JPS623092A - Production of bapbo3 based oxide superconductor single crystal by solution pulling up method - Google Patents
Production of bapbo3 based oxide superconductor single crystal by solution pulling up methodInfo
- Publication number
- JPS623092A JPS623092A JP14318985A JP14318985A JPS623092A JP S623092 A JPS623092 A JP S623092A JP 14318985 A JP14318985 A JP 14318985A JP 14318985 A JP14318985 A JP 14318985A JP S623092 A JPS623092 A JP S623092A
- Authority
- JP
- Japan
- Prior art keywords
- single crystal
- melt
- mixed
- crystal
- microcrystal
- 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
- 239000013078 crystal Substances 0.000 title claims abstract description 65
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 238000000034 method Methods 0.000 title claims description 12
- 239000002887 superconductor Substances 0.000 title claims description 8
- 239000000155 melt Substances 0.000 claims abstract description 24
- 239000013081 microcrystal Substances 0.000 claims abstract description 12
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims abstract 6
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims abstract 5
- 229910001626 barium chloride Inorganic materials 0.000 claims abstract 5
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims abstract 5
- 229910016063 BaPb Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 229910000464 lead oxide Inorganic materials 0.000 claims 4
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims 2
- 229910000416 bismuth oxide Inorganic materials 0.000 claims 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052697 platinum Inorganic materials 0.000 abstract description 8
- 239000007858 starting material Substances 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 230000003247 decreasing effect Effects 0.000 abstract 2
- 238000000151 deposition Methods 0.000 abstract 1
- 230000006698 induction Effects 0.000 abstract 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000011369 resultant mixture Substances 0.000 abstract 1
- 238000010586 diagram Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 4
- 239000011810 insulating material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000013076 target substance Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- TUQAPGNDQWHJGE-UHFFFAOYSA-L 2-oxo-1,3,2-dioxaplumbetan-4-one Chemical compound [Pb+2]=O.[O-]C([O-])=O TUQAPGNDQWHJGE-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000015241 bacon Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000048 melt cooling Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
- Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、ＢａＰｂＯ，またはＢａＰＪ−！Ｂ１ｚＯ
ｓ単結晶忙よるＢ ａ Ｐ ｂ Ｏｓ系酸化物超伝導体
単結晶の溶液引上げ法による製造方法忙関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention provides BaPbO, or BaPJ-! B1zO
The present invention relates to a method for producing a B a P b Os based oxide superconductor single crystal using a solution pulling method.
従来、高融点物質や包晶反応する物質の単結晶を得る手
段としては、通常、目的物質を溶剤中に混合し、その混
合融液を降温することにより混合融液な過飽和濃度以上
の状態にし、上記目的物質を融液から単結晶として析出
させ得るフランクス法が用いられていた。Conventionally, the method of obtaining a single crystal of a substance with a high melting point or a substance that undergoes a peritectic reaction is to mix the target substance in a solvent and lower the temperature of the mixed melt to bring it to a state above the supersaturation concentration of the mixed melt. The Franks method, which allows the target substance to be precipitated as a single crystal from a melt, was used.
ＢａＰｂ１−ｘＢｕｚｚｓはぺｐズス力イト展をもつ酸
化物で、Ｂｌの組成比Ｘが０または０．３５以下の場合
忙低温で超伝導を示す。特に、ｘ＝０．２５ＶＣおい１
超伝導転移温度Ｔ、が約１３にとなり、遷移金属′を含
まない超伝導物質では最高の転移温度を示す酸化物超伝
導体として知られている。極低温嵩子としてこれからの
応用が考えられ、そのためｋは大型の実質な単結晶が必
要とされ、その製造方法の開発が期待されている。BaPb1-xBuzzs is an oxide with a Pep-zu-Site expansion, and exhibits superconductivity at extremely low temperatures when the Bl composition ratio X is 0 or 0.35 or less. In particular, x=0.25VCoi1
It has a superconducting transition temperature T of approximately 13, and is known as an oxide superconductor that exhibits the highest transition temperature among superconducting materials that do not contain transition metals. It is thought that it will be applied in the future as a cryogenic bulking material, and therefore a large, substantial single crystal is required for k, and the development of a method for producing it is expected.
本発明者は、先に、ＢａＰｂ＋−１Ｂ １ｚＯｓ単結晶
の製造方法を提案した（Ｊａｐａｎ＠ｓｅ Ｊｏｕｒｎ
ａｌ ｏｆ Ａｐｐ−１ｔｅｄ Ｐｈｙｓｌｅｉ Ｌｓ
ｔｔｓｒ、 ２３巻１０号、Ｌ、？７０頁、昭和５９年
１０月発行、参照）。この製造方法は、Ｂ ａ ＣＯｓ
Ｐ ｂ Ｏ（炭酸バリクムー酸化鉛］系の相平衡図
を作成し明らかにすることで、この相平衡図を基本的に
変化させない程度の量のＢｌｚ０寥（酸化ビスマスンを
添加すること忙より、ＢａＰ ｂ ＋ −ｚ Ｂ ｌ
ｘ Ｏｓ単結晶ｆｔＢａｃＯｓ とｐｂｏ とＢｌ、
Ｏ。The present inventor previously proposed a method for manufacturing BaPb+-1B 1zOs single crystal (Japan@se Journal
al of App-1ted Physley Ls
ttsr, Volume 23, No. 10, L,? 70 pages, published October 1982, see). This manufacturing method uses B a COs
By creating and clarifying the phase equilibrium diagram of the P b O (baricum carbonate lead oxide) system, we can add BaP in an amount that does not fundamentally change this phase equilibrium diagram. b + -z B l
x Os single crystal ftBacOs and pbo and Bl,
O.
の３者を混合し約１０５０℃に熱した融液から融液降温
速度２〜１０℃／ｈ、結晶引上げ速度０．３ｎ
り製造するものである。It is produced from a melt mixed with the above three materials and heated to about 1050°C at a melt cooling rate of 2 to 10°C/h and a crystal pulling rate of 0.3n.
ところで、上記のような従来の製造方法によると、直径
３５ Ｘ ３０ ｍｍ 、厚さｌ ｍｍの大きさのＢａ
Ｐｂ＋−！Ｂｌ、Ｏｓ単結晶を得ることができたが１円
板状に育成され、厚さのより大きいものを製造すること
ができないとい５問題点があった。By the way, according to the conventional manufacturing method as described above, Ba of the size 35 x 30 mm in diameter and 1 mm in thickness
Pb+-! Although it was possible to obtain a Bl, Os single crystal, there were five problems in that it was grown in the shape of a single disk and it was not possible to manufacture one with a larger thickness.
この発明は、上記問題点を解決するためになされたもの
で％製造時間を長くとることにより十分な厚さのあるＢ
ａＰｂＯｘまたはＢａＰｂ＋−ｘＢｌ、 Ｏｓ （ｘ
＝ ０．４以下）の大型の単結晶を得る製造方法を提供
するものである。This invention was made in order to solve the above-mentioned problems, and by increasing the production time, it is possible to obtain a sufficient thickness of B.
aPbOx or BaPb+-xBl, Os (x
= 0.4 or less) is provided.
この発明忙かかるＢａＰｂＯ１系酸化物超伝導体単結晶
の溶液引上げ法による製造方法は、ＰｂＯとＢ＆Ｃｏｗ
とＢａＣ１１（塩化バリワム）またはｐｂｏと３ａＣＯ
ｓとＢｈＯｍ とＢａＣ１，とを混合し”Ｉ： ９０
０〜１２００℃の温度に加熱融解して融液を生成し、次
いで、この融液を降温しなからＢａＰ ｂ Ｏｓ また
はＢ１Ｐｂ、−ｘＢ ｉ ｘ Ｏ＊ （ｘ ＝０．４以
下）の微結晶を析出させ、この微結晶を同じ（ＢａＰｂ
Ｏ５またはＢａＰ ｂｔ、Ｂｌｚ Ｏｓの種子結晶であ
る単結晶上に結晶して成長させたものである。This inventive manufacturing method of BaPbO1-based oxide superconductor single crystal by solution pulling method is based on PbO and B&Cow.
and BaC11 (Baliwum chloride) or pbo and 3aCO
s, BhOm, and BaC1, "I: 90
A melt is produced by heating and melting at a temperature of 0 to 1200°C, and then the temperature of this melt is lowered to form microcrystals of BaP b Os or B1Pb, -xB i x O* (x = 0.4 or less). is precipitated, and the same (BaPb
It is crystallized and grown on a single crystal that is a seed crystal of O5, BaP bt, or Blz Os.
ＢａＰｂＯ１またはＢａＰｂ＋−２Ｂｔｚ Ｏｓ種子結
晶を徐々に降温しているＢａＰｂ０ｍまたはＢ ＆ Ｐ
ｂ Ｉ−１Ｂ ｉｘ Ｏｓが過飽和濃度以上に混合され
ている融液に接触させると、最も温度の低い種子結晶と
接触し工いる融液の界ＩＮＫ ＢａＰｂ０ｍまたはＢａ
Ｐｂ、−、Ｂｉ！ｏ＊微結晶が少しずつ析出してきて種
子結晶である単結晶上に結晶化する。BaPbO1 or BaPb+-2Btz Os seed crystals are gradually cooled to BaPb0m or B&P.
b When I-1B ix Os is brought into contact with the melt mixed at a supersaturation concentration or higher, the melt boundary INK BaPb0m or Ba
Pb, -, Bi! o* Microcrystals are precipitated little by little and crystallized onto a single crystal that is a seed crystal.
まず、この発明の原理について説明する。 First, the principle of this invention will be explained.
溶剤の役割を果すＰｂＯとＢａＣ１４の混合融液に結晶
成分となるＢ ａ ＣＯｓとｐｂｏとＢ ｌ ＊ Ｏｓ
から構成される化合物ＢａＰ ｂ、−！ｎ ｉｆ ｏ、
をこの溶剤に対して過飽和濃度以上の割合で混合し、加
熱融解して融液な生成する。その後、この混合融液を徐
々゛に冷却し工い（と、過飽和になった分のＢａＰｂ１
−ｘ”つ０、が微結晶どなって析出してくる。この微結
晶を同じ成分の単結晶である。Ｂ ａ Ｐ ｂ、、Ｂ
ｌ工Ｏ３種子結晶上に析出せしめ、それを育成させ工引
き上げる製造方法でおる。B a COs, pbo, and B l *Os, which become crystal components, are added to the mixed melt of PbO and BaC14, which acts as a solvent.
A compound consisting of BaP b, -! n if o,
are mixed with this solvent at a ratio of at least the supersaturation concentration, and heated and melted to form a melt. After that, this mixed melt was gradually cooled (and the BaPb1 that became supersaturated was
-x" 0, precipitates as microcrystals. These microcrystals are single crystals of the same components. B a P b,,B
This is a production method in which O3 is precipitated on a seed crystal and then grown and pulled up.
第１図（ａ）、 （ｂ）はこの発明の一実施例を説明す
るためＫＢａＣＯ＊ とｐｂｏとＢａＣ１，どＢｌｚ０
．との４者の混合比を変九℃単績晶育成を実施し、それ
を作図し、たＢａ、ＣＯ３ＰｂＯ刊３ａＣ１ｇの単結晶
育成可能の組成範囲を示す図である。これらの図におい
て、黒丸印はＢ ＆ Ｐ ｂ、−０Ｂ ｌ ｘ Ｏｓ大
３１１３結晶（５Ｘ ５ Ｘ ２ ｍｍ以上）の育成可
能であることを示す。FIGS. 1(a) and 1(b) show KBaCO*, pbo, BaC1, and Blz0 in order to explain an embodiment of the present invention.
．． It is a diagram showing the composition range in which a single crystal of Ba, CO3PbO, 3aC1g can be grown. In these figures, the black circles indicate that B & P b, -0 B l x Os large 3113 crystals (5 x 5 x 2 mm or more) can be grown.
ここで、第１図（ａ）は重量比でＢｌｚＯ＊ ／ｐｂ
Ｏが０ ／ １００のとき１３ａＰｂｏｓ大型単結晶の
育成範囲はｐｂｏが６５〜９０重量％、８ａＣＯｓが５
〜２５重量％、ＢａＣ１５が２〜ｚｓ菫量％であること
が示されている。Here, Fig. 1(a) shows the weight ratio of BlzO*/pb
When O is 0/100, the growth range of 13aPbos large single crystal is 65 to 90% by weight of pbo and 5% of 8aCOs.
-25% by weight, BaC15 is shown to be 2-zs violet%.
第１図（ｂ）では重量比で旧＊Ｏｓ／ＰｂＯが２０／８
０のとき、ＢａＰｂ＋−ｚＢｌｘ Ｏｎ大型単結晶の育
成範囲はｐｂｏ が７５〜８８重量％、Ｂａｃｏｎが８
〜１８重量％＊ ＢａＣＬ、 が２〜１５ｊｔ量％で
あることが示されている。In Figure 1(b), the weight ratio of old *Os/PbO is 20/8.
0, the growth range of BaPb+-zBlx On large single crystal is 75-88% by weight for pbo and 8% for Bacon.
~18 wt%* BaCL, is shown to be 2 to 15 jt wt%.
＠２図はＢａ Ｐ ｂ ０３またはＢ ａＰｂ＋−Ｊｌ
ｘＯ＊単結晶の溶液引上げ法を実施するための製造装置
を示す構成図で、１は水冷シャフト、２は前記水冷シャ
ツ）ＩＫ接続された白金シャフト、３は保温材、４は前
記保温材３の外周に巻回された高周波加熱コイル、５は
熱電対、６は前記白金シャフト２の先端に取り付けられ
たＢａＰｂ０ｍまたはＢ ａ Ｐ ｂ ５−ｘＢｌ、Ｏ
ｓ の種子結晶である単結晶、Ｔは出発原料、８は前
記出発原料７を入れる白金るつぼ、Ｓは前記るつぼ８を
支持する支持部材である。@2 Figure is Ba P b 03 or Ba Pb+-Jl
This is a configuration diagram showing a manufacturing apparatus for carrying out the solution pulling method of xO* single crystal, in which 1 is a water cooling shaft, 2 is a platinum shaft connected to the IK (water cooling shirt), 3 is a heat insulating material, and 4 is the above heat insulating material 3. 5 is a thermocouple, 6 is a BaPb0m or BaPb 5-xBl, O attached to the tip of the platinum shaft 2.
s is a single crystal which is a seed crystal, T is a starting material, 8 is a platinum crucible in which the starting material 7 is placed, and S is a support member that supports the crucible 8.
次に、ＢａＰｂ＋−１Ｂ１！Ｏｎ単結晶の製造方法の一
例忙つい工説明する。Next, BaPb+-1B1! An example of a method for producing On single crystals will be explained below.
Ｂｌとｐｂの比であるＸの所望の数値のＢａＰｂ１−！
ＢｌｘＯｓ単結晶を製造する場合、融液に混入したＰｂ
ＯとＢ１０．の重量比の約６０〜７５％の値のＢｉがＰ
ｂ Ｋ１ｆｆ１換（すなわちＸの値ンされたＢａＰｂ＋
−ＸＢＩＩＯ１単結晶力；育成されることが実験により
明らかＫなっている。このことを考えに入れて、ＰｂＯ
が６５〜９０重量％、ＢａＣＱｌが５〜２５重量％。BaPb1-! of the desired value of X, which is the ratio of Bl and pb.
When producing BlxOs single crystal, Pb mixed in the melt
O and B10. Bi has a value of about 60 to 75% of the weight ratio of P
b K1ff1 conversion (i.e. BaPb+ with the value of X
-XBIIO1 single crystal strength; experiments have shown that it can be grown. Taking this into consideration, PbO
is 65 to 90% by weight, and BaCQl is 5 to 25% by weight.
ＢａＣ１，が２〜２５％を混合したものに、ｐｂ。PB to a mixture of 2 to 25% BaCl.
ｋ対して重量比で８１，０．を５ｏ％まで混合した４者
の融液な作り、これを出発原料７とする。このような出
発原料１を第２図に、示す口径５０ｍｍ５高さ３５ｍ、
ｍの発熱体を兼ねた白金るつぼ８に入れ、高周波加熱コ
イル４による誘導加熱法忙より約１０５０℃まで加熱し
て融解させた後、白金シャフト２の先端に取り付けた種
子結晶である棒状のＢａＰｂ５−ｘＢｌ、Ｏｓ単結晶で
ある棒状のＢａＰｂａ−、Ｊ３１゜０、の種子結晶であ
る単結晶６を融液表面に接触させる。次いで、融液を徐
々に降温させると、最も温度の低い種子結晶である単結
晶６と接触している融液の界面Ｋ Ｂ ａ Ｐ ｂ、−
ｘＢ ｉ ｚ Ｏｓ微結晶が少しずつ析出してきて種子
結晶であるＢａＰｂ１，８１ｘＯ寥の単結晶Ｂ上に結晶
化する。この上５に成長してきた単結晶を融液から回転
させながら引き上げる。The weight ratio to k is 81.0. A melt of the four materials was prepared by mixing up to 50% of the following, and this was used as starting material 7. Such a starting material 1 is shown in FIG. 2, with a diameter of 50 mm, a height of 35 m, and
A rod-shaped BaPb5 which is a seed crystal is attached to the tip of the platinum shaft 2. A single crystal 6, which is a rod-shaped BaPba-, J31°0, seed crystal, which is a -xBl, Os single crystal, is brought into contact with the surface of the melt. Next, when the temperature of the melt is gradually lowered, the interface of the melt in contact with the single crystal 6, which is the seed crystal with the lowest temperature, K B a P b, -
xB i z Os microcrystals are precipitated little by little and crystallized on the single crystal B of BaPb1,81xO which is a seed crystal. The single crystal that has grown on top 5 is pulled out of the melt while rotating.
すなわち、融液を降温させながら育Ｍ、された単結晶の
引上げを同時に行５のである。この時の調造条件として
種子結晶であるＢａＰｂｘ−２Ｂ１ｚＯｍめ単結晶６の
引き上げ速度は０．３〜ｏ、 ｓ ｍｍ／ｈ、 １１１
液降温速度２〜５℃／ｈ 、種子結晶であるＢａＰｂ＋
−、Ｂ１ｘＯ８の単結晶６０回転数は約５０〜６０ ｒ
、ｐ、 ｍ。That is, in line 5, the grown single crystal is pulled while the temperature of the melt is lowered. As for the preparation conditions at this time, the pulling speed of the BaPbx-2B1zOm single crystal 6, which is a seed crystal, is 0.3 to o, s mm/h, 111
Liquid cooling rate 2-5℃/h, seed crystal BaPb+
-, B1xO8 single crystal 60 rotation speed is about 50-60 r
, p, m.
雰囲気は有毒なＰｂＯ蒸気が外部に出ないように密閉容
器内の空気中で行う。この溶液引上げ法で現在までＩｌ
Ｃ５０Ｘ３５Ｘ４ｒｎの単結晶の育成に成功している。The atmosphere is air in a closed container to prevent toxic PbO vapor from escaping. With this solution pulling method, Il
We have successfully grown a single crystal of C50X35X4rn.
以上説明したようＫこの発明は、ＰｂＯとＢａＯＯｓと
ＢａＣ１＊またはＰｂＯとＢａＣ０ｍとＢ１重ＯｓとＢ
ａＣ１ｇとを混合して９００〜１２００℃の温度に加熱
融解し工融液を生成し、次いで、この融液を降温しなか
らＢ１Ｐｂ０）またはＢａＰ ｂ、−、ｎ ｔ！ ｏｌ
（Ｘ ＝０−４以下λの微結晶を析出させ、この微結
晶を同じ＜ＢａＰｂ０ｚまたはＢａＰｂ１．Ｂ５０ｓの
種子結晶である単結晶上に結晶し″ｃ成長させたので、
製造時間を長（、また、出発原料を充填する白金るつぼ
を大きくすることにより、どのような大聖結晶でも製造
できるきわめ１丁ぐれた利点を有する。As explained above, this invention combines PbO, BaOOs and BaC1* or PbO and BaC0m and B1 heavy Os and B
1 g of aC is mixed and heated and melted at a temperature of 900 to 1200°C to produce a technical melt, and then the temperature of this melt is lowered. ol
(X = 0-4 or less λ microcrystal was precipitated, and this microcrystal was crystallized on the same < BaPb0z or BaPb1.B50s seed crystal single crystal and allowed to grow,
By lengthening the production time and increasing the size of the platinum crucible filled with starting materials, it has the extremely unique advantage of being able to produce any type of Daisei Crystal.
ＩＡ１図（ａ） 、（ｂ）はこの発明の一実施例を説明
するためのＢａＣＯ５ＰｂＯ−ＢａＣ１５系のＢａＰｂ
、−、ＢｉｘＯｓ単結晶育成可能組成範囲を示すもので
、第１図（＆）はＢ１雪Ｏｘの混入なしの場合を示す図
、第１図（ｂンはＢｉｘ０３をｐｂｏの重量に比して２
０／８０混入した場合を示す図、第２図はこの発明を実
施するだめの製造装置を示す構成図である。
図中、１は水冷シャフト、２は白金シャフト。
１・ｔ±保温材、４は高周波コイル、５は熱電対、６は
単結晶、７は出発原料、８は白金るつぼ、９はるつぼ支
持部材である。IA1 diagrams (a) and (b) are BaCO5PbO-BaC15 system BaPb for explaining one embodiment of this invention.
, -, shows the composition range in which BixOs single crystal growth is possible. Figure 1 (&) shows the case without B1 snow Ox mixed in, Figure 1 (b) shows the composition range in which Bix03 is compared to the weight of pbo. 2
FIG. 2 is a diagram showing a case where 0/80 is mixed, and FIG. 2 is a configuration diagram showing a manufacturing apparatus for carrying out the present invention. In the figure, 1 is a water cooling shaft and 2 is a platinum shaft. 1.t± heat insulating material, 4 is a high frequency coil, 5 is a thermocouple, 6 is a single crystal, 7 is a starting material, 8 is a platinum crucible, and 9 is a crucible support member.
Claims (3)
て９００〜１２００℃の温度に加熱融解して融液を生成
し、次いで、この融液を降温しながらＢａＰｂＯ＿３の
微結晶を析出させ、この微結晶を同じくＢａＰｂＯ＿３
の種子結晶である単結晶上に結晶して成長させることを
特徴とするＢａＰｂＯ＿３系酸化物超伝導体単結晶の溶
液引上げ法による製造方法。(1) Lead oxide, barium carbonate, and barium chloride are mixed and heated and melted at a temperature of 900 to 1200°C to generate a melt, and then, while cooling this melt, fine crystals of BaPbO_3 are precipitated, This microcrystal is also BaPbO_3
1. A method for producing a BaPbO_3-based oxide superconductor single crystal by a solution pulling method, the method comprising crystallizing and growing the BaPbO_3-based oxide superconductor single crystal on a single crystal that is a seed crystal.
ウムとを混合して９００〜１２００℃の温度に加熱して
融液を生成し、次いで、この融液を降温しながら一般式
ＢａＰｂ＿１＿−＿ｘＢｉ＿ｘＯ＿３（ただし、ｘ＝０
．４以下）の微結晶を析出させ、この微結晶を同じくＢ
ａＰｂ＿１＿−＿ｘＢｉ＿ｘＯ＿３の種子結晶である単
結晶上に結晶して成長させることを特徴とするＢａＰｂ
Ｏ＿３系酸化物超伝導体単結晶の溶液引上げ法による製
造方法。(2) Lead oxide, barium carbonate, bismuth oxide, and barium chloride are mixed and heated to a temperature of 900 to 1200°C to form a melt, and then while cooling this melt, the general formula BaPb_1_-_xBi_xO_3( However, x=0
．． 4 or less) is precipitated, and this microcrystal is also
BaPb characterized by being crystallized and grown on a single crystal that is a seed crystal of aPb_1_-_xBi_xO_3
A method for producing an O_3-based oxide superconductor single crystal using a solution pulling method.
晶を得る溶液の組成範囲は、酸化鉛が６５〜９０重量％
、炭酸バリウムが５〜２５重量％、塩化バリウムが２〜
２５重量％の組成に３者を混合したものに対して酸化ビ
スマスを前記酸化鉛に対して重量比で５０％まで混合し
た４者の混合融液である特許請求の範囲第（２）項記載
のＢａＰｂＯ＿３系酸化物超伝導体単結晶の溶液引上げ
法による製造方法。(3) The composition range of the solution for obtaining a large single crystal of BaPb_1_-_xBi_xO_3 is 65 to 90% by weight of lead oxide.
, barium carbonate 5-25% by weight, barium chloride 2-25% by weight
Claim (2) describes a mixed melt of four components in which bismuth oxide is mixed in a weight ratio of up to 50% with respect to the lead oxide in a composition of 25% by weight of the three components. A method for producing a BaPbO_3-based oxide superconductor single crystal using a solution pulling method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14318985A JPH0243717B2 (en) | 1985-06-28 | 1985-06-28 | BAPBO3KEISANKABUTSUCHODENDOTAITANKETSUSHONOYOEKIHIKIAGEHONYORUSEIZOHOHO |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14318985A JPH0243717B2 (en) | 1985-06-28 | 1985-06-28 | BAPBO3KEISANKABUTSUCHODENDOTAITANKETSUSHONOYOEKIHIKIAGEHONYORUSEIZOHOHO |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS623092A true JPS623092A (en) | 1987-01-09 |
| JPH0243717B2 JPH0243717B2 (en) | 1990-10-01 |
Family
ID=15332942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14318985A Expired - Lifetime JPH0243717B2 (en) | 1985-06-28 | 1985-06-28 | BAPBO3KEISANKABUTSUCHODENDOTAITANKETSUSHONOYOEKIHIKIAGEHONYORUSEIZOHOHO |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0243717B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5162297A (en) * | 1987-06-11 | 1992-11-10 | Kabushiki Kaisha Toshiba | Liquid phase epitaxial growth of high temperature superconducting oxide wafer |
| US6094404A (en) * | 1996-01-23 | 2000-07-25 | Seiko Epson Corporation | Display structure with solar cell, and electronic devices and timepiece powered by solar cell |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03279017A (en) * | 1990-03-28 | 1991-12-10 | Mazda Motor Corp | Power train construction for vehicle |
-
1985
- 1985-06-28 JP JP14318985A patent/JPH0243717B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5162297A (en) * | 1987-06-11 | 1992-11-10 | Kabushiki Kaisha Toshiba | Liquid phase epitaxial growth of high temperature superconducting oxide wafer |
| US6094404A (en) * | 1996-01-23 | 2000-07-25 | Seiko Epson Corporation | Display structure with solar cell, and electronic devices and timepiece powered by solar cell |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0243717B2 (en) | 1990-10-01 |
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