JPH01239027A - Oxide superconductor and production of film made thereof - Google Patents
Oxide superconductor and production of film made thereofInfo
- Publication number
- JPH01239027A JPH01239027A JP63065871A JP6587188A JPH01239027A JP H01239027 A JPH01239027 A JP H01239027A JP 63065871 A JP63065871 A JP 63065871A JP 6587188 A JP6587188 A JP 6587188A JP H01239027 A JPH01239027 A JP H01239027A
- Authority
- JP
- Japan
- Prior art keywords
- film
- thickness
- oxide superconductor
- oxide
- heat treatment
- 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
- 239000002887 superconductor Substances 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000000151 deposition Methods 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 230000007704 transition Effects 0.000 abstract description 22
- 238000010438 heat treatment Methods 0.000 abstract description 10
- 229910001637 strontium fluoride Inorganic materials 0.000 abstract description 9
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 abstract description 9
- 230000008021 deposition Effects 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 7
- 229910052797 bismuth Inorganic materials 0.000 abstract description 6
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 abstract description 5
- 229910001634 calcium fluoride Inorganic materials 0.000 abstract description 5
- 229910052802 copper Inorganic materials 0.000 abstract description 5
- 238000010894 electron beam technology Methods 0.000 abstract 1
- 150000002222 fluorine compounds Chemical class 0.000 abstract 1
- 238000007740 vapor deposition Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 49
- 150000001875 compounds Chemical class 0.000 description 14
- 239000010409 thin film Substances 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 3
- 238000005566 electron beam evaporation Methods 0.000 description 3
- 229910052712 strontium Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004876 x-ray fluorescence Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 241000282887 Suidae Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002356 single layer 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)
- Compositions Of Oxide Ceramics (AREA)
- Physical Vapour Deposition (AREA)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、液体窒素温度（絶対温度７７Ｋ）以上の絶対
温度１１０にで超伝導転移をもつ新たな組成物および１
１０に以下で超伝導体となる薄膜の形成法に関するもの
である。Detailed Description of the Invention (Industrial Application Field) The present invention provides a new composition having a superconducting transition at an absolute temperature of 110 degrees above the liquid nitrogen temperature (absolute temperature of 77 K) and
Section 10 below relates to a method for forming a thin film that becomes a superconductor.
（従来の技術）
１９８７年に化学式ＬｎＢａ２ＣｕｓＯｘ （Ｌｎ：Ｙ
、ランタノイド元素）で与えられる酸化物化合物か絶対
温度ｇｏ度（摂氏マイナス１８３℃）の超伝導転移温度
をもつことが公知となって以来、より高い超伝導転移温
度をもつ酸化物超伝導物質の探索が盛んである。(Prior art) In 1987, the chemical formula LnBa2CusOx (Ln:Y
Since it became known that the oxide compounds given by the lanthanide elements have a superconducting transition temperature of 0 degrees absolute (-183 degrees Celsius), oxide superconducting materials with higher superconducting transition temperatures have been developed. There is a lot of exploration going on.
１９８８年１月２２日に、Ｂｉ、Ｓｒ、Ｃａ、Ｃｕで構
成された酸化物化合物である化学式Ｂ １ＳｒＣａＣｕ
２０ｘが絶対温度１０５にと７５事に超伝導転移をもつ
物質であることが報道された。On January 22, 1988, chemical formula B 1SrCaCu is an oxide compound composed of Bi, Sr, Ca, and Cu.
It was reported that 20x is a material with an absolute temperature of 105 and a superconducting transition.
上述した物質は転移温度が異なる化合物（相）か共存（
あるいは混在）しているもので、高温転、移（１０５Ｋ
）相の化合物の同定は未解決である。この報道以後、絶
対温度が１０５Ｋを越える化合物組成についての知見は
報告されていない。The above-mentioned substances are either compounds (phases) with different transition temperatures or coexist (
or mixed), high temperature transition, transfer (105K
) phase remains unresolved. Since this report, no findings regarding the composition of compounds whose absolute temperature exceeds 105K have been reported.
本発明は、エレクトロニクス応用に欠かせない絶対温度
１０５Ｋを越す超伝導転移温度を有するＢｉ−５ｒ−Ｃ
ｕ−０化合物および高い超伝導転移温度を有する薄膜の
製造方法を提供することを目的とす〔課題を解決するた
めの手段］
本発明酸化物超伝導体は組成式Ｂｉ、ＳｒｖＣａｗＩ：
ｕｘｏ。The present invention utilizes Bi-5r-C which has a superconducting transition temperature exceeding 105 K, which is essential for electronics applications.
An object of the present invention is to provide a method for producing a u-0 compound and a thin film having a high superconducting transition temperature [Means for Solving the Problems] The oxide superconductor of the present invention has the composition formula Bi, SrvCawI:
uxo.
で表され、ｕ：Ｖ：Ｗ：Ｘの比が０．７〜１．１＋１．
４〜３．１＋０．８５〜１．１：２であることを特徴と
する。It is expressed as follows, and the ratio of u:V:W:X is 0.7 to 1.1+1.
It is characterized by a ratio of 4 to 3.1+0.85 to 1.1:2.
本発明製造方法は上述した酸化物超伝導体を、２５００
Å以下の厚さで基板上に堆積することを特徴とする。In the manufacturing method of the present invention, the above-mentioned oxide superconductor is
It is characterized by being deposited on a substrate to a thickness of Å or less.
さらに本発明製造方法は上述した酸化物超伝導体を２５
００Å以下の厚さで基板上に堆積し、熱処理する工程を
複数回繰り返すことを特徴とする。Furthermore, the manufacturing method of the present invention uses the above-mentioned oxide superconductor at 25
It is characterized by repeating the steps of depositing it on a substrate to a thickness of 00 Å or less and heat-treating it multiple times.
（作 用〕
ロ１−５ｒ−Ｃａ−Ｃｕ−０四元（酸素を含めると三元
）系酸化物で、Ｂｉ：Ｓｒ：Ｃａ：Ｃｕ−０，７〜１．
１＋１．４〜３．１＋０．８５〜１．１：２．０の比を
もつ化合物が絶対温度約１１０８で超伝導転移を示す新
物質であり、この転移温度を保った薄膜を形成するには
１回の堆積膜厚を２５００Å以下とすることで実現でき
る。(Function) Bi:Sr:Ca:Cu-0,7-1.
A compound with a ratio of 1+1.4 to 3.1+0.85 to 1.1:2.0 is a new material that exhibits a superconducting transition at an absolute temperature of about 1108, and it is necessary to form a thin film that maintains this transition temperature. This can be achieved by setting the thickness of the deposited film at one time to 2500 Å or less.
（実施例） 以下に図面を参照して本発明の詳細な説明する。(Example) The present invention will be described in detail below with reference to the drawings.
実施例１
電子ビーム蒸着法により金属Ｃｕ、Ｂｉおよびフッ化物
ＣａＦ２，５ｒＦｚの順に基板ＭｇＯ（１（１０）面上
にＣｕ：［ｌｉ：Ｃａ：５ｒ＝２：１：１：１．５ に
なるように、Ｃｕ約９０人、Ｂｉ約１３０人、ＣａＦ２
約 １６０人、ＳｒＦ２約 ５２０人を積層した。ただ
し、この膜厚は堆積中の膜厚計での指標で、実際の全膜
厚は７７５人であった。この積層膜を酸素中で約８７０
℃１時間熱処理をしてフッ化物を分解するとともに酸化
し、酸化物化合物薄膜とした。熱処理後の酸化膜をＸ線
蛍光分析法により組成分析をしたところ、各元素の比は
Ｃｕ：Ｂｉ：Ｃａ：５ｒ−２，０：１．０８：１．０８
：１．４３であった。分析誤差は各元素に対して±１０
９６以下である。Example 1 Metals Cu, Bi, and fluoride CaF2,5rFz are deposited on a substrate MgO (1(10) plane in the order of Cu:[li:Ca:5r=2:1:1:1.5) by electron beam evaporation. As such, Cu approximately 90 people, Bi approximately 130 people, CaF2
About 160 people and about 520 people of SrF2 were stacked. However, this film thickness was an index measured by a film thickness meter during deposition, and the actual total film thickness was 775. This laminated film was heated to approximately 870°C in oxygen.
C. for 1 hour to decompose and oxidize the fluoride to form an oxide compound thin film. When the composition of the oxide film after heat treatment was analyzed by X-ray fluorescence analysis, the ratio of each element was Cu:Bi:Ca:5r-2,0:1.08:1.08
:1.43. Analysis error is ±10 for each element
96 or less.
通常の四端子法によりこの酸化膜の電気抵抗の温度変化
を測定した結果を第１図に示す。約１１［１にで電気抵
抗が急激に下がって、約１００にで抵抗がゼロとなる超
伝導性を示している。この組成が１１０に転移温度をも
つ酸化物化合物であることは本発明者が見出したもので
ある。FIG. 1 shows the results of measuring temperature changes in the electrical resistance of this oxide film using the usual four-terminal method. At about 11 [1], the electrical resistance drops rapidly, and at about 100, the resistance becomes zero, indicating superconductivity. The present inventor discovered that this composition is an oxide compound having a transition temperature of 110°C.
実施例２
電子ビーム蒸着により、金属Ｃｕ 、 Ｂ ｉ 、フッ
化物のＣａＦ２．ＳｒＦ２の順に基板ＭｇＯ（ｔｏｏ）
面上にＣｕ約１７０人、 Ｂｉ約 ２４０人、ＣａＦ
２約 ３００人、ＳｒＦ２約 ９１１１人を積層堆積し
た。この厚みは膜厚計での換算であり、実際には全膜厚
は１９９３人であった。この積層膜を酸素中で約８７０
℃、１時間熱処理をし、フッ化物を分解させると同時に
酸化し、酸化物化合物とした。この酸化膜をＸ線蛍光分
析により組成分析をしたところ、Ｃｕ：Ｂｉ：Ｃａ：５
ｒ＝２．Ｏ：０．９４：０．８８＋１．４であった。分
析誤差は各元素に対して±１０堀以内である。Example 2 Metal Cu, B i , fluoride CaF2. Substrate MgO (too) in the order of SrF2
Approximately 170 Cu, 240 Bi, CaF on the surface
Approximately 300 layers of SrF2 and approximately 9111 layers of SrF2 were deposited. This thickness was calculated using a film thickness meter, and the actual total film thickness was 1,993 people. This laminated film was heated to approximately 870°C in oxygen.
C. for 1 hour to decompose and oxidize the fluoride to form an oxide compound. When this oxide film was analyzed for composition by X-ray fluorescence analysis, it was found that Cu:Bi:Ca:5
r=2. O:0.94:0.88+1.4. Analytical errors are within ±10 hogs for each element.
通常の四端子法でこの酸化膜の電気抵抗の温度変化を測
定した結果を第２図に示す。約１１０にで電気抵抗が急
激に低下しており、１１０１’１転移温度の超伝導体で
ある。但し、抵抗が約１０８に以下で据をひいて９０に
で抵抗ゼロとなっていることが判った。Figure 2 shows the results of measuring temperature changes in the electrical resistance of this oxide film using the usual four-terminal method. The electrical resistance decreases rapidly at about 110°C, making it a superconductor with a 1101'1 transition temperature. However, it was found that the resistance remained constant below about 108 and became zero at 90.
分析精度内で実施例１の酸化膜の組成とほぼ同じである
ことから、この電気抵抗の据ひきは膜厚の違いと云える
。すなわち実施例１に比へ全膜厚は約２．６倍になって
おり、この膜厚の違いが膜内の組成均一性を左右してい
る結果、電気抵抗の据びきを生じせしめている。この事
は実施例３て明らかとなったことでもある。Since the composition is almost the same as that of the oxide film in Example 1 within the analysis accuracy, it can be said that this stagnation in electrical resistance is due to the difference in film thickness. In other words, the total film thickness is approximately 2.6 times that of Example 1, and this difference in film thickness affects the composition uniformity within the film, resulting in the electrical resistance remaining unchanged. . This fact was also made clear in Example 3.
実施例３
電子ビーム蒸着により、金属Ｃｕ、Ｂｉ、フッ化物Ｃａ
Ｆ２．ＳｒＦ２の１ｌｌｔ’ｔ ｔＺ Ｃｕ＋Ｂｉ：Ｃ
ａ：５ｒ−２：１．５ ：１：ｌになるように、Ｃｕ約
２５５人、Ｂｉ約 ３６０人、ＣａＦ２約４５０人、
ＳｒＦ２約１３５０人を積層堆積した。この厚さは堆積
中の膜厚計からの換算で、実際の全膜厚は２８１４人で
あった。この積層膜と酸素中で約８７０℃１時間熱処理
することで、フッ化物を分解させると同時に酸化物化合
物とした。Ｘ線蛍光分析による組成分析では、Ｃｕ：Ｂ
ｉ：Ｃａ：５ｒ−２，０：０．９３：！、１１：１４８
てあり、分析誤差は各元素に対して±ｌＯ％以下である
。Example 3 Metallic Cu, Bi, fluoride Ca by electron beam evaporation
F2. SrF2 1llt'tZ Cu+Bi:C
a:5r-2:1.5:1:l, about 255 Cu, about 360 Bi, about 450 CaF2,
Approximately 1,350 layers of SrF2 were deposited. This thickness was calculated from a film thickness meter during deposition, and the actual total film thickness was 2,814. This laminated film was heat-treated in oxygen at about 870° C. for 1 hour to decompose the fluoride and simultaneously convert it into an oxide compound. In composition analysis by X-ray fluorescence analysis, Cu:B
i:Ca:5r-2,0:0.93:! , 11:148
The analysis error is less than ±10% for each element.
通常の四端法でこの酸化膜の電気抵抗の温度変化を測定
した結果を第３図に示す。約１１０にで抵抗か急激に下
がるものの、約１０７に以下で抵抗が残存し、約６０に
で抵抗がゼロとなる、二段の変化を示している。FIG. 3 shows the results of measuring temperature changes in the electrical resistance of this oxide film using the usual four-edge method. Although the resistance drops sharply at about 110, resistance remains below about 107 and becomes zero at about 60, showing a two-step change.
組成分析の精度内でこの酸化膜の化合物は実施例１およ
び２の化合物と同しであることから、この二段の抵抗変
化、言い換えれば１１０Ｋにのみ超伝導転移を示す膜は
初期の堆積膜厚の違いによることに他ならない。すなわ
ち、実施例２の場合に比べＣａ濃度が測定精度（誤差±
１ｏｆｔ； ）内であるが、膜厚は１．４倍厚い。Since the compound of this oxide film is the same as the compounds of Examples 1 and 2 within the accuracy of compositional analysis, this two-step resistance change, in other words, the film showing superconducting transition only at 110K is an early deposited film. This is simply due to the difference in thickness. That is, compared to the case of Example 2, the Ca concentration has a lower measurement accuracy (error ±
), but the film thickness is 1.4 times thicker.
第４図に実施例１および実施例３で得られた酸化膜のＸ
線回折像を示す。曲線（ａ）は実施例１で得られた膜厚
７７５人の膜、曲線（ｂ）は実施例３で得られた２８１
４人の１漠の回折図形である。第４図に示すように各試
料は同じパターンを示し、ＢｆＳｒ、、 ５ＣａＣｕ２
０Ｘ（ｘは不明）の酸化物化合物が基板上に配向してい
ることを示し、はぼ同一の構造か出来ている。しかし、
実施例３での厚い膜の場合には２θ＝３２°のピークが
僅かに現われ、これが電気抵抗の低温での据びきの原因
と云える。膜りが２５００Å以下ではほぼ１１０に転移
温度の超伝導体となっていることが結論され、この事は
組成とともに本発明者らが見出したものである。Figure 4 shows the X of the oxide films obtained in Example 1 and Example 3.
A line diffraction image is shown. Curve (a) shows the film thickness of 775 people obtained in Example 1, and curve (b) shows the film thickness of 281 people obtained in Example 3.
This is a diffraction pattern of four people. As shown in Figure 4, each sample shows the same pattern, BfSr, 5CaCu2
This shows that an oxide compound of 0X (x is unknown) is oriented on the substrate, and almost the same structure is formed. but,
In the case of the thick film in Example 3, a peak at 2θ=32° slightly appears, and this can be said to be the cause of the electrical resistance remaining unchanged at low temperatures. It was concluded that when the film thickness is 2500 Å or less, it becomes a superconductor with a transition temperature of approximately 110 Å, and this fact was discovered by the present inventors along with the composition.
実施例４
実施例２で行った積層堆積（初期膜厚１９９３人）をし
た後に同様に酸化熱処理を行い、約１１０にの超伝導転
移を確認した後、再び同じ組成になるように約２０００
人のＢｉｏ９４Ｓｒ＋、 ４０ｃａ０．６６Ｃｕ２．
ＯＯｘを堆積し、やはり酸素中で８７０℃１時間酸化熱
処理を行った。Example 4 After performing the layered deposition (initial film thickness of 1993) as in Example 2, oxidation heat treatment was performed in the same manner, and after confirming the superconducting transition to about 110, the layer was deposited to about 2000 to have the same composition again.
Human Bio94Sr+, 40ca0.66Cu2.
OOx was deposited, and oxidation heat treatment was performed at 870° C. for 1 hour in oxygen as well.
この酸化膜は約４０００人の膜厚をもつ。通常の四端子
法て電気抵抗の温度変化を測定した結果を第５図に示す
。膜厚約２８００人の実施例３では電気抵抗の温度変化
は二段になって約７０８で抵抗ゼロになったが、本実施
例のように２０００人膜厚の堆積・熱処理を繰返して約
４０００人の膜にしたときには、２５００ Ａ膜厚単層
の抵抗温度変化と大差なく、約１１０にで抵抗か急激に
低下して約９５にで抵抗ゼロの超伝導体厚膜が得られた
。すなわち、２５００Å以下の膜の堆積・熱処理を多数
回繰返すことによってより厚い１１０に転移温度をもつ
膜が得られる。This oxide film has a thickness of about 4,000 people. Figure 5 shows the results of measuring the temperature change in electrical resistance using the usual four-terminal method. In Example 3 with a film thickness of about 2,800 people, the temperature change in electrical resistance was in two steps and reached zero resistance at about 708, but as in this example, repeating the deposition and heat treatment to a film thickness of 2,000 people resulted in a temperature change of about 4,000. When it was made into a human film, the resistance temperature change was not much different from that of a single layer with a thickness of 2500 A, but the resistance suddenly decreased at about 110 A, and a superconductor thick film with zero resistance was obtained at about 95 A. That is, by repeating the deposition and heat treatment of a film with a thickness of 2500 Å or less many times, a thicker film with a transition temperature of 110 can be obtained.
２５００Å以下の膜厚であればよい事は実施例１〜３の
結果からも明らかで、薄い膜はど超伝導転移での電気抵
抗の据が小さいことから容易に判断できる。It is clear from the results of Examples 1 to 3 that a film thickness of 2500 Å or less is sufficient, and it can be easily determined from the fact that the thinner the film, the smaller the electrical resistance at the superconducting transition.
実施例５
電子ビーム蒸着により金属Ｃｕ、Ｂｉおよびフッ化物Ｃ
ｕＦ２．ＳｒＦ２の順に基板ＭｇＯ（１００）面上に堆
積した。膜厚は２００６人であった。この膜を酸素中で
約８７０℃１時間熱処理して酸化物薄膜とした。四端子
法によって測定したこの膜の電気の温度変化を第６図に
示す。約１１０にで電気抵抗が急激に下がって、約１０
８にて電気抵抗がゼロとなる超伝導性を示している。Example 5 Metal Cu, Bi and fluoride C by electron beam evaporation
uF2. SrF2 was deposited on the MgO (100) surface of the substrate. The film thickness was 2006 people. This film was heat-treated in oxygen at about 870° C. for 1 hour to form an oxide thin film. Figure 6 shows the electrical temperature change of this film measured by the four-terminal method. At about 110, the electrical resistance suddenly decreases to about 10
8 shows superconductivity with zero electrical resistance.
本発明の酸化物超伝導体は
Ｂｉｌ、 ｏｓｒ＋、 ５Ｃａ１．０Ｃ１１２，００１
１を中心組成とし、Ｂｉ、Ｓｒ。The oxide superconductor of the present invention is Bil, osr+, 5Ca1.0C112,001
1 as the main composition, Bi, Sr.
ＣａおよびＣｕの原子比が、Ｃｕを２とした時、Ｂｉが
０．７〜１．１．５ｒが１．４〜３．１．Ｃａが０．８
５〜１．１ である。この組成範囲をはずれると、良好
な超伝導特性が得られない。When the atomic ratio of Ca and Cu is 2 for Cu, 0.7 to 1.1.5 for Bi and 1.4 to 3.1. Ca is 0.8
5 to 1.1. If the composition is outside this range, good superconducting properties cannot be obtained.
実施例では、アルカリ土類元素の蒸発源としてＣａＦ２
．ＳｒＦ２を用いたが、金属Ｃａ、Ｓｒでもよく、また
膜堆積法についても本発明は限定、あるいは制約される
ものではない。本発明においては、上述した組成の酸化
物を厚さ２５００Å以下で基板上に堆積させ、または２
５００Å以下の厚さの膜の堆積と熱処理とを繰返して酸
化物超伝導体膜を形成することによって、高い超伝導転
移温度を得ることができる。In the example, CaF2 is used as an evaporation source of alkaline earth elements.
．． Although SrF2 is used, metallic Ca or Sr may also be used, and the present invention is not limited or restricted to the film deposition method. In the present invention, an oxide having the above-mentioned composition is deposited on a substrate to a thickness of 2500 Å or less, or
A high superconducting transition temperature can be obtained by forming an oxide superconductor film by repeatedly depositing a film with a thickness of 500 Å or less and heat treatment.
〔発明の効果］
以上説明したように、Ｂ１−５ｒ−Ｃａ−Ｃｕ−０回元
（酸素を含めると三元）系酸化物で、Ｂｉ：Ｓｒ：Ｃａ
：Ｃｕ−，０７〜１．１・１．４〜３．１：０．８５〜
１．１：２．０の比をもつ化合物が絶対温度的１１０に
で超伝導転移を示す新物質であり、この転移温度を保っ
た薄膜を形成するには１回の堆積膜厚を２５００Å以下
とすることで実現できる。この結果、液体窒素温度７７
よりも３０度以上転移温度が高いことから、この組成比
をもつ薄膜により７７にで安定して動作する種々のエレ
クトロニクスデバイスが実現できる。[Effect of the invention] As explained above, the B1-5r-Ca-Cu-0-component (ternary if oxygen is included) based oxide, Bi:Sr:Ca
:Cu-, 07~1.1・1.4~3.1:0.85~
A compound with a ratio of 1.1:2.0 is a new material that exhibits a superconducting transition at an absolute temperature of 110°C, and in order to form a thin film that maintains this transition temperature, the thickness of a single deposition must be 2500 Å or less. This can be achieved by doing this. As a result, the liquid nitrogen temperature was 77
Since the transition temperature is 30 degrees higher than that of 77°C, various electronic devices that operate stably at 77°C can be realized using thin films with this composition ratio.
第１図は初期膜厚７７５人の
Ｂｌ １． ＋）８ｓｒ＋、 ４．Ｃａ＋、 ０８ｃｕ
２． Ｏｏ、薄膜の電気抵抗の温度変化を示す特性図、
第２図は初期膜厚１９９３人の
Ｂｉｏ、 ９４ｓｒ１４ｏｃａｏ、 ａａＣｕ２． ｏ
ｏ。薄膜の電気抵抗の温度変化を示す特性図、
第３図は初期膜圧２８１４人の
Ｂｉｏ９５５ｒ１．４８Ｃａ１． ｌ０ｃｕ２．００ｘ
薄膜の電気抵抗の温度変化を示す特性図、
第４図は本発明による基板ＭｇＯ上の
Ｂ１−５ｒ−Ｃａ−Ｃｕ−０超伝導薄膜のＸ線回折図、
第５図は堆積と熱処理を繰返し行った膜厚約４０００人
の薄膜の電気抵抗の温度変化を示す特性図、
第６図は月莫厚２００６人の
Ｂｉｏ、 ９２ｓｒ３． ｏａｃａ＋、 ０４ＣＩＪ２
． ＯＯＸ薄膜の電気抵抗の温度変化を示す特性図であ
る。
特許出願人 日本電信電話株式会社Figure 1 shows the initial film thickness of 775 people. +)8sr+, 4. Ca+, 08cu
2. Oo, a characteristic diagram showing the temperature change of electrical resistance of a thin film. Figure 2 shows an initial film thickness of 1993 Bio, 94sr14ocao, aaCu2. o
o. A characteristic diagram showing temperature changes in electrical resistance of a thin film. Figure 3 shows an initial film pressure of 2814 people Bio955r1.48Ca1. l0cu2.00x
FIG. 4 is an X-ray diffraction diagram of a B1-5r-Ca-Cu-0 superconducting thin film on a MgO substrate according to the present invention;
Figure 5 is a characteristic diagram showing the temperature change in electrical resistance of a thin film with a thickness of approximately 4,000 after repeated deposition and heat treatment. oaca+, 04CIJ2
．． FIG. 2 is a characteristic diagram showing temperature changes in electrical resistance of an OOX thin film. Patent applicant Nippon Telegraph and Telephone Corporation
Claims (1)
表され、ｕ：ｖ：ｗ：ｘの比が０．７〜１．１：１．４
〜３．１：０．８５〜１．１：２であることを特徴とす
る酸化物超伝導体。 ２）請求項１に記載された酸化物超伝導体を、２５００
Å以下の厚さで基板上に堆積することを特徴とする酸化
物超伝導体膜の製造方法。 ３）請求項１に記載された酸化物超伝導体を２５００Å
以下の厚さで基板上に堆積し、熱処理する工程を複数回
繰り返すことを特徴とする酸化物超伝導体膜の製造方法
。[Claims] 1) It is represented by the compositional formula Bi_uSr_vCa_wCu_xO_y, and the ratio of u:v:w:x is 0.7 to 1.1:1.4.
An oxide superconductor characterized in that the ratio is 3.1:0.85 to 1.1:2. 2) The oxide superconductor according to claim 1 is
A method for producing an oxide superconductor film, characterized in that it is deposited on a substrate to a thickness of Å or less. 3) The oxide superconductor described in claim 1 has a thickness of 2500 Å.
A method for producing an oxide superconductor film, characterized by repeating the steps of depositing it on a substrate to a thickness below and heat-treating it multiple times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63065871A JP2635355B2 (en) | 1988-03-22 | 1988-03-22 | Method for producing oxide superconductor film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63065871A JP2635355B2 (en) | 1988-03-22 | 1988-03-22 | Method for producing oxide superconductor film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01239027A true JPH01239027A (en) | 1989-09-25 |
| JP2635355B2 JP2635355B2 (en) | 1997-07-30 |
Family
ID=13299478
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63065871A Expired - Fee Related JP2635355B2 (en) | 1988-03-22 | 1988-03-22 | Method for producing oxide superconductor film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2635355B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH054897A (en) * | 1991-06-24 | 1993-01-14 | Kokusai Chodendo Sangyo Gijutsu Kenkyu Center | Bi-sr-ca-cu-o-based superconductor film and production thereof |
| JPH05254995A (en) * | 1992-03-06 | 1993-10-05 | Kokusai Chodendo Sangyo Gijutsu Kenkyu Center | Multilayer film consisting of superconducting layer of bisrcacuo system and bismuth oxide insulating layer and its production |
| US6613855B1 (en) | 1997-04-09 | 2003-09-02 | Sanyo Chemical Industries, Ltd. | Polymerizable resin, and cured resins, insulators, components of electrical appliances, and electrical appliances made by using the same |
-
1988
- 1988-03-22 JP JP63065871A patent/JP2635355B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| JAPANESE JOURNAL OF APPLIED PHYSICS=1988 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH054897A (en) * | 1991-06-24 | 1993-01-14 | Kokusai Chodendo Sangyo Gijutsu Kenkyu Center | Bi-sr-ca-cu-o-based superconductor film and production thereof |
| JPH05254995A (en) * | 1992-03-06 | 1993-10-05 | Kokusai Chodendo Sangyo Gijutsu Kenkyu Center | Multilayer film consisting of superconducting layer of bisrcacuo system and bismuth oxide insulating layer and its production |
| US6613855B1 (en) | 1997-04-09 | 2003-09-02 | Sanyo Chemical Industries, Ltd. | Polymerizable resin, and cured resins, insulators, components of electrical appliances, and electrical appliances made by using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2635355B2 (en) | 1997-07-30 |
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