JPH01148795A - Production of oxide superconductor crystal - Google Patents
Production of oxide superconductor crystalInfo
- Publication number
- JPH01148795A JPH01148795A JP62304632A JP30463287A JPH01148795A JP H01148795 A JPH01148795 A JP H01148795A JP 62304632 A JP62304632 A JP 62304632A JP 30463287 A JP30463287 A JP 30463287A JP H01148795 A JPH01148795 A JP H01148795A
- Authority
- JP
- Japan
- Prior art keywords
- flux
- oxide superconductor
- crystal
- superconductor crystal
- producing
- 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 55
- 239000002887 superconductor Substances 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 230000004907 flux Effects 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 5
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 3
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 3
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 3
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 3
- 229910052765 Lutetium Inorganic materials 0.000 claims abstract description 3
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract 2
- 229910052727 yttrium Inorganic materials 0.000 claims abstract 2
- 239000007788 liquid Substances 0.000 claims description 15
- 239000007791 liquid phase Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 abstract description 7
- COHDHYZHOPQOFD-UHFFFAOYSA-N arsenic pentoxide Inorganic materials O=[As](=O)O[As](=O)=O COHDHYZHOPQOFD-UHFFFAOYSA-N 0.000 abstract description 3
- 229910008750 Li2O-B2O3 Inorganic materials 0.000 abstract 1
- 229910008569 Li2O—B2O3 Inorganic materials 0.000 abstract 1
- 229910003252 NaBO2 Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- 238000010587 phase diagram Methods 0.000 description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
Description
【発明の詳細な説明】
［発明の目的］
（産業上の利用分野）
本発明は、多元系酸化物超電導体結晶の製造方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Field of Industrial Application) The present invention relates to a method for producing a multi-component oxide superconductor crystal.
（従来の技術）
最近、液体窒素温度程度の高温で超電導を示す高温超電
導体材料として、ペロブスカイト構造の多元系酸化物超
電導体が注目されている。これまでに報告されている酸
化物超電導体の代表的なものは、ＹＢａ Ｃｕ Ｏ
や２ ３７−δ
（Ｌａ、Ｂａ） ２Ｃｕ３Ｏ７−δ等である。これら
の４−ｙ
酸化物超電導材料は、焼結法、蒸着法、スパッタ法等に
より得られている。(Prior Art) Recently, multi-component oxide superconductors with a perovskite structure have attracted attention as high-temperature superconductor materials that exhibit superconductivity at temperatures as high as liquid nitrogen temperatures. Typical oxide superconductors reported so far are YBa Cu O
and 2 37-δ (La, Ba) 2Cu3O7-δ. These 4-y oxide superconducting materials are obtained by sintering, vapor deposition, sputtering, or the like.
今後これらの酸化物超電導体を具体的な素子に応用する
に当たって、超電導転移温度を高く安定に保ち、また大
きい臨界電流を得、素子特性の均一性、信頼性を優れた
ものとするためには、ある程度大きい面積の単結晶基板
或いは単結晶層として実現することが強く望まれる。こ
の種の酸化物超電導体の製造には、誘電体酸化物単結晶
の場合と同様にチョクラルスキー法（ＣＺ法）を用いる
ことが考えられる。しかし、結晶材料融液を用いるＣＺ
法では非常に高い温度での結晶成長になり、酸化物超電
導体は相転移を生じるため、所望の超 −電導体を得る
ことができない。When applying these oxide superconductors to specific devices in the future, it is necessary to maintain a high and stable superconducting transition temperature, obtain a large critical current, and achieve excellent uniformity and reliability of device characteristics. It is strongly desired to realize this as a single-crystal substrate or a single-crystal layer with a relatively large area. For the production of this type of oxide superconductor, it is possible to use the Czochralski method (CZ method) as in the case of dielectric oxide single crystals. However, CZ using a crystalline material melt
In this method, crystal growth occurs at extremely high temperatures, and the oxide superconductor undergoes a phase transition, making it impossible to obtain the desired superconductor.
（発明が解決しようとする問題点）
以上のように、多元系酸化物超電導材料の素子応用に当
たっては、その単結晶化が望まれるが、これまでそのよ
うな酸化物単結晶を形成する有効な方法は提案されてい
ない。(Problems to be Solved by the Invention) As described above, when applying multi-component oxide superconducting materials to devices, it is desirable to make them into single crystals, but so far there has been no effective way to form such oxide single crystals. No method has been proposed.
本発明は上記した点に鑑み、多元系酸化物超電導体の結
晶の製造方法を提供することを目的とする。In view of the above-mentioned points, an object of the present invention is to provide a method for producing a crystal of a multi-component oxide superconductor.
［発明の構成］
（問題点を解決するための手段）
本発明の方法は、アルカリ金属酸化物を含む２元系酸化
物をフラックスとして用いた液相成長法（キポラス法）
により多元系酸化物超電導体結晶を製造することを特徴
とする。[Structure of the Invention] (Means for Solving the Problems) The method of the present invention is a liquid phase growth method (Kiporas method) using a binary oxide containing an alkali metal oxide as a flux.
The method is characterized by producing a multi-component oxide superconductor crystal.
具体的に本発明で用いるフラックスとしては、ＬＩ Ｂ
Ｏ２−Ｎａ ＢＯ２系混合液やＮａ２Ｏ−−Ｂ２Ｏ３系
、Ｋ２Ｏ− Ｖ２Ｏ−５系、Ｋ２Ｏ−Ｂ２Ｏ−３系、
Ｋ２Ｏ− Ａｓ ２Ｏ−５系、Ｋ２Ｏ−Ｐ２Ｏ５系、
Ｌｉ ２Ｏ−Ｂ２ｏ、系等の各種混合液がある。Specifically, the flux used in the present invention is LI B
O2-Na BO2 system mixture, Na2O--B2O3 system, K2O-V2O-5 system, K2O-B2O-3 system,
K2O- As 2O-5 system, K2O-P2O5 system,
There are various mixed liquids such as Li 2 O-B 2 o and the like.
（作用）
本発明によれば、上述のようなフラックスを用いたキポ
ラス法により、低い温度で多元系酸化物超電導体結晶の
成長が可能であり、超電導体の相転移が効果的に防止さ
れ、良好な多元系酸化物超電導体結晶を得ることができ
る。(Function) According to the present invention, multi-component oxide superconductor crystals can be grown at low temperatures by the Kiporus method using the above-mentioned flux, and phase transition of the superconductor is effectively prevented. A good multi-component oxide superconductor crystal can be obtained.
（実施例）
以下、本発明の詳細な説明する。実施例では、ＹＢａ
Ｃｕ Ｏ結晶の製造法を説明す２ ３７−δ
る。(Example) The present invention will be described in detail below. In the example, YBa
A method for producing CuO crystals will be explained below.
第１図は、その結晶の引上げ装置を示す。第１図におい
て１は、アルミナシールド材であり、この中に白金ヒー
タ２が配置され、その中心部に白金ルツボ３が支持台４
上に配置されている。支持台４は炉外部とつながる支持
棒５と一体化され、回転可能になっている。６は熱雷対
である。ルツボ３内には、Ｌｉ ＢＯ２−Ｎａ ＢＯ２
混合液からなるフラックスを形成し、これに、必要な原
料酸化物を溶解した溶液７を形成する。FIG. 1 shows the crystal pulling apparatus. In FIG. 1, reference numeral 1 denotes an alumina shield material, in which a platinum heater 2 is arranged, and a platinum crucible 3 is placed in the center of the material on a support base 4.
placed above. The support stand 4 is integrated with a support rod 5 connected to the outside of the furnace, and is rotatable. 6 is a thermal lightning pair. Inside crucible 3, Li BO2-Na BO2
A flux consisting of a mixed liquid is formed, and a solution 7 is formed in which a necessary raw material oxide is dissolved.
第２図は、ＬＩ ＢＯ２−Ｎａ ＢＯ２の相図であり、
この系で適当なモル比を選ぶことにより、９００℃以下
で液相状態が得られる。従ってこの系をフラックスとし
て用いることにより、比較的低温でＹ−Ｂａ−Ｃｕ−０
系結晶を引上げるための溶液を得ることが可能である。FIG. 2 is a phase diagram of LI BO2-Na BO2,
By selecting an appropriate molar ratio in this system, a liquid phase state can be obtained at 900° C. or lower. Therefore, by using this system as a flux, Y-Ba-Cu-0
It is possible to obtain a solution for pulling system crystals.
このようにしてルツボ３内に所望の溶液７を形成し、こ
れを１２Ｏ−０〜１３００℃で約１０時間放置した後、
溶液温度を下げて約９００〜１０００℃に設定する。そ
してこの溶液７に引上げ軸８の先端に取付けられたＹＣ
ｕ Ｏ単結晶からなる種子結晶を浸し、十分にこの種子
結晶を馴染ませる。その後、０．１〜０．５℃／ｈとい
う小さい冷却速度で結晶９を引上げる。この引上げに際
し、溶液７の表面にはガス導入パイプ１２を介して酸素
ガスを１００ｔｒ＋ｊ？／ｍ１ｎ程度供給する。After forming the desired solution 7 in the crucible 3 in this way and leaving it at 12O-0 to 1300°C for about 10 hours,
The solution temperature is lowered and set to about 900-1000°C. Then, a YC attached to the tip of the pulling shaft 8 is added to this solution 7.
A seed crystal consisting of a uO single crystal is immersed in the solution, and the seed crystal is sufficiently absorbed. Thereafter, the crystal 9 is pulled up at a low cooling rate of 0.1 to 0.5°C/h. During this pulling, oxygen gas is supplied to the surface of the solution 7 through the gas introduction pipe 12 at a rate of 100tr+j? /m1n is supplied.
１０は内部観察用光入射窓であり、１１は内部観察窓で
ある。10 is a light entrance window for internal observation, and 11 is an internal observation window.
こうしてこの実施例によれば、キポラス法によって比較
的低温で、従って相転移を生じることなく、良質のＹＢ
ａ Ｃｕ Ｏ結晶を引上げる２ ３７−に
とができる。この場合、結晶引上げに際して酸素ガスを
供給することにより、溶液中および成長結晶中の酸素欠
陥の発生を防止することができる。Thus, according to this example, good quality YB can be obtained by the Kiporus method at a relatively low temperature and therefore without phase transition.
a 2 37- to pull up the CuO crystal. In this case, by supplying oxygen gas during crystal pulling, it is possible to prevent the generation of oxygen defects in the solution and in the grown crystal.
次に、フラックスとして、Ｎａ２Ｏ−−Ｂ２Ｏ３系混合
液を用いた場合を説明する。第３図は、Ｎａ２Ｏ−
Ｂ２Ｏ−３系の相図であり、この系で適当なモル比を選
ぶことにより、やはり９００℃程度以下で液相状態が得
られる。このＮａ２Ｏ−−Ｂ２Ｏ３混合液（Ｂ２Ｏ−３
が６０〜９０モル％）をフラックスとして用いて先の実
施例と同様に必要な原料を溶解した溶液を形成し、９０
０〜１０００℃で約１０時間放置した後、溶液温度を下
げて８００〜９００℃に設定する。この後先の実施例と
同様にして、ＹＢａ Ｃｕ Ｏ結晶２ ３７−δ
を引上げる。Next, a case will be described in which a Na2O--B2O3-based mixed liquid is used as the flux. Figure 3 shows Na2O-
This is a phase diagram of the B2O-3 system, and by selecting an appropriate molar ratio in this system, a liquid phase state can also be obtained at about 900°C or lower. This Na2O--B2O3 mixed solution (B2O-3
60 to 90 mol%) was used as a flux to form a solution in which the necessary raw materials were dissolved in the same manner as in the previous example.
After leaving the solution at 0-1000°C for about 10 hours, the solution temperature is lowered and set at 800-900°C. After this, YBa Cu O crystal 2 37-δ is pulled in the same manner as in the previous example.
この実施例によっても先の実施例と同様、良質のＹＢａ
Ｃｕ Ｏ結晶を得ることができる。In this example, as well as in the previous example, high quality YBa is used.
CuO crystals can be obtained.
２ ３７−δ
次に、フラックスとして、Ｋ２Ｏ− Ｖ２Ｏ−５系混
合液を用いた場合を説明する。第４図は、Ｋ２Ｏ−
Ｖ２Ｏ−５系の相図であり、この系で適当なモル比を選
ぶことにより、やはり９００°Ｃ程度以下で液相状態が
得られる。このに２〇−Ｂ２Ｏ５混合液（Ｖ２Ｏ３が６
５モル％以下）をフラックスとして用いて先の実施例と
同様に必要な原料を溶解した溶液を形成し、１０００°
Ｃで約１０時間放置した後、溶液温度を下げて８５０〜
９００℃に設定する。この後先の実施例と同様にして、
ＹＢａ Ｃｕ Ｏ結晶を引上げる。2 37-δ Next, a case will be described in which a K2O-V2O-5 mixed liquid is used as the flux. Figure 4 shows K2O-
This is a phase diagram of the V2O-5 system, and by selecting an appropriate molar ratio in this system, a liquid phase state can be obtained at temperatures below about 900°C. Add to this 20-B2O5 mixture (V2O3 is 6
5 mol% or less) as a flux to form a solution in which the necessary raw materials were dissolved in the same manner as in the previous example, and heated at 100°
After leaving it for about 10 hours at C, lower the solution temperature to 850~
Set to 900℃. After this, in the same manner as in the previous example,
Pull up the YBa Cu O crystal.
２ ３７−δ
この実施例によっても先の実施例と同様、良質のＹＢａ
Ｃｕ Ｏ結晶を得ることができる。2 37-δ In this example, as well as in the previous example, good quality YBa
CuO crystals can be obtained.
２ ３７−δ
次に、フラックスとして、Ｋ２ＯＢ２Ｏ３系混合液を用
いた場合を説明する。第５図は、Ｋ２Ｏ− Ｂ２Ｏ−
３系の相図であり、この系で適当なモル比を選ぶことに
より、やはり９００℃程度以下で液相状態が得られる。2 37-δ Next, a case will be described in which a K2OB2O3-based mixed liquid is used as the flux. Figure 5 shows K2O- B2O-
This is a phase diagram of three systems, and by selecting an appropriate molar ratio in this system, a liquid phase state can be obtained at about 900° C. or lower.
このに２Ｏ−Ｂ２Ｏ−３混合液（Ｂ２Ｏ−３が５０〜８
０モル％）をフラックスとして用いて先の実施例と同様
に必要な原料を溶解した溶液を形成し、１２Ｏ−０〜１
３００℃で約１０時間放置した後、溶液温度を下げて９
００〜１０００℃に設定する。この後先の実施例と同様
にして、ＹＢａ Ｃｕ Ｏ結２ ３７−δ
晶を引上げる。Add to this a 2O-B2O-3 mixed solution (B2O-3 is 50 to 8
0 mol%) was used as a flux to form a solution in which the necessary raw materials were dissolved in the same manner as in the previous example, and 12O-0 to 1
After leaving it at 300°C for about 10 hours, lower the solution temperature and
Set at 00-1000°C. Thereafter, the YBa Cu O crystal 2 37-δ crystal is pulled up in the same manner as in the previous example.
この実施例によっても先の実施例と同様、良質のＹＢａ
Ｃｕ Ｏ結晶を得ることができる。In this example, as well as in the previous example, high quality YBa is used.
CuO crystals can be obtained.
２ ３７−δ
次に、フラックスとして、Ｋ２Ｏ−Ａｓ２Ｏ５系混合液
を用いた場合を説明する。第６図は、Ｋ２Ｏ−Ａｓ２Ｏ
５系の相図であり、この系で適当なモル比を選ぶことに
より、やはり９００°Ｃ程度以下で液相状態が得られる
。このに２Ｏ−Ａｓ ２Ｏ−５混合液（ＡＳ２Ｏ−５が
４０〜６０モル％）をフラックスとして用いて先の実施
例と同様に必要な原料を溶解した溶液を形成し、１２Ｏ
−０〜１３００℃で約１０時間放置した後、溶液温度を
下げて９００〜１０００℃に設定する。2 37-δ Next, a case will be described in which a K2O-As2O5-based mixed liquid is used as the flux. Figure 6 shows K2O-As2O
This is a phase diagram of a 5-system system, and by selecting an appropriate molar ratio in this system, a liquid phase state can also be obtained at about 900°C or lower. In this, a 2O-As 2O-5 mixed solution (40 to 60 mol% AS2O-5) was used as a flux to form a solution in which the necessary raw materials were dissolved in the same manner as in the previous example.
After leaving the solution at -0 to 1300°C for about 10 hours, the solution temperature is lowered and set to 900 to 1000°C.
この後先の実施例と同様にして、ＹＢａ Ｃｕ３０．
。After this, YBa Cu30.
.
結晶を引上げる。Pull up the crystal.
この実施例によっても先の実施例と同様、良質のＹＢａ
Ｃｕ Ｏ結晶を得ることができる。In this example, as well as in the previous example, high quality YBa is used.
CuO crystals can be obtained.
２ ３７−δ
次に、フラックスとして、Ｋ２Ｏ− Ｐ２Ｏ−５系混
合液を用いた場合を説明する。第７図は、Ｋ２Ｏ−−
Ｐ ２Ｏ−５系の相図であり、この系で適当なモル比を
選ぶことにより、やはり９００℃程度以下で液相状態が
得られる。このに２Ｏ−Ｂ２Ｏ５混合液をフラックスと
して用いて先の実施例と同様に必要な原料を溶解した溶
液を形成し、１２Ｏ−０〜１３００℃で約１０時間放置
した後、溶液温度を下げて９００〜１０００°Ｃに設定
する。この後先の実施例と同様にして、ＹＢａ Ｃｕ
Ｏ結晶を引上げる。2 37-δ Next, a case will be described in which a K2O-P2O-5 mixed liquid is used as the flux. Figure 7 shows K2O--
This is a phase diagram of the P 2 O-5 system, and by selecting an appropriate molar ratio in this system, a liquid phase state can be obtained at about 900° C. or lower. Using the 2O-B2O5 mixture as a flux, a solution containing the necessary raw materials was formed in the same manner as in the previous example, and after being left at 12O-0 to 1300°C for about 10 hours, the solution temperature was lowered to 900°C. Set to ~1000°C. After this, in the same manner as in the previous example, YBa Cu
Pull up the O crystal.
２ ３７−δ
この実施例によっても先の実施例と同様、良質のＹＢａ
Ｃｕ Ｏ結晶を得ることができる。2 37-δ In this example, as well as in the previous example, good quality YBa
CuO crystals can be obtained.
２ ３ ７−δ
次に、フラックスとして、Ｌｌ ２Ｏ− Ｂ２Ｏ−３
系混合液を用いた場合を説明する。第８図は、Ｋ２ＯＰ
２Ｏ５系の相図であり、この系で適当な比を選ぶことに
より、９００℃以下で液相状態が得られる。このＬｌ。2 3 7-δ Next, as a flux, Ll 2O- B2O-3
The case where a system mixture is used will be explained. Figure 8 shows K2OP
This is a phase diagram of the 2O5 system, and by selecting an appropriate ratio in this system, a liquid phase state can be obtained at temperatures below 900°C. This Ll.
０−Ｂ２Ｏ３混合液をフラックスとして用いて先の実施
例と同様に必要な原料を溶解した溶液を形成し、１２Ｏ
−０〜１３００°Ｃで約１０時間放置した後、溶液温度
を下げて９００〜１０００℃に設定する。この後先の実
施例と同様にして、ＹＢａ Ｃｕ Ｏ結２ ３７−
δ
晶を引上げる。Using the 0-B2O3 mixture as a flux, a solution containing the necessary raw materials was formed in the same manner as in the previous example, and 12O
After leaving the solution at -0 to 1300°C for about 10 hours, the solution temperature is lowered and set to 900 to 1000°C. After this, in the same manner as in the previous example, YBa Cu O bond 2 37-
Pull up the δ crystal.
この実施例によっても先の実施例と同様、良質のＹＢａ
Ｃｕ Ｏ結晶を得ることができる。In this example, as well as in the previous example, high quality YBa is used.
CuO crystals can be obtained.
２ ３７−δ
以上の実施例では、ＹＢａ Ｃｕ Ｏ結晶２ ３７
−δ
を引上げる場合を説明したが、Ｙの代わりにＹｂ。2 37-δ In the above examples, YBa Cu O crystal 2 37
We have explained the case where -δ is raised, but Yb is used instead of Y.
Ｈｏ、Ｄｙ、Ｅｕ、Ｅｒ、Ｔｍ、Ｌｕなど他の希土類元
素が入った酸化物超電導体結晶の場合にも本発明は有効
であり、また、Ｓｃ −Ｂａ −Ｃｕ −Ｏ系、Ｓｒ
−Ｌａ −Ｃｕ−０系、更にＳ「をＢａ。The present invention is also effective for oxide superconductor crystals containing other rare earth elements such as Ho, Dy, Eu, Er, Tm, and Lu;
-La-Cu-0 system, and further S' and Ba.
Ｃａなどで置換した系等、他のペロブスカイト構造を有
する多元系酸化物超電導体結晶を成長させる場合にも本
発明は有効である。また実施例では結晶引上げを説明し
たが、本発明は多元系酸化物超電導体層のエピタキシャ
ル成長にも有効である。The present invention is also effective when growing multi-component oxide superconductor crystals having other perovskite structures, such as those substituted with Ca or the like. Further, although crystal pulling has been explained in the embodiment, the present invention is also effective for epitaxial growth of a multi-component oxide superconductor layer.
その池水発明はその趣旨を逸脱しない範囲で種々変形し
て実施することができる。The pond water invention can be implemented with various modifications without departing from the spirit thereof.
［発明の効果］
以上述べたように本発明によれば、アルカリ金属酸化物
を含む２元系酸化物をフラックスとするキボラス法によ
り、多元系酸化物超電導体の良質の結晶を得ることがで
きる。[Effects of the Invention] As described above, according to the present invention, high-quality crystals of a multi-component oxide superconductor can be obtained by the Quiboras method using a binary oxide containing an alkali metal oxide as a flux. .
第１図は本発明の一実施例のＹ−Ｂａ−Ｃｕ−〇系結晶
の引上げ装置を示す図、第２図は、ＬＩ ＢＯ２−Ｎａ
ＢＯ２系の相図、第３図は、Ｎａ ２Ｏ− Ｂ２Ｏ
−３系の相図、第４図は、Ｋ２Ｏ−ｖ２Ｏ−．系の相図
、第５図はに２Ｏ−−８２Ｏ−３系の相図、第６図は、
Ｋ２Ｏ−Ａｓ２Ｏ５系の相図、第７図は、Ｋ ２Ｏ−
Ｐ ２Ｏ−５系の相図、第８図は、Ｌ１２Ｏ− Ｂ
２Ｏ３系の相図である。
１・・・アルミナシールド材、２・・・白金ヒータ、３
・・・白金ルツボ、４・・・支持台、５・・・支持棒、
６・・・熱電対、７・・・フラックスを含む溶液、８・
・・引上げ軸、９・・・ＹＢａ Ｃｕ Ｏ結晶、１
０・・・内部観察２ ３７−δ
用光照射窓、１１・・・内部観察窓、１２・・・ガス導
入バイブ。
出願人代理人 弁理士 鈴江武彦
第１図
ＬｉｚＯ−Ｎａ２Ｏ−−ＢｚＯ３
Ｌｉ２Ｏ−．Ｂ２Ｏ３Ｎａ２Ｏ−−Ｂ２Ｏ−３Ｎａ２Ｏ
−Ｂ２Ｏ−３モル比（’１０）第２図
Ｎａ２Ｏ−８２Ｏ−３
Ｎａ２Ｏ−
Ｂ２Ｏ−３８２Ｏ−３玉ル比 （’／、）
第３区
混廖 （°Ｃ）
に２Ｏ−ＡＳ２Ｏ−Ｓ
Ａｓ２Ｏ−ｓ ３
に２Ｏ−．ＡＳ２Ｏ−５に２Ｏ− モル片（０ん）
モル）ｌｔＰ２Ｏ−５
に２Ｏ−−Ｐ２Ｏ−ＳFIG. 1 is a diagram showing an apparatus for pulling Y-Ba-Cu-〇-based crystal according to an embodiment of the present invention, and FIG.
Phase diagram of BO2 system, Figure 3 shows Na2O- B2O
The phase diagram of the -3 system, Figure 4, shows the K2O-v2O-. The phase diagram of the system, Figure 5, is the phase diagram of the 2O--82O-3 system, Figure 6 is,
Phase diagram of K2O-As2O5 system, Figure 7 shows K2O-
Phase diagram of P2O-5 system, Figure 8 shows L12O-B
It is a phase diagram of the 2O3 system. 1... Alumina shield material, 2... Platinum heater, 3
...Platinum crucible, 4...Support stand, 5...Support rod,
6... Thermocouple, 7... Solution containing flux, 8...
... Pulling axis, 9 ... YBa Cu O crystal, 1
0... Light irradiation window for internal observation 2 37-δ, 11... Internal observation window, 12... Gas introduction vibrator. Applicant's representative Patent attorney Takehiko Suzue Figure 1 LizO-Na2O--BzO3 Li2O-. B2O3Na2O--B2O-3Na2O
-B2O-3 molar ratio ('10) Figure 2 Na2O-82O-3 Na2O-
B2O-382O-3 ratio ('/,) 3rd section mixture (°C) 2O-AS2O-S As2O-s 3
2O-. AS2O-5 to 2O- mole piece (0 mm) ltP2O-5 to 2O--P2O-S
Claims (9)
クスとして用いた液相成長法により多元系酸化物超電導
体結晶を成長させることを特徴とする酸化物超電導体結
晶の製造方法。(1) A method for producing an oxide superconductor crystal, which comprises growing a multi-component oxide superconductor crystal by a liquid phase growth method using a binary oxide containing an alkali metal oxide as a flux.
Ｈｏ、Ｄｙ、Ｅｕ、Ｅｒ、Ｔｍ、Ｌｕから選ばれた一種
）である特許請求の範囲第１項記載の酸化物超電導体結
晶の製造方法。(2) The multi-component oxide superconductor is ABa_2Cu_3O_7_-_δ (A is Y, Yb,
The method for producing an oxide superconductor crystal according to claim 1, wherein the oxide superconductor crystal is one selected from Ho, Dy, Eu, Er, Tm, and Lu.
系混合液である特許請求の範囲第１項記載の酸化物超電
導体結晶の製造方法。(3) The flux is LiBO_2-NaBO_2
The method for producing an oxide superconductor crystal according to claim 1, which is a mixed liquid.
混合液である特許請求の範囲第１項記載の酸化物超電導
体結晶の製造方法。(4) The method for producing an oxide superconductor crystal according to claim 1, wherein the flux is a Na_2O-B_2O_3-based mixed liquid.
合液である特許請求の範囲第１項記載の酸化物超電導体
結晶の製造方法。(5) The method for producing an oxide superconductor crystal according to claim 1, wherein the flux is a K_2O-V_2O_5-based mixed liquid.
合液である特許請求の範囲第１項記載の酸化物超電導体
結晶の製造方法。(6) The method for producing an oxide superconductor crystal according to claim 1, wherein the flux is a K_2O-B_2O_3-based mixed liquid.
混合液である特許請求の範囲第１項記載の酸化物超電導
体結晶の製造方法。(7) The method for producing an oxide superconductor crystal according to claim 1, wherein the flux is a K_2O-As_2O_5-based mixed liquid.
合液である特許請求の範囲第１項記載の酸化物超電導体
結晶の製造方法。(8) The method for producing an oxide superconductor crystal according to claim 1, wherein the flux is a K_2O-P_2O_5-based mixed liquid.
混合液である特許請求の範囲第１項記載の酸化物超電導
体結晶の製造方法。(9) The method for producing an oxide superconductor crystal according to claim 1, wherein the flux is a Li_2O-B_2O_3-based mixed liquid.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62304632A JP2637123B2 (en) | 1987-12-03 | 1987-12-03 | Method for producing oxide superconductor crystal |
| US07/205,177 US5162297A (en) | 1987-06-11 | 1988-06-10 | Liquid phase epitaxial growth of high temperature superconducting oxide wafer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62304632A JP2637123B2 (en) | 1987-12-03 | 1987-12-03 | Method for producing oxide superconductor crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01148795A true JPH01148795A (en) | 1989-06-12 |
| JP2637123B2 JP2637123B2 (en) | 1997-08-06 |
Family
ID=17935371
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62304632A Expired - Lifetime JP2637123B2 (en) | 1987-06-11 | 1987-12-03 | Method for producing oxide superconductor crystal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2637123B2 (en) |
-
1987
- 1987-12-03 JP JP62304632A patent/JP2637123B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| JAPANESE JOURNAL OF APPLIED PHYSICS=1987 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2637123B2 (en) | 1997-08-06 |
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