JPH04270197A - Production of single crystal of oxide superconductor - Google Patents
Production of single crystal of oxide superconductorInfo
- Publication number
- JPH04270197A JPH04270197A JP3053926A JP5392691A JPH04270197A JP H04270197 A JPH04270197 A JP H04270197A JP 3053926 A JP3053926 A JP 3053926A JP 5392691 A JP5392691 A JP 5392691A JP H04270197 A JPH04270197 A JP H04270197A
- Authority
- JP
- Japan
- Prior art keywords
- single crystal
- flux
- oxide superconductor
- 1cuno4
- oxide
- 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 22
- 239000013078 crystal Substances 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 230000004907 flux Effects 0.000 claims abstract description 14
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000011812 mixed powder Substances 0.000 claims abstract description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 abstract description 8
- 230000008020 evaporation Effects 0.000 abstract description 8
- 108091006629 SLC13A2 Proteins 0.000 abstract 2
- 238000000034 method Methods 0.000 description 5
- 229910002480 Cu-O Inorganic materials 0.000 description 3
- 229910052810 boron oxide Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000238366 Cephalopoda Species 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000005292 diamagnetic effect Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000005291 magnetic effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 238000000605 extraction Methods 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
- 238000005259 measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- LPHBARMWKLYWRA-UHFFFAOYSA-N thallium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tl+3].[Tl+3] LPHBARMWKLYWRA-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、各種の超伝導応用装置
や超伝導素子に使用される酸化物超伝導体単結晶の製造
方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing oxide superconductor single crystals used in various superconducting application devices and superconducting elements.
【０００２】0002
【従来の技術】金属・合金系超伝導材料，化合物超伝導
材料は、ジョセフソン素子や超伝導マグネットの線材と
して既に広く利用されている。ジョセフソン接合はその
磁場に対する高い感度のためＳＱＵＩＤを初めとする精
密計測に応用されているほか、その高速性から電子計算
機への応用が期待されている。また、通常導体では得ら
れないような高磁場を発生できる超伝導マグネットは、
ＮＭＲ−ＣＴなどの医療機器や浮上型リニアモーターカ
ー等にも応用されている。2. Description of the Related Art Metal/alloy superconducting materials and compound superconducting materials are already widely used as wire materials for Josephson elements and superconducting magnets. Josephson junctions are used in precision measurements such as SQUIDs due to their high sensitivity to magnetic fields, and are expected to be used in electronic computers due to their high speed. In addition, superconducting magnets can generate high magnetic fields that cannot be obtained with ordinary conductors.
It is also applied to medical equipment such as NMR-CT and floating linear motor cars.
【０００３】超伝導体の応用を考えた場合、超伝導転移
温度Ｔｃはできる限り高いことが望まれる。金属・合金
系超伝導体や化合物系超伝導体は、冷媒として高価で希
少な液体ヘリウムを用いなければならず、このことがこ
れらの超伝導体の広い分野への応用を妨げる一因となっ
ている。この点では銅酸化物系超伝導体は、従来の超伝
導体よりもはるかに優れており、１９８７年にＢａ−Ｙ
−Ｃｕ−Ｏ系超伝導体が発見されて以来、Ｂｉ−Ｓｒ−
Ｃａ−Ｃｕ−Ｏ系，Ｔｌ−Ｂａ−Ｃａ−Ｃｕ−Ｏ系など
の液体窒素温度を越えるＴｃをもつ超伝導体が相次いで
発見されている。これらの酸化物超伝導体が実用化され
れば、今まで考えられなかったような分野にまでその応
用の可能性が広がるとして、現在も研究開発が盛んに行
われている。When considering the application of superconductors, it is desired that the superconducting transition temperature Tc be as high as possible. Metal/alloy-based superconductors and compound-based superconductors require the use of expensive and rare liquid helium as a coolant, and this is one of the factors that prevents the application of these superconductors in a wide range of fields. ing. In this respect, cuprate-based superconductors are far superior to conventional superconductors, and in 1987 Ba-Y
Since the discovery of -Cu-O superconductors, Bi-Sr-
Superconductors having Tc exceeding the liquid nitrogen temperature have been discovered one after another, such as Ca-Cu-O and Tl-Ba-Ca-Cu-O. If these oxide superconductors are put into practical use, their potential applications will expand to fields that were previously unimaginable, and research and development efforts are currently underway.
【０００４】0004
【発明が解決しようとする課題】現在研究されている酸
化物超伝導体試料のほとんどは多結晶体である。超伝導
体の多結晶試料では、その結晶粒界に無数の超伝導の弱
結合が存在するため、望む特性を持つジョセフソン接合
を制御性良く作ることが困難である。また、多結晶体が
含んでいる各種の欠陥や不均質性が超伝導特性の安定性
に悪い影響を与えることも考えられるため、デバイスな
どへの応用には単結晶体を用いることが望ましい。[Problems to be Solved by the Invention] Most of the oxide superconductor samples currently being studied are polycrystalline. In polycrystalline superconductor samples, there are countless superconducting weak bonds at the grain boundaries, making it difficult to controllably create Josephson junctions with desired properties. Furthermore, since various defects and inhomogeneities contained in polycrystals may have a negative effect on the stability of superconducting properties, it is desirable to use single crystals for applications such as devices.
【０００５】Ｔｌ系超伝導体単結晶を得る方法の１つと
して、ＫＣｌ／ＮａＣｌやＰｂＣｌ２フラックスを用い
る方法がある。これらのフラックスは、水溶性のため出
来上がった結晶を容易に取り出すことができるという利
点があるが、同時に結晶成長を行う９００℃程度の温度
域での蒸気圧が高いため、成長中にどんどん蒸発してい
くという問題点がある。One of the methods for obtaining a Tl-based superconductor single crystal is to use KCl/NaCl or PbCl2 flux. These fluxes have the advantage that the formed crystals can be easily taken out because they are water-soluble, but at the same time, their vapor pressure is high in the temperature range of about 900°C where crystal growth occurs, so they evaporate rapidly during growth. There is a problem with how to proceed.
【０００６】そこで本発明の目的は、ＫＣｌ／ＮａＣｌ
やＰｂＣｌ２フラックスを用いたＴｌ系超伝導体単結晶
の製造時におけるフラックスの蒸発を押える方法を提供
することにある。[0006] Therefore, the object of the present invention is to
An object of the present invention is to provide a method for suppressing flux evaporation during the production of a Tl-based superconductor single crystal using PbCl2 flux.
【０００７】[0007]
【課題を解決するための手段】前記目的を達成するため
、本発明に係る酸化物超伝導体単結晶の製造方法におい
ては、Ｔｌ２Ｂａ２Ｃａｎ−１ＣｕｎＯ４＋２ｎ（ｎ＝
１，２，３）と表される酸化物超伝導体単結晶を、ＫＣ
ｌ又はＫＣｌ＋ＮａＣｌ又はＰｂＣｌ２をフラックスと
して用いて製造する製造方法において、酸化物超伝導体
材料をなす混合粉末に、酸化ほう素（Ｂ２Ｏ３）を添加
するものである。[Means for Solving the Problems] In order to achieve the above object, in the method for manufacturing an oxide superconductor single crystal according to the present invention, Tl2Ba2Can-1CunO4+2n (n=
KC
In a manufacturing method using 1 or KCl+NaCl or PbCl2 as a flux, boron oxide (B2O3) is added to a mixed powder constituting an oxide superconductor material.
【０００８】[0008]
【作用】本発明は、Ｔｌ２Ｂａ２Ｃａｎ−１ＣｕｎＯ４
＋２ｎをＫＣｌ又はＫＣｌ＋ＮａＣｌ又はＰｂＣｌ２フ
ラックスで合成する際にＢ２Ｏ３を添加することにより
、フラックスの蒸発量が押えられ、良質のＴｌ２Ｂａ２
Ｃａｎ−１ＣｕｎＯ４＋２ｎ単結晶が得られることを見
いだしたものである。この原理に基づき、Ｔｌ２Ｂａ２
ＣｕＯ６＋２０ＫＣｌ＋５Ｂ２Ｏ３組成の混合粉から、
最高温度９２０℃，徐冷速度５℃／ｈｏｕｒで作製した
単結晶は数ｍｍ角で厚み０．１ｍｍ程度の大きさで、８
５Ｋで超伝導に転移した。単体のＫＣｌの蒸発量が特に
多い９２０℃から８５０℃の温度範囲を１０時間以上か
けて徐冷したにもかかわらず実際のＫＣｌの蒸発はほと
んどなかった。[Operation] The present invention provides Tl2Ba2Can-1CunO4
By adding B2O3 when synthesizing +2n with KCl or KCl+NaCl or PbCl2 flux, the amount of evaporation of the flux is suppressed and high quality Tl2Ba2 is produced.
It was discovered that a Can-1CunO4+2n single crystal could be obtained. Based on this principle, Tl2Ba2
From the mixed powder of CuO6 + 20KCl + 5B2O3 composition,
The single crystal produced at a maximum temperature of 920°C and a slow cooling rate of 5°C/hour has a size of several mm square and a thickness of about 0.1 mm.
It transitioned to superconductivity at 5K. Although the temperature range from 920° C. to 850° C., where the amount of evaporation of simple KCl is especially large, was slowly cooled for more than 10 hours, there was almost no actual evaporation of KCl.
【０００９】[0009]
【実施例】以下実施例により、本発明を具体的に説明す
る。[Examples] The present invention will be explained in detail with reference to Examples below.
【００１０】（実施例１）出発原料として純度９９．９
％以上の酸化タリウム（Ｔｌ２Ｏ３），酸化バリウム（
ＢａＯ），酸化カルシウム（ＣａＯ），酸化第二銅（Ｃ
ｕＯ）を使用した。これらの原料をＴｌ２Ｂａ２Ｃａｎ
−１ＣｕｎＯ４＋２ｎの比になるように混合し、プレス
した後、金箔で包んだ８６０℃〜９００℃で３〜５時間
焼結した。
得られた焼結体を粉砕しＴｌ２Ｂａ２Ｃａｎ−１Ｃｕｎ
Ｏ４＋２ｎ＋１０（ＫＣｌ＋ＮａＣｌ）＋ｘＢ２Ｏ３な
る一般式でｎ，ｘについては表１に示す配合比になるよ
うに混合した。混合粉を直径２０ｍｍ，深さ２５ｍｍの
金坩堝中で７００℃〜９００℃で１〜１０時間融解させ
たのち、１時間に１０℃以下の速度で６００℃まで徐冷
した。６００℃から室温までは１時間１００℃の割合で
冷却した。
単結晶試料はＫＣｌ，ＮａＣｌおよびＢ２Ｏ３を水で洗
い流すことによって取り出した。(Example 1) Purity 99.9 as starting material
% or more of thallium oxide (Tl2O3), barium oxide (
BaO), calcium oxide (CaO), cupric oxide (C
uO) was used. These raw materials are Tl2Ba2Can
The mixture was mixed to a ratio of -1CunO4+2n, pressed, and then sintered at 860°C to 900°C for 3 to 5 hours while wrapped in gold foil. The obtained sintered body was crushed to form Tl2Ba2Can-1Cun.
They were mixed in a general formula of O4+2n+10(KCl+NaCl)+xB2O3, with n and x in the compounding ratio shown in Table 1. The mixed powder was melted in a metal crucible with a diameter of 20 mm and a depth of 25 mm at 700°C to 900°C for 1 to 10 hours, and then gradually cooled to 600°C at a rate of 10°C or less per hour. Cooling was performed at a rate of 100°C for 1 hour from 600°C to room temperature. Single crystal samples were removed by washing away KCl, NaCl and B2O3 with water.
【００１１】[0011]
【表１】[Table 1]
【００１２】（実施例２）実施例１と同様の試薬を出発
原料としＴｌ２Ｂａ２Ｃａｎ−１ＣｕｎＯ４＋２ｎ焼結
体を合成した。得られた焼結体を粉砕しＴｌ２Ｂａ２Ｃ
ａｎ−１ＣｕｎＯ４＋２ｎ＋２０ＰｂＣｌ２＋ｘＢ２Ｏ
３なる一般式でｎ，ｘについては表２に示す配合比にな
るように混合した。融解，固化，単結晶の取り出しは実
施例１と同様の条件で行った。(Example 2) Using the same reagent as in Example 1 as a starting material, a Tl2Ba2Can-1CunO4+2n sintered body was synthesized. The obtained sintered body is crushed and Tl2Ba2C
an-1CunO4+2n+20PbCl2+xB2O
In the general formula 3, n and x were mixed so as to have the compounding ratio shown in Table 2. Melting, solidification, and single crystal extraction were performed under the same conditions as in Example 1.
【００１３】得られた単結晶の抵抗率，反磁性磁化率の
測定、及び組成分析を行った。抵抗率は金線をリードと
する４端子法で、反磁性磁化率はＳＱＵＩＤマグネトメ
ーターでそれぞれ測定した。組成分析はＥＰＭＡを用い
て行った。The resistivity and diamagnetic susceptibility of the obtained single crystal were measured, and the composition was analyzed. Resistivity was measured using a four-terminal method using a gold wire as a lead, and diamagnetic susceptibility was measured using a SQUID magnetometer. Compositional analysis was performed using EPMA.
【００１４】[0014]
【表２】[Table 2]
【００１５】表１，表２に得られた単結晶の典型的な大
きさとＴｃを示す。Ｂ２Ｏ２量が少なすぎると蒸発を押
える効果があまりないため、９００℃以上の温度で単結
晶育成が難しい。またＢ２Ｏ３が多すぎると原料，フラ
ックスチャージ量が減ってしまうので実用的ではない。Tables 1 and 2 show typical sizes and Tc of the single crystals obtained. If the amount of B2O2 is too small, there will be little effect in suppressing evaporation, making it difficult to grow single crystals at temperatures above 900°C. Moreover, if B2O3 is too large, the amount of raw materials and flux charge will be reduced, which is not practical.
【００１６】[0016]
【発明の効果】本発明の製造方法によれば、フラックス
の蒸発を押えてＴｌ２Ｂａ２Ｃａｎ−１ＣｕｎＯ４＋２
ｎの良質な単結晶を得ることができるため、超伝導材料
の工業利用にとって極めて有用なものである。Effects of the Invention According to the production method of the present invention, evaporation of flux is suppressed and Tl2Ba2Can-1CunO4+2
Since it is possible to obtain a high quality single crystal of n, it is extremely useful for industrial use of superconducting materials.
Claims (1)
２ｎ（ｎ＝１，２，３）と表される酸化物超伝導体単結
晶を、ＫＣｌ又はＫＣｌ＋ＮａＣｌ又はＰｂＣｌ２をフ
ラックスとして用いて製造する製造方法において、酸化
物超伝導体材料をなす混合粉末に、酸化ほう素（Ｂ２Ｏ
３）を添加することを特徴とする酸化物超伝導体単結晶
の製造方法。[Claim 1] Tl2Ba2Can-1CunO4+
In a manufacturing method for manufacturing an oxide superconductor single crystal expressed as 2n (n = 1, 2, 3) using KCl or KCl + NaCl or PbCl2 as a flux, a mixed powder constituting the oxide superconductor material is , boron oxide (B2O
3) A method for producing an oxide superconductor single crystal, characterized by adding the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3053926A JP2697334B2 (en) | 1991-02-26 | 1991-02-26 | Method for producing oxide superconductor single crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3053926A JP2697334B2 (en) | 1991-02-26 | 1991-02-26 | Method for producing oxide superconductor single crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04270197A true JPH04270197A (en) | 1992-09-25 |
| JP2697334B2 JP2697334B2 (en) | 1998-01-14 |
Family
ID=12956330
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3053926A Expired - Fee Related JP2697334B2 (en) | 1991-02-26 | 1991-02-26 | Method for producing oxide superconductor single crystal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2697334B2 (en) |
-
1991
- 1991-02-26 JP JP3053926A patent/JP2697334B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2697334B2 (en) | 1998-01-14 |
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