JPH01148794A - Production of oxide superconductor crystal - Google Patents
Production of oxide superconductor crystalInfo
- Publication number
- JPH01148794A JPH01148794A JP62304631A JP30463187A JPH01148794A JP H01148794 A JPH01148794 A JP H01148794A JP 62304631 A JP62304631 A JP 62304631A JP 30463187 A JP30463187 A JP 30463187A JP H01148794 A JPH01148794 A JP H01148794A
- Authority
- JP
- Japan
- Prior art keywords
- oxide superconductor
- flux
- crystal
- superconductor crystal
- crystals
- 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.)
- Pending
Links
- 239000013078 crystal Substances 0.000 title claims abstract description 40
- 239000002887 superconductor Substances 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 230000004907 flux Effects 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 13
- 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 4
- 239000007791 liquid phase Substances 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 abstract 2
- 239000000203 mixture Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 239000012071 phase Substances 0.000 description 3
- 238000010587 phase diagram Methods 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
- 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
- 239000002994 raw material Substances 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
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） ＣｕＯ等である。これら４−ｙ
の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) CuO. 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
This method requires crystal growth at extremely high temperatures, which causes a phase transition in the oxide superconductor, 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−に記した点に鑑み、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 points mentioned in -, 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、遷移金属を含む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 to produce a multi-component oxide superconductor by a liquid phase growth method (Kiporas method) using a binary oxide containing a transition metal as a flux. It is characterized by producing crystals.
具体的に本発明で用いるフラックスとしては、Ｐｂ ０
−Ｂ２ｏ３系混合液中Ｃｕ０−Ｖ２０５系混合液がある
。Specifically, the flux used in the present invention is Pb 0
-There is a Cu0-V205 based mixed solution in the B2o3 based mixed solution.
（作用）
本発明によれば、キポラス法を用いることにより、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る。(Function) According to the present invention, multi-component oxide superconductor crystals can be grown at low temperatures by using the Kiporus method.
例えば、Ｐｂ ０−Ｂ２ｏ３系フラックスを用いると、
４９３〜８００℃の７Ｈ度で結晶成長が可能であり、Ｃ
ｕ０−Ｖ２０５系フラックスを用いると、６３０〜７２
０℃で結晶成長が可能である。この結果本発明によれば
、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。For example, if Pb 0-B2o3-based flux is used,
Crystal growth is possible at 493-800°C, 7H degree, and C
When u0-V205 series flux is used, 630-72
Crystal growth is possible at 0°C. As a result, according to the present invention, phase transition of the superconductor is effectively prevented, and 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は熱電対
である。ルツボ３内には、ＰｂＯＢ２Ｏ３混合液（Ｂ２
０３が５０〜７０モル％）からなるフラックスを形成し
、これに、Ｙ２０３ 、Ｂａ Ｏ，Ｃｕ Ｏ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 thermocouple. Inside the crucible 3 is a PbOB2O3 mixed solution (B2
A solution 7 is formed by dissolving Y203, BaO, and CuO in this flux.
第２図は、Ｐｂ ０−Ｂ２ｏ３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１１
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。Figure 2 is a phase diagram of Pb0-B2o3, and by selecting an appropriate molar ratio in this system, the liquid 11
The state is obtained. Therefore, by using this system as a flux, it is possible to obtain a solution for pulling Y-Ba-Cu-0 system crystals at a relatively low temperature.
このよ・フにしてルツボ３内に所望の溶液７を形成し、
これを９００〜１０００℃で約１０時間放置した後、溶
液温度を下げて約８００〜９００℃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ＹＣｕ
Ｏ’ド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バイブ１２を介して酸素ガ
スを１００ｍ１！／ｌｌｌ１ｎ程度供給する。１０は内
部観察用光入射窓であり、１１は内部観察窓である。In this way, a desired solution 7 is formed in the crucible 3,
After leaving this at 900-1000°C for about 10 hours, the solution temperature is lowered and set at about 800-900°C. Then, the YCu plate attached to the tip of the pulling shaft 8 is added to this solution 7.
Seed crystals made of O' do crystals are immersed in the solution and thoroughly absorbed. Thereafter, the crystal 9 is pulled up at a low cooling rate of 0.1 to 0.5°C/h. During this pulling, 100 ml of oxygen gas is applied to the surface of the solution 7 via the gas introducing vibrator 12! /lll1n is supplied. 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−δ
ことができる。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 CuO crystal can be pulled up 237-δ. 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、Ｃｕ０−Ｖ２０５混合液を用
いた場合を説明する。第３図は、Ｃｕ０−Ｖ２Ｏ３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℃程度で液相状態が得られる。このＣｕｂ
−Ｖ２Ｑ５混合液（Ｃｕ Ｏが４０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、９００〜１０００℃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結晶を引上げる。Next, a case will be described in which a Cu0-V205 mixed solution is used as the flux. Figure 3 is a phase diagram of the Cu0-V2O3 system, and by selecting an appropriate molar ratio in this system,
After all, a liquid phase state is obtained at about 900°C. This Cub
-V2Q5 mixed solution (40 mol% or less of CuO) 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 after being left at 900 to 1000 °C for about 10 hours, the solution temperature was Lower the temperature and set it to 800-900℃. After this, in the same manner as in the previous example, YBa Cu
Pull up the O crystal.
２ ３７づ
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 In this example, as well as in the previous example, high quality YBa was 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 −０系、Ｓｒ
−Ｌａ −Ｃｕ−０系、更にＳｒをＢａ。The present invention is also effective in the case of oxide superconductor crystals containing other rare earth elements such as Ho, Dy, Eu, Er, Tm, and Lu.
-La -Cu-0 system, further Sr and Ba.
Ｃａなとで置換した系等、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. Furthermore, although crystal pulling has been explained in the embodiment, the present invention is also effective for epitaxial growth of multi-component oxide superconductors.
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、遷移金属を含む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 a transition metal as a flux.
第１図は本発明の一実施例のＹ−Ｂａ −Ｃｕ−０系結
晶の引上げ装置を示す図、第２図は、Ｐｂ ０−８２０
３系の相図、第３図は、Ｃｕ０−Ｖ２Ｏ３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
入パイプ。
出願人代理人 弁理士 鈴江武彦
第１図
浸宸（°Ｃ）FIG. 1 is a diagram showing a pulling apparatus for Y-Ba-Cu-0 system crystal according to an embodiment of the present invention, and FIG.
Figure 3 is a phase diagram of the Cu0-V2O3 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 shaft, 9 ... YBa Cu O crystal, 1
0... Light irradiation window for internal observation 2 37-δ, 11... Internal observation window, 12... Gas introduction pipe. Applicant's representative Patent attorney Takehiko Suzue Figure 1 (°C)
Claims (4)
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 a transition metal 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.
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 method for producing an oxide superconductor crystal according to claim 1, wherein the flux is a PbO-B_2O_3-based mixed liquid.
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 CuO-V_2O_5-based mixed liquid.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62304631A JPH01148794A (en) | 1987-12-03 | 1987-12-03 | Production of 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 |
|---|---|---|---|
| JP62304631A JPH01148794A (en) | 1987-12-03 | 1987-12-03 | Production of oxide superconductor crystal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01148794A true JPH01148794A (en) | 1989-06-12 |
Family
ID=17935358
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62304631A Pending JPH01148794A (en) | 1987-06-11 | 1987-12-03 | Production of oxide superconductor crystal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01148794A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5602081A (en) * | 1993-05-10 | 1997-02-11 | International Superconductivity Technology Center | Method of preparing metal oxide crystal |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS606913A (en) * | 1983-06-24 | 1985-01-14 | Matsushita Electric Ind Co Ltd | Lens moving device |
-
1987
- 1987-12-03 JP JP62304631A patent/JPH01148794A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS606913A (en) * | 1983-06-24 | 1985-01-14 | Matsushita Electric Ind Co Ltd | Lens moving device |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5602081A (en) * | 1993-05-10 | 1997-02-11 | International Superconductivity Technology Center | Method of preparing metal oxide crystal |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Klemenz et al. | Liquid phase epitaxy of high-Tc superconductors | |
| JP2651481B2 (en) | How to make superconducting materials | |
| US5407907A (en) | Method of preparing metal oxide crystal | |
| JPH09100193A (en) | Preparation of oxide crystal | |
| JP2672533B2 (en) | Method for producing oxide superconductor crystal | |
| JPH01148794A (en) | Production of oxide superconductor crystal | |
| JP2637123B2 (en) | Method for producing oxide superconductor crystal | |
| JPS63310799A (en) | Production of oxide superconducting crystal | |
| JPH01131098A (en) | Production of oxide superconductor crystal | |
| JPS63310798A (en) | Production of oxide superconducting element wafer | |
| JP2550253B2 (en) | Method for producing oxide high temperature superconductor | |
| JP3936767B2 (en) | Preparation method of oxide crystals | |
| JP2833640B2 (en) | Method for producing Pr123 crystal | |
| JP3205646B2 (en) | Method for producing Sm-based 123 crystal | |
| JP2733197B2 (en) | Method for producing rare earth element-containing single crystal | |
| JP2963604B2 (en) | Method for producing ReBa2Cu3Oy crystal from melt | |
| JPH059059A (en) | Production of oxide superconductor | |
| JP2833639B2 (en) | Preparation method of oxide crystal | |
| JP2852405B2 (en) | Bi (2) (Sr, Ca) (3) Cu (2) O (8) Single crystal production method by solution pulling method | |
| JP2000247795A (en) | Production of re123 oxide superconductive bulk body | |
| RU2051210C1 (en) | High-temperature super-conducting material and method for production thereof | |
| JPH0818910B2 (en) | Method for producing oxide superconducting single crystal | |
| JPH0471876B2 (en) | ||
| JPS63310796A (en) | Oxide superconducting element wafer | |
| JPH04182394A (en) | Production of single crystal superconductor |