JPS63274696A - Production of cupric acid-lanthanum single crystal - Google Patents
Production of cupric acid-lanthanum single crystalInfo
- Publication number
- JPS63274696A JPS63274696A JP62109518A JP10951887A JPS63274696A JP S63274696 A JPS63274696 A JP S63274696A JP 62109518 A JP62109518 A JP 62109518A JP 10951887 A JP10951887 A JP 10951887A JP S63274696 A JPS63274696 A JP S63274696A
- Authority
- JP
- Japan
- Prior art keywords
- single crystal
- la2cuo4
- crystal
- cuo
- lanthanum
- 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 59
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 229910052746 lanthanum Inorganic materials 0.000 title claims description 10
- 239000000155 melt Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910017569 La2(CO3)3 Inorganic materials 0.000 claims abstract description 5
- 238000002844 melting Methods 0.000 claims abstract description 3
- 230000008018 melting Effects 0.000 claims abstract description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 10
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 claims description 4
- 229960001633 lanthanum carbonate Drugs 0.000 claims description 4
- 239000013081 microcrystal Substances 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims 2
- 239000005751 Copper oxide Substances 0.000 claims 2
- 229910000431 copper oxide Inorganic materials 0.000 claims 2
- 229910002282 La2CuO4 Inorganic materials 0.000 abstract description 14
- 238000010586 diagram Methods 0.000 abstract description 9
- 238000001816 cooling Methods 0.000 abstract description 8
- 239000012071 phase Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000007790 solid phase Substances 0.000 abstract description 3
- 238000004455 differential thermal analysis Methods 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 abstract 2
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract 2
- 230000008021 deposition Effects 0.000 abstract 1
- 230000003028 elevating effect Effects 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000007716 flux method Methods 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 3
- 229910052802 copper Chemical group 0.000 description 2
- 239000008710 crystal-8 Substances 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000013076 target substance Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000048 melt cooling Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
- C30B29/225—Complex oxides based on rare earth copper oxides, e.g. high T-superconductors
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B13/00—Single-crystal growth by zone-melting; Refining by zone-melting
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B9/00—Single-crystal growth from melt solutions using molten solvents
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N60/00—Superconducting devices
- H10N60/80—Constructional details
- H10N60/85—Superconducting active materials
- H10N60/855—Ceramic materials
- H10N60/857—Ceramic materials comprising copper oxide
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
この発明は溶液ひきあげ法による銅酸ランタン（Ｌａ２
Ｃｕ０４）単結晶の製造方法に関するものである。[Detailed description of the invention] [Industrial application field] This invention is a method for producing lanthanum cuprate (La2) by a solution drawing method.
The present invention relates to a method for manufacturing a Cu04) single crystal.
［従来の技術］
１ａ２ｃｕ０４は層状ペロブスカイト型結晶構造をもつ
酸化物で、Ｌａ原子の位置を少量Ｓ「やＢａ原子で置き
換えると３０〜４０にの低温で超伝導を示す、極低温素
子としてこれからの応用が考えられ、そのためには大型
の良質な単結晶が必要となり、その製造方法の開発が望
まれている。[Prior art] 1a2cu04 is an oxide with a layered perovskite crystal structure, and when the La atoms are replaced with a small amount of S or Ba atoms, it exhibits superconductivity at a low temperature of 30 to 40 degrees. Applications are considered, and for this purpose large, high-quality single crystals are required, and the development of a manufacturing method is desired.
従来高温で分解溶融し、通常のひきあげ法で単結晶を育
成できない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、その混合溶液を
降温することによってその混合溶液を過飽和濃度以上の
状態にし、目的物質を融液から単結晶として析出させて
得るフラックス法が用いられる。 Ｌａ２ＣｕＯ４は高
温にしてゆくと１０５０℃付近で分解溶融するため、単
結晶と同−組成の原料から単結晶を製造することができ
ない。Conventionally, the method of obtaining a single crystal of a substance that undergoes a peritectic reaction, which decomposes and melts at high temperatures and cannot be grown as a single crystal by ordinary pulling methods, is usually by mixing the target substance in a solvent and cooling the mixed solution. A flux method is used in which the mixed solution is made to have a supersaturation concentration or higher, and the target substance is precipitated as a single crystal from the melt. Since La2CuO4 decomposes and melts at around 1050 DEG C. when the temperature is increased, a single crystal cannot be produced from a raw material having the same composition as a single crystal.
そのためチョクラルスキー法が適用でとない、そのため
通常フラックス法が適用されるが最大で８ｘ８ｘ２ｍａ
＋のものができているにすぎない。Therefore, the Czochralski method cannot be applied, so the flux method is usually applied, but the maximum is 8x8x2ma.
It's just a result of +.
［発明が解決しようとする問題点〕
上述したようにフラックス法において育成される単結晶
はあまり大ぎいとはいえない。しかも結晶育成に３〜７
日と長時間を要する欠点がある。[Problems to be Solved by the Invention] As mentioned above, the single crystal grown by the flux method cannot be said to be very large. Moreover, 3-7 for crystal growth
It has the disadvantage of requiring many days and long hours.
また結晶育成後に溶剤だけを薬品で取り去るか、徐冷中
にるつぼを炉から取り出して固化していない溶剤を捨て
去るか溶液表面に浮んでいる単結晶をすくい取るという
操作をしなければ単結晶の分離はできないという問題点
があった。In addition, single crystals cannot be separated unless the solvent is removed using chemicals after crystal growth, the crucible is removed from the furnace during slow cooling, and the unsolidified solvent is discarded, or the single crystals floating on the surface of the solution are scooped out. The problem was that it couldn't be done.
［問題点を解決するための手段］
この発明はこのような点に鑑みなされたもので、目的物
であるＬａ２ＣｕＯ４を析出させ得る組成範囲内に酸化
ランタンおよび炭酸ランタンのうちの少なくとも一種と
酸化鋼を混合し、その融液を降温させることにより融液
中に析出してくるＬａ２ＣｕＯ４微結晶を融液に接触さ
せた種結晶上に結晶化させ、これを溶液ひきあげ法によ
ってＬａ２ＣｕＯ４−Ｑ’結晶を製造する方法であり、
フラックス法とは異なり種子結晶によって望みの方向に
任意の大ぎさの良質な単結晶が短時間に製造で診るよう
にしたものである。[Means for Solving the Problems] The present invention was made in view of the above points, and includes at least one of lanthanum oxide and lanthanum carbonate and oxidized steel within a composition range that can precipitate the target product, La2CuO4. By mixing and cooling the melt, the La2CuO4 microcrystals precipitated in the melt are crystallized on seed crystals in contact with the melt, and then La2CuO4-Q' crystals are formed by a solution pulling method. It is a method of manufacturing
Unlike the flux method, this method uses seed crystals to produce high-quality single crystals of any size in a desired direction in a short time.
［作 用］
まず、この発明の原理について述べる。第１図は示差熱
分析と急冷加熱法の結果から作図したＬａ２０３−Ｃｕ
Ｏ系の相平衡図である。図中、黒点で示すのは測定結果
である。例えばＬａ、０．が５０モル％、 ＣｕＯが５
０モル％の組成からなるＬａ２ＣｕＯ４を加熱昇温させ
ると１０５０℃付近で分解溶融してしまう、そのため融
液と同一組成の結晶をひきあげるチョクラルスキー法は
適用できない。次に液相線式−Ｂ間の組成比、すなわち
Ｌａ、０３の２１１．９〜７．１モル％、ＣｕＯの７１
．１〜９２．９モル％の範囲に混合した原料を約１３３
０〜１０４０℃において加熱融解したのち、融液を徐々
に降温させると、融液の組成は液相線＾−Ｂに沿って図
のＣｕＯ側へずれてゆき、Ｌａ２Ｃｕｂ４が固相となっ
て析出してくる。[Operation] First, the principle of this invention will be described. Figure 1 shows La203-Cu plotted from the results of differential thermal analysis and rapid cooling/heating method.
It is a phase equilibrium diagram of O system. In the figure, the black dots indicate the measurement results. For example, La, 0. is 50 mol%, CuO is 5
When La2CuO4 having a composition of 0 mol% is heated to an elevated temperature, it decomposes and melts at around 1050°C. Therefore, the Czochralski method of pulling up crystals having the same composition as the melt cannot be applied. Next, the composition ratio between the liquidus equation -B, that is, La, 211.9 to 7.1 mol% of 03, 71% of CuO
．． Approximately 133% of raw materials mixed in a range of 1 to 92.9 mol%
After heating and melting at 0 to 1040°C, when the temperature of the melt is gradually lowered, the composition of the melt shifts toward the CuO side in the figure along the liquidus line^-B, and La2Cub4 becomes a solid phase and precipitates. I'll come.
ｒａ 液の組成が共晶点ＢよりＣｕＯ側であれば、冷却
時にまずＣｕＯが析出し、融液の組成がＡ点よりＬａ２
Ｏ２側であれば、冷却時にまずＬａ２０．側の結晶が析
出し、いずれもＬａ２Ｃｕｂ、が析出成長することがで
きない。この相平衡図においてＬａ原子およびＣｕ原子
位置に何らかの異種元素を少量混合したときに相平衡図
が特性的に変わらない場合には同じＬａ２ＣｕＯ４固溶
体が固相となって析出してくる。この発明ではこれらの
結晶を同一のＬａ２ＣｕＯ，またはおなし層状ペロブス
カイト型種子結晶上に析出してぎたＬａ、Ｃｕｂ４１結
晶を育成させてひぎあげる。ra If the composition of the liquid is closer to CuO than the eutectic point B, CuO will first precipitate during cooling, and the composition of the melt will be closer to La2 than point A.
If it is on the O2 side, La20. Crystals on the sides precipitate, and La2Cub cannot precipitate and grow in either case. In this phase equilibrium diagram, when a small amount of some kind of different element is mixed at the La atom and Cu atom positions, if the phase equilibrium diagram does not change in characteristics, the same La2CuO4 solid solution will precipitate as a solid phase. In this invention, these crystals are grown by growing La and Cub41 crystals precipitated on the same La2CuO or layered perovskite seed crystal.
［実施例］ 以下に実施例によって本発明の詳細な説明する。[Example] The present invention will be explained in detail below by way of examples.
及胤■ユ
１ａ２ｃＵＯ４単結晶を溶液引きあげ法によって製造し
た。A 1a2cUO4 single crystal was produced by a solution pulling method.
第２図に使用した単結晶引きあげ装置を示す。Figure 2 shows the single crystal pulling device used.
図において、ｌは水冷シャフト、２は白金シャフト、３
は保温材、４は高周波加熱コイル、５は熱電対、６はる
つぼ支持物、７は種結晶、８は成長した単結晶、９は出
発原料、ｌＯは白金るつぼである。In the figure, l is a water-cooled shaft, 2 is a platinum shaft, and 3 is a water-cooled shaft.
4 is a heat insulating material, 4 is a high-frequency heating coil, 5 is a thermocouple, 6 is a crucible support, 7 is a seed crystal, 8 is a grown single crystal, 9 is a starting material, and 1O is a platinum crucible.
Ｌ、ａ２０ｓとＣｕＯをモル比にして１５ ： ８５に
混合し、その混合物２００ｇを、口径５ｈｍ、高さ３５
０１の発熱体を兼ねた白金るつぼＩＯに入れ、高周波加
熱コイル４による話導加熱方式により約１２００℃まで
加熱し溶融させた後、種結晶であるＬａ２Ｃｕ（１４単
結晶７を融液表面に接触させる。融液を徐々に降温させ
ると、融液中で最も温度の低い種結晶と接触している融
液の界面にＬａ２ＣｕＯ４微結晶が少しずつ析出してき
て種結晶７上に結晶化し成長する。このようにして成長
した単結晶８を融液から徐々にひとあげる。すなわち、
融液を降温しながら、育成された単結晶のひ幹あげを同
時におこなってゆくのである。このときの製造条件とし
てはＬａ２ＣｕＯｘ ’Ｌ結晶８のひきあげ速度は０．
３〜１ ｉｓ／ｈｒ 、融液降温速度２〜ｌＯ℃／ｈｒ
、結晶回転数ＬＯ〜３０ｒｐｍ 、雰囲気は空気中で
ある。Ｌａ２ＣｕＯ４単結晶成長を完了するまでに要す
る時間は大きさ９Ｘ７Ｘ４ａｌ１１１．重さ１ｇの単結
晶を得るのに９〜ＩＯ時間要しただけであった。酸素雰
囲気中でも単結晶の成長は可能である。L, a20s and CuO were mixed at a molar ratio of 15:85, and 200 g of the mixture was placed into a tube with a diameter of 5 hm and a height of 35 mm.
01 is placed in a platinum crucible IO that also serves as a heating element, and heated to approximately 1200°C by a conduction heating method using a high-frequency heating coil 4 to melt it. When the temperature of the melt is gradually lowered, La2CuO4 microcrystals are gradually precipitated at the interface of the melt that is in contact with the seed crystal having the lowest temperature in the melt, and crystallize and grow on the seed crystal 7. Gradually lift the single crystal 8 grown in this way from the melt. That is,
While cooling the melt, the grown single crystal is simultaneously raised. As for the manufacturing conditions at this time, the pulling speed of La2CuOx 'L crystal 8 is 0.
3-1 is/hr, melt cooling rate 2-10°C/hr
, the crystal rotation speed was LO ~ 30 rpm, and the atmosphere was air. The time required to complete the growth of a La2CuO4 single crystal is 9X7X4al111. It took only 9-IO hours to obtain a single crystal weighing 1 g. Single crystal growth is possible even in an oxygen atmosphere.
去１０１ス
（Ｌａｏ、 ｇＢａａ、 ＋）ｚｃｕ０４なる組成につ
いて溶液ひきあげ法により固溶体単結晶を製造した。９
０モル％Ｌａ２０．、 ＋ １０モル％２ＢａＣＯ，な
る組成の混合物とＣｕＯをモル比にして＋５ ： ８５
に混合し、実施例１と同様の操作により同様の経過を経
て８Ｘ７Ｘ３ｍｍ＋の（Ｌａｏ、 ｅＢａｏ、 １）ｚ
ｃｕｏ４固溶体単結晶を得た。この発明の製造方法では
結晶中のＬａ原子の位置をＢａで置き換えても第１図の
Ｌａ２０３−ＣｕＯ系の相平衡図が木質的に変わらない
ため（Ｌａｏ、 Ｊａｏ、 ＋）２ｃｕｏａ ！結晶が
製造できた。A solid solution single crystal of the composition 101st (Lao, gBaa, +)zcu04 was produced by the solution pull-up method. 9
0 mol% La20. , +10 mol% 2BaCO, and CuO in a molar ratio of +5:85.
8X7X3mm+ (Lao, eBao, 1)z
A cuo4 solid solution single crystal was obtained. In the production method of the present invention, even if the position of the La atom in the crystal is replaced with Ba, the phase equilibrium diagram of the La203-CuO system in Figure 1 does not change in a woody manner (Lao, Jao, +)2cuoa! Crystals have been produced.
同様に結晶中のＬａ原子およびＣｕ原子の位置に何らか
の異種元素を少量混合したとぎに相平衡図が定性的に変
わらない場合は上記と全く同一の方法、条件によってこ
の異種元素を混入したＬａ２ＣｕＯ４固溶体単結晶を製
造することも可能である。Similarly, if the phase equilibrium diagram does not qualitatively change after mixing a small amount of some kind of different element at the position of La and Cu atoms in the crystal, a La2CuO4 solid solution containing this different kind of element can be obtained using exactly the same method and conditions as above. It is also possible to produce single crystals.
Ｌａ２Ｃｕｂ４．！１．結晶の作製に際し、酸化ランタ
ン（ＬａｚＯ＊）でなく、炭酸ランタン（Ｌａ２（ＣＯ
３） ３）を出発物質として用いることもでざる。Ｌａ
ｚ （ＣＯ３） ｓは加熱中に
Ｌａｗ（ＣＯ３）ｔ ＝Ｌａ２０３ ＋ ３ ＣＯ２↑
なる反応を起こし、Ｌａ２０＊に変化する。従って出発
物質としてＬａ２ （ＣＯ３） ｓとＣｕＯを用いても
、結果として第１図と全く同様の相平衡図が得られ、前
述した各実施例と同様の操作によってＬａ２ＣｕＯ，単
結晶およびＬａの一部を８８またはＳｒで置換した単結
晶を得ることかできた。La2Cub4. ! 1. When producing crystals, lanthanum carbonate (La2(CO
3) It is also not possible to use 3) as a starting material. La
z (CO3) s during heating Law (CO3)t = La203 + 3 CO2↑
A reaction occurs and it changes to La20*. Therefore, even if La2(CO3)s and CuO are used as starting materials, a phase equilibrium diagram exactly the same as that shown in FIG. It was possible to obtain a single crystal in which moieties were substituted with 88 or Sr.
［発明の効果］
以上説明したように、この発明によればＬａ２ＣｕＯ４
単結晶を引きあげ法によって製造することができる。ま
た、ＢａおよびＳ「を少量混合した単結晶を作製するこ
とができる。このように本発明によって３０〜４０にで
超伝導を示す酸化物超伝導単結晶も製造することが可能
となった。[Effect of the invention] As explained above, according to this invention, La2CuO4
Single crystals can be produced by the pulling method. Furthermore, it is possible to produce a single crystal containing a small amount of Ba and S. In this way, the present invention has made it possible to produce an oxide superconducting single crystal exhibiting superconductivity at 30 to 40 nm.
第１図はこの発明の詳細な説明するためのＬａＪｉ−Ｃ
ｕＯ系の相平衡図、
第２図はこの発明の一実施例を説明するためのＬａ２Ｃ
ｕＯａ ！結晶製造装置の構成図である。
１・・・水冷シャフト、
２・・・白金シャフト。
３・・・保温材、
４・・・高周波加熱コイル、
５・・・熱電対、
６・・・るつぼ支持物、
７− Ｌａ２ＣｕＯ４１ｍ結晶、
８ ＝ Ｌａ、Ｃｕｂ、単結晶、
９・・・出発原料、
１０・・・白金るつぼ。
第１図FIG. 1 shows LaJi-C for detailed explanation of this invention.
Figure 2 is a phase equilibrium diagram of the uO system.
uOa! FIG. 1 is a configuration diagram of a crystal manufacturing apparatus. 1...Water cooling shaft, 2...Platinum shaft. 3... Heat insulating material, 4... High frequency heating coil, 5... Thermocouple, 6... Crucible support, 7- La2CuO41m crystal, 8 = La, Cub, single crystal, 9... Starting material , 10... Platinum Crucible. Figure 1
Claims (1)
も一種と酸化銅を混合して加熱融解したのち、融液を降
温させ、一般式Ｌａ＿２ＣｕＯ＿４で表わされる微結晶
を種結晶上に析出、成長させることを特徴とする銅酸ラ
ンタン単結晶の製造方法。 ２）前記酸化ランタンおよび炭酸ランタンのうちの少な
くとも一種と前記酸化銅の混合比が２８．９〜７．１モ
ル％対７１．１〜９２．９モル％であることを特徴とす
る特許請求の範囲第１項記載の銅酸ランタン単結晶の製
造方法。 ３）前記銅酸ランタンが少量の異種元素を含むことを特
徴とする特許請求の範囲第１項記載の銅酸ランタン単結
晶の製造方法。[Claims] 1) After mixing copper oxide with at least one of lanthanum oxide and lanthanum carbonate and heating and melting the mixture, the temperature of the melt is lowered, and microcrystals represented by the general formula La_2CuO_4 are precipitated on the seed crystal. A method for producing a lanthanum cuprate single crystal, the method comprising growing a lanthanum cuprate single crystal. 2) The mixing ratio of at least one of the lanthanum oxide and lanthanum carbonate and the copper oxide is 28.9 to 7.1 mol% to 71.1 to 92.9 mol%. A method for producing a lanthanum cuprate single crystal according to scope 1. 3) The method for producing a lanthanum cuprate single crystal according to claim 1, wherein the lanthanum cuprate contains a small amount of a different element.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62109518A JPS63274696A (en) | 1987-05-01 | 1987-05-01 | Production of cupric acid-lanthanum single crystal |
| US07/168,021 US4956334A (en) | 1987-05-01 | 1988-03-14 | Method for preparing a single crystal of lanthanum cuprate |
| EP88104090A EP0288709B1 (en) | 1987-05-01 | 1988-03-15 | method for preparing a single crystal of lanthanum cuprate |
| DE8888104090T DE3872922T2 (en) | 1987-05-01 | 1988-03-15 | METHOD FOR THE PRODUCTION OF LANTHANE SUPER SINGLE CRYSTAL. |
| US07/521,624 US5057492A (en) | 1987-05-01 | 1990-05-10 | Method for preparing a single crystal of lanthanum cuprate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62109518A JPS63274696A (en) | 1987-05-01 | 1987-05-01 | Production of cupric acid-lanthanum single crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63274696A true JPS63274696A (en) | 1988-11-11 |
| JPH0471876B2 JPH0471876B2 (en) | 1992-11-16 |
Family
ID=14512294
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62109518A Granted JPS63274696A (en) | 1987-05-01 | 1987-05-01 | Production of cupric acid-lanthanum single crystal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63274696A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001063021A1 (en) * | 2000-02-23 | 2001-08-30 | Ceracomp Co., Ltd. | Method for single crystal growth of perovskite oxides |
-
1987
- 1987-05-01 JP JP62109518A patent/JPS63274696A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001063021A1 (en) * | 2000-02-23 | 2001-08-30 | Ceracomp Co., Ltd. | Method for single crystal growth of perovskite oxides |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0471876B2 (en) | 1992-11-16 |
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