを特
徴とするスクリーン印刷によるＢｉ−Ｓｒ−Ｃａ−Ｃｕ
−Ｏ系超伝導膜の製造方法。(1) Bi-Sr-Ca-Cu-O complex oxide powder or a mixed powder of a single compound of each metal component is kneaded using an organic medium to make a paste, and this paste is mixed with yttria (Yttria).
) Stabilized zirconia (YSZ), SrTiO_3, Mg
After screen printing on a substrate made of one of O, alumina and sapphire, drying and heating at 800-900°C
Bi-Sr-Ca-Cu by screen printing, characterized in that a superconducting film is obtained by sintering at a temperature of
-A method for producing an O-based superconducting film.
原子割合）Ｂｉ：Ｓｒ：Ｃａ：Ｃｕが１：１：（０．５
〜１）：（１．５〜２）となるように調整されたもので
ある請求項１記載の方法。(2) The compound powder and mixture powder have a metal component composition ratio (
Atomic ratio) Bi:Sr:Ca:Cu is 1:1:(0.5
1): (1.5 to 2).
ＳｒＣＯ＿３、ＣａＣＯ＿３及びＣｕＯから作成する請
求項１又は２記載の方法。(3) The compound powder and mixture powder are Bi_2O_3,
3. The method according to claim 1, wherein the method is made from SrCO_3, CaCO_3 and CuO.
後、８００〜９００℃で焼結する請求項１記載の方法。(4) When the substrate is YSZ or MgO, the method according to claim 1, wherein the substrate is sintered at 800 to 900°C after screen printing.
、８５０℃以下で焼結する請求項１記載の方法。(5) The method according to claim 1, wherein when the substrate is SrTiO_3, sintering is performed at 850° C. or lower after screen printing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63052351A JP2817048B2 (en) | 1988-03-04 | 1988-03-04 | Method for producing Bi-Sr-Ca-Cu-O-based superconducting film by screen printing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63052351A JP2817048B2 (en) | 1988-03-04 | 1988-03-04 | Method for producing Bi-Sr-Ca-Cu-O-based superconducting film by screen printing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01226783A true JPH01226783A (en) | 1989-09-11 |
| JP2817048B2 JP2817048B2 (en) | 1998-10-27 |
Family
ID=12912386
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63052351A Expired - Fee Related JP2817048B2 (en) | 1988-03-04 | 1988-03-04 | Method for producing Bi-Sr-Ca-Cu-O-based superconducting film by screen printing |
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| Country | Link |
|---|---|
| JP (1) | JP2817048B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01234305A (en) * | 1988-03-11 | 1989-09-19 | I M C:Kk | Superconducting material and its production |
| JPH01235103A (en) * | 1988-03-15 | 1989-09-20 | Toray Ind Inc | Superconducting material |
| US6809042B2 (en) | 2001-11-22 | 2004-10-26 | Dowa Mining Co., Ltd. | Oxide superconductor thick film and method for manufacturing the same |
| CN105575545A (en) * | 2015-12-29 | 2016-05-11 | 北京英纳超导技术有限公司 | Bi2223 oxide film and industrial preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01201060A (en) * | 1988-02-05 | 1989-08-14 | Showa Denko Kk | Production of superconductor |
| JPH01208360A (en) * | 1988-02-15 | 1989-08-22 | Showa Denko Kk | Production of superconductor |
-
1988
- 1988-03-04 JP JP63052351A patent/JP2817048B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01201060A (en) * | 1988-02-05 | 1989-08-14 | Showa Denko Kk | Production of superconductor |
| JPH01208360A (en) * | 1988-02-15 | 1989-08-22 | Showa Denko Kk | Production of superconductor |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01234305A (en) * | 1988-03-11 | 1989-09-19 | I M C:Kk | Superconducting material and its production |
| JPH01235103A (en) * | 1988-03-15 | 1989-09-20 | Toray Ind Inc | Superconducting material |
| US6809042B2 (en) | 2001-11-22 | 2004-10-26 | Dowa Mining Co., Ltd. | Oxide superconductor thick film and method for manufacturing the same |
| CN105575545A (en) * | 2015-12-29 | 2016-05-11 | 北京英纳超导技术有限公司 | Bi2223 oxide film and industrial preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2817048B2 (en) | 1998-10-27 |
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