JP2733197B2 - Method for producing rare earth element-containing single crystal - Google Patents
Method for producing rare earth element-containing single crystalInfo
- Publication number
- JP2733197B2 JP2733197B2 JP6053172A JP5317294A JP2733197B2 JP 2733197 B2 JP2733197 B2 JP 2733197B2 JP 6053172 A JP6053172 A JP 6053172A JP 5317294 A JP5317294 A JP 5317294A JP 2733197 B2 JP2733197 B2 JP 2733197B2
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- single crystal
- raw material
- solvent
- material rod
- superconductor
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、ＲＢａ2 Ｃｕ3 Ｏy 単
結晶等の希土類元素含有単結晶のフローティングゾーン
法による製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a rare earth element-containing single crystal such as an RBa 2 Cu 3 O y single crystal by a floating zone method.
【０００２】[0002]
【従来の技術】ＲＢａ2 Ｃｕ3 Ｏ7 （以下、Ｒは希土類
元素を表す）単結晶は８０〜９０Ｋの低温で超伝導体と
なり、安価な液体窒素を用いた極低温素子として、今後
の応用が期待されている。このため大型の良質な単結晶
が望まれ、その製造方法の開発が望まれている。 2. Description of the Related Art A single crystal of RBa 2 Cu 3 O 7 (hereinafter, R represents a rare earth element) becomes a superconductor at a low temperature of 80 to 90 K, and is used as a cryogenic element using inexpensive liquid nitrogen. Is expected. For this reason, a large-sized high-quality single crystal is desired, and development of a manufacturing method thereof is desired.
【０００３】ところが、ＲＢａ2 Ｃｕ3 Ｏy は高温にし
てゆくと９２０℃付近から分解溶融してしまうため、単
結晶と同一組成の原料から単結晶を製造することができ
ない。このためフラックス法や溶液引き上げ法で結晶育
成がされている。However, as RBa 2 Cu 3 O y is decomposed and melted at around 920 ° C. as the temperature is increased, a single crystal cannot be produced from a raw material having the same composition as a single crystal. For this reason, crystals are grown by a flux method or a solution pulling method.
【０００４】フラックス法では、育成時間が３〜７日で
最大４ｍｍ×５ｍｍ×０．５〜１ｍｍの大きさの単結晶
が現在までに育成されている（参考文献１：Ａ．Ｋａｔ
ｓｕｉ，Ｙ．Ｈｉｄａｋａ ａｎｄ Ｈ．Ｏｈｔｓｕｋ
ａ Ｊｐｎ．Ｊ．Ａｐｐｌ．Ｐｈｙｓ．Ｖｏｌ．２６，
Ｎｏ．９（１９８７）Ｌ１５２１）。[0004] In the flux method, single crystals having a maximum size of 4 mm x 5 mm x 0.5 to 1 mm have been grown to date with a growth time of 3 to 7 days (Reference 1: A. Kat).
sui, Y .; Hidaka and H.S. Ohtsuk
a Jpn. J. Appl. Phys. Vol. 26,
No. 9 (1987) L1521).
【０００５】しかしながら、フラックス法では、結晶育
成に時間を要するうえに、その育成結晶の大きさが小さ
く、融剤から育成結晶を分離する操作が必要であった。However, in the flux method, it takes a long time to grow the crystal, the size of the grown crystal is small, and an operation of separating the grown crystal from the flux is required.
【０００６】これに対し、比較的高速での単結晶の製造
が可能な溶液引き上げ法では、ＮｄＢａ2 Ｃｕ3 Ｏ7 −
ｙ単結晶 （参考文献２：Ｋ．Ｏｋａ，Ｍ．Ｓａｉｔ
ｏ，Ｍ．Ｉｔｏ，Ｋ．Ｎａｋａｎｅ，Ｋ．Ｍｕｒａｔ
ａ，Ｙ．Ｎｉｓｈｉｈａｒａ ａｎｄ Ｈ．Ｕｎｏｋ
ｉ，Ｊｐｎ．Ｊ．Ａｐｐｌ．Ｐｈｙｓ．Ｖｏｌ．２８，
Ｎｏ．２（１９８９）Ｌ２１９）、ＹＢａ2 Ｃｕ3 Ｏ7
−δ単結晶 （参考文献３：Ａ．Ｏｄａｇａｗａ，Ｙ．
Ｅｎｏｍｏｔｏ，Ｙ．Ｙａｍａｄａ，Ｙ．Ｓｈｉｏｈａ
ｒａ ａｎｄ Ｓ．Ｔａｎａｋａ，Ｐｈｙｓｉｃａ Ｃ
２１７（１９９３）２２２）、ＰｒＢａ2 Ｃｕ3 Ｏ7 −
δ単結晶 （参考文献４：Ｍ．Ｔａｇａｍｉ，Ｍ．Ｓｕ
ｍｉｄａ，Ｃ．Ｋｒａｕｎｓ，Ｙ．Ｙａｍａｄａ，Ｔ．
Ｕｍｅｄａ ａｎｄ Ｙ．Ｓｈｉｏｈａｒａ，Ｉｎｔ．
Ｓｙｍｐｏ．Ｓｕｐｅｒ ’９３ Ｐｒｏｃｅｅｄ．印
刷中）、ＳｍＢａ2 Ｃｕ3 Ｏ7 単結晶（参考文献５：’
９３ １０．２２ 日刊工業新聞他）が育成され、特に
ＳｍＢａ2 Ｃｕ3 Ｏ7 単結晶では最大２５ｍｍ角の大き
さまで育成されたことが知られている。On the other hand, in the solution pulling method capable of producing a single crystal at a relatively high speed, NdBa 2 Cu 3 O 7 −
y single crystal (Reference 2: K. Oka, M. Sait
o, M. Ito, K .; Nakane, K .; Murat
a, Y. Nishihara and H.S. Unok
i, Jpn. J. Appl. Phys. Vol. 28,
No. 2 (1989) L219), YBa 2 Cu 3 O 7
-Δ single crystal (Reference 3: A. Odagawa, Y .;
Enomoto, Y .; Yamada, Y .; Shioha
ra and S.R. Tanaka, Physica C
217 (1993) 222), PrBa 2 Cu 3 O 7 −
δ single crystal (Reference 4: M. Tagami, M. Su
mida, C.I. Krauns, Y .; Yamada, T .;
Umeda and Y. Shiohara, Int.
Sympo. Super '93 Proceed. (During printing), SmBa 2 Cu 3 O 7 single crystal (reference 5: '
93 10.22 Nikkan Kogyo Shimbun, etc.), and in particular, it is known that SmBa 2 Cu 3 O 7 single crystal was grown to a maximum size of 25 mm square.
【０００７】しかしながら、溶液引き上げ法では、かな
り高度の結晶育成技術や装置が必要であり、容器に充填
した出発原料はごく少量が単結晶となるだけであり、大
部分が容器に残り数回の結晶成長で純度の低下のために
高価な原料を捨てなければならないというコスト面の問
題があった。また、両方法とも容器材料が溶液中に流出
し育成結晶に不純物として混入する等の問題があった。[0007] However, the solution pulling method requires a very high degree of crystal growth technology and equipment, and only a small amount of the starting material filled in the container becomes a single crystal, and most of the starting material remains in the container several times. There is a cost problem that expensive raw materials must be discarded due to a decrease in purity during crystal growth. Further, both methods have a problem that the container material flows out into the solution and is mixed with the grown crystal as an impurity.
【０００８】これらの問題を解決するフローティングゾ
ーン法の適用が考えられている。The application of the floating zone method to solve these problems has been considered.
【０００９】ところで、一般にＲＢａ2 Ｃｕ3 Ｏy 系の
単結晶では、その中に酸素が十分含まれていないと良い
超伝導性を示さない。このため、従来のフラックス法等
を用いた単結晶製造は大気中あるいは酸素中で行われて
おり、この技術的な常識はフローティングゾーン法にも
同様に適用されてきた。[0009] In the general RBa 2 Cu 3 O y system of a single crystal, it does not exhibit good superconducting properties of oxygen therein does not contain enough. For this reason, single crystal production using a conventional flux method or the like is performed in the air or in oxygen, and this technical common sense has been similarly applied to the floating zone method.
【００１０】しかしながら、このような技術常識を適用
したフローティング法によれば、原料棒と種結晶の間に
設けた溶媒が溶融すると原料棒に著しく浸潤したり、溶
媒の粘性が低いため種結晶に流れ出し溶融帯を保持でき
ず、この方法でＲＢａ2 Ｃｕ3 Ｏy 単結晶育成に成功し
た報告例はまだ知られてない。However, according to the floating method to which such technical common sense is applied, when the solvent provided between the raw material rod and the seed crystal is melted, the raw material rod is remarkably infiltrated, or the viscosity of the solvent is low, so that the raw material rod has low viscosity. There has been no known example of a report that the Rba 2 Cu 3 O y single crystal was successfully grown by this method because the flow-out molten zone could not be maintained.
【００１１】[0011]
【発明が解決しようとする課題】本発明の目的は、比較
的短時間に良質の希土類元素含有単結晶を製造できるフ
ローティングゾーン法を用いた単結晶の製造方法を提供
することにある。SUMMARY OF THE INVENTION It is an object of the present invention to provide a single crystal production method using a floating zone method, which can produce a high quality rare earth element-containing single crystal in a relatively short time.
【００１２】[0012]
【課題を解決するための手段】上記目的を達成するため
に、本発明は、上記事情に鑑み、ＹＢａ2 Ｃｕ3 Ｏ7相
平衡図（参考文献６：Ｋ．Ｏｋａ，Ｋ．Ｎａｋａｎｅ，
Ｍ．Ｉｔｏ，Ｍ．Ｓａｉｔｏ ａｎｄ Ｈ．Ｕｎｏｋ
ｉ，Ｊｐｎ．Ｊ．Ａｐｐｌ．Ｐｈｙｓ．Ｖｏｌ．２７，
Ｎｏ．６（１９８８）Ｌ１０６５） やＮｄＢａ2 Ｃｕ
3 Ｏ7 の相平衡図（参考文献２）に基づき、実際のＲＢ
ａ2 Ｃｕ3 Ｏy 単結晶製造に適したフローティングゾー
ン法を研究した結果開発されたものであり、ＲＢａ2 Ｃ
ｕ3 Ｏy 原料棒と種結晶の間に希土類酸化物と酸化バリ
ウムあるいは炭酸バリウムのうちの少なくとも１種と酸
化銅を元素比にして１：４：６から１：２９：６６の組
成からなる溶媒を設け、溶媒を９２０〜１１００℃に加
熱して浮遊溶融帯を形成し、浮遊溶融帯を原料棒側に移
動させることにより種結晶に単結晶を析出させるように
したことを特徴とする。SUMMARY OF THE INVENTION In order to achieve the above object, the present invention has been made in view of the above circumstances, and in view of the above, a YBa 2 Cu 3 O 7 phase equilibrium diagram (Reference 6: K. Oka, K. Nakane,
M. Ito, M .; Saito and H.S. Unok
i, Jpn. J. Appl. Phys. Vol. 27,
No. 6 (1988) L1065) and NdBa 2 Cu
Based on the phase equilibrium diagram of 3 O 7 (Reference 2), the actual RB
a 2 Cu 3 O y are those floating zone method results studied were developed which are suitable for producing a single crystal, RBa 2 C
A composition of a rare earth oxide and at least one of barium oxide or barium carbonate and copper oxide in an element ratio of 1: 4: 6 to 1:29:66 between the u 3 O y raw material rod and the seed crystal. A solvent is provided, and the solvent is heated to 920 to 1100 ° C. to form a floating molten zone, and the floating molten zone is moved to the raw material rod side to precipitate a single crystal in the seed crystal.
【００１３】なお、雰囲気としてアルゴンあるいは窒素
のうちの少なくとも１種を用い、このガス中に酸素を０
〜５％混入したものを用いること、すなわち雰囲気の酸
素分圧を極端に少なくすることにより、溶融した溶媒が
原料棒へ浸潤することが少なくなり、安定した浮遊溶融
帯を保持することができるようになった。しかし、良質
な単結晶を得るために結晶成長速度すなわち浮遊溶融帯
の移動速度を０．１〜１．０ｍｍ／ｈｒにすると焼成し
た原料棒では溶媒の浸潤の影響がでてくるので、一度高
速で、浮遊溶融帯を走査させ結晶化した原料棒を作成し
た後、その結晶化させた原料棒を用いて良質なＲＢａ2
Ｃｕ3 Ｏy 単結晶を製造できることを可能とした。しか
るのち、酸素中において熱処理を行い超伝導単結晶とす
る。[0013] At least one of argon and nitrogen is used as an atmosphere, and oxygen is contained in the gas.
By using a mixture mixed with 〜5%, that is, by extremely reducing the oxygen partial pressure of the atmosphere, the infiltration of the molten solvent into the raw material rod is reduced, and a stable floating molten zone can be maintained. Became. However, if the crystal growth speed, that is, the moving speed of the floating molten zone is set to 0.1 to 1.0 mm / hr in order to obtain a good single crystal, the fired raw material rod is affected by the infiltration of the solvent. Then, the floating molten zone is scanned to form a crystallized raw material rod, and then the high-quality RBa 2
It has become possible to produce a Cu 3 O y single crystal. Thereafter, heat treatment is performed in oxygen to obtain a superconducting single crystal.
【００１４】すなわち、請求項１記載の発明は、原料棒
と種結晶との間に溶媒を設け、該溶媒を加熱溶融して溶
融帯を形成し、前記原料棒を下方向に移動させることに
より前記溶融帯を移動させて前記種結晶上に単結晶を析
出させるフローティングゾーン法による希土類元素含有
単結晶の製造方法において、前記原料棒として、ＲＢａ
2 Ｃｕ3 Ｏy （Ｒは、Ｙ，Ｌａ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅ
ｕ，Ｇｄ，Ｔｂ，Ｄｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂからな
る希土類元素群から選択された一元素を表し、ｙは６．
０〜７．０である。）からなり、前記溶融帯を２〜１５
ｍｍ／ｈｒの速度で移動させて作成した結晶化原料棒を
用い、前記結晶化原料棒を構成する希土類元素の酸化物
と、酸化バリウムあるいは炭酸バリウムのうち少なくと
も一種と、酸化銅とを元素比にして１：４：６〜１：２
９：６６の範囲で配合した混合物で構成した溶媒であっ
て、前記結晶化原料棒と前記種結晶との間に設けたもの
からなる溶融帯を０．１〜１．０ｍｍ／ｈｒの速度で移
動させるとともに、該溶媒の加熱温度を９２０〜１１０
０℃の範囲とし、少なくとも前記溶媒の加熱雰囲気を５
％以下の酸素を含む不活性ガスとし、該不活性ガスはア
ルゴンガスまたは窒素ガスのうち少なくとも１種のガス
であることを特徴とする。That is, according to the first aspect of the present invention, a solvent is provided between a raw material rod and a seed crystal, the solvent is heated and melted to form a molten zone, and the raw material rod is moved downward. In the method for producing a rare-earth element-containing single crystal by a floating zone method in which a single crystal is deposited on the seed crystal by moving the melting zone, RBa is used as the raw material rod.
2 Cu 3 O y (R is Y, La, Pr, Nd, Sm, E
u, Gd, Tb, Dy, Ho, Er, Tm, Yb represents one element selected from the group of rare earth elements, and y is 6.
0 to 7.0. ), Wherein the molten zone is 2-15
Using a crystallization raw material rod prepared by moving at a speed of mm / hr, an oxide of a rare earth element constituting the crystallization raw material rod, at least one of barium oxide or barium carbonate, and copper oxide have an element ratio. 1: 4: 6 to 1: 2
A solvent composed of a mixture compounded in the range of 9:66, wherein a molten zone formed between the crystallization raw material rod and the seed crystal is formed at a speed of 0.1 to 1.0 mm / hr. While moving, the heating temperature of the solvent is 920 to 110
0 ° C., and at least the heating atmosphere of the solvent is 5
% Or less of oxygen, wherein the inert gas is at least one of argon gas and nitrogen gas.
【００１５】請求項２記載の発明は、超伝導体の製造方
法であって、請求項１記載の希土類元素含有単結晶の製
造方法によって得られた単結晶を酸素雰囲気中で熱処理
することを特徴とする。According to a second aspect of the present invention, there is provided a method for producing a superconductor, wherein the single crystal obtained by the method for producing a rare earth element-containing single crystal according to the first aspect is heat-treated in an oxygen atmosphere. And
【００１６】請求項３記載の発明は、請求項２記載の超
伝導体の製造方法における前記熱処理を、２段階で行っ
てもよい。According to a third aspect of the present invention, in the method of manufacturing a superconductor according to the second aspect, the heat treatment may be performed in two stages.
【００１７】請求項４記載の発明は、請求項３記載の超
伝導体の製造方法における前記熱処理の第１段階を５０
０℃で２５時間行ってもよい。According to a fourth aspect of the present invention, in the method for manufacturing a superconductor according to the third aspect, the first step of the heat treatment is performed by 50 times.
It may be performed at 0 ° C. for 25 hours.
【００１８】請求項５記載の発明は、請求項３または４
に記載の超伝導体の製造方法における前記熱処理の第２
段階を４００℃で６０時間行ってもよい。The invention according to claim 5 is the invention according to claim 3 or 4.
2. The second step of the heat treatment in the method for producing a superconductor described in
The steps may be performed at 400 ° C. for 60 hours.
【００１９】[0019]
【００２０】[0020]
【００２１】[0021]
【００２２】[0022]
【００２３】[0023]
【作用】まず、本発明の原理について述べる。図１は示
差熱分析と加熱急冷法の結果から作図したＹＢａ2 Ｃｕ
3 Ｏ7 −Ｂａ3 Ｃｕ7 Ｏ10系の相平衡図である。例え
ば、ＹＢａ2 Ｃｕ3 Ｏ7 を加熱上昇させると９９５℃付
近で分解溶融してしまう。次に液相線Ａ−Ｂ間の組成
比、すなわちＹＢａ2 Ｃｕ3 Ｏ7-y が１５〜３モル％、
Ｂａ3 Ｃｕ7 Ｏ10が８５〜９７モル％の範囲に混合した
原料を約９２０〜９９５℃において加熱融解したのち
に、融液を徐々に降温させると、融液の組成は液相線Ａ
−Ｂに沿って図１のＢａ3 Ｃｕ7 Ｏ10側へずれてゆき、
ＹＢａ2 Ｃｕ3Ｏ7 −ｙ が固相となって析出してく
る。融液の組成が共晶点ＢよりＢａ3 Ｃｕ 7 Ｏ10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ＹＢａ2 Ｃｕ3 Ｏ7 側であれば、冷却時にまずＹ2
ＢａＣｕＯ5 造の結晶が析出し、いずれもＹＢａ2 Ｃｕ
3 Ｏ7 単結晶が析出成長することができない。First, the principle of the present invention will be described. Figure 1 shows
YBa plotted from the results of differential thermal analysis and heating / quenching methodTwo Cu
Three O7 -BaThree Cu7 OTenIt is a phase equilibrium diagram of a system. example
For example, YBaTwo CuThree O7 When heated to 995 ° C
Decomposition and melting nearby. Next, the composition between the liquidus lines AB
Ratio, ie YBaTwo CuThree O7-y Is 15 to 3 mol%,
BaThree Cu7 OTenWas mixed in the range of 85 to 97 mol%.
After heating and melting the raw materials at about 920 to 995 ° C
Then, when the temperature of the melt is gradually lowered, the composition of the melt becomes liquidus A
1 along the line -B.Three Cu7 OTenIt shifts to the side,
YBaTwo CuThreeO7 -Y is precipitated as a solid phase
You. Melt composition is Ba from eutectic point BThree Cu 7 OTenOn the side
Then, upon cooling, CuO precipitates first, and the composition of the melt becomes point A.
More YBaTwo CuThree O7 Side, when cooling, first YTwo
BaCuOFive Crystal is precipitated, and both are YBaTwo Cu
Three O7 Single crystals cannot be deposited and grown.
【００２４】本発明においては、フローティングゾーン
法においてＲＢａ2 Ｃｕ3 Ｏy 原料棒と種結晶の間に設
けられた溶媒の成分組成を希土類酸化物と酸化バリウム
あるいは炭酸バリウムのうちの少なくとも１種と酸化銅
を元素比にして１：４：６から１：２９：６６の組成に
し、雰囲気としてアルゴンあるいは窒素のうちの少なく
とも１種を用い、このガス中に酸素を０〜５％混入し、
溶媒を９２０〜１１００℃に加熱溶融して、上記溶融組
成を安定に保ちながら原料棒側に移動させ、種結晶にＲ
Ｂａ2 Ｃｕ3 Ｏy 単結晶を成長させることができる。特
に結晶化させた原料棒を用いることにより結晶成長速度
をより遅くでき、さらに良質の単結晶を製造できる。In the present invention, the composition of the solvent provided between the RBa 2 Cu 3 O y raw material rod and the seed crystal in the floating zone method is changed to the rare earth oxide and at least one of barium oxide and barium carbonate. Copper oxide has an elemental ratio of 1: 4: 6 to 1:29:66, and at least one of argon and nitrogen is used as an atmosphere, and 0 to 5% of oxygen is mixed into this gas.
The solvent is heated and melted at 920 to 1100 ° C., and is moved to the raw material rod side while keeping the above-mentioned molten composition stable.
Ba 2 Cu 3 O y single crystals can be grown. In particular, by using a crystallized raw material rod, the crystal growth rate can be further reduced, and a high-quality single crystal can be produced.
【００２５】[0025]
【実施例】以下、本発明の実施例を詳細に説明する。Embodiments of the present invention will be described below in detail.
【００２６】図２は、本発明の希土類元素含有単結晶の
製造方法を実施することが可能なフローティングゾーン
単結晶製造装置の構成を示す縦断面図である。図２にお
いて１は原料棒、２は種結晶、３は溶融帯域（溶媒）、
４および５はそれぞれ回転軸、６は石英管、７はハロゲ
ンランプ、８は回転楕円鏡、９は観察窓、１０はレン
ズ、１１は観察用スクリーンである。図２に示した単結
晶製造装置においては、回転楕円鏡８の一方の焦点上に
ハロゲンランプ７が配置され、他方の焦点上に溶融帯域
３が形成されるようになっている。原料棒１の上端部は
上部回転軸４の下端部の把持機構により把持されてい
る。この上部回転軸４の回転方向と、種結晶２を保持す
る下部回転軸５の回転方向とは互いに反対回りに回転す
る。一方の焦点上に置かれたハロゲンランプ７の赤外光
が回転楕円鏡８に反射し、石英管６を透過して他方の焦
点に配置された溶融帯部に集光する。これにより溶融帯
域３が常に一定の位置に形成される。種結晶２の部分と
原料棒１を溶融帯域に対して相対的に下方へ移動させる
ことにより、単結晶成長を行うことができる。FIG. 2 is a longitudinal sectional view showing the configuration of a floating zone single crystal manufacturing apparatus capable of implementing the method for manufacturing a rare earth element-containing single crystal of the present invention. In FIG. 2, 1 is a raw material rod, 2 is a seed crystal, 3 is a melting zone (solvent),
Reference numerals 4 and 5 denote rotation axes, 6 denotes a quartz tube, 7 denotes a halogen lamp, 8 denotes a spheroid mirror, 9 denotes an observation window, 10 denotes a lens, and 11 denotes an observation screen. In the single crystal manufacturing apparatus shown in FIG. 2, the halogen lamp 7 is arranged at one focal point of the spheroidal mirror 8 and the melting zone 3 is formed at the other focal point. The upper end of the raw material rod 1 is gripped by a gripping mechanism at the lower end of the upper rotating shaft 4. The rotation direction of the upper rotation shaft 4 and the rotation direction of the lower rotation shaft 5 holding the seed crystal 2 rotate in opposite directions. The infrared light of the halogen lamp 7 placed on one focal point is reflected by the spheroidal mirror 8, passes through the quartz tube 6, and is condensed on the fusion zone located at the other focal point. As a result, the melting zone 3 is always formed at a fixed position. By moving the portion of the seed crystal 2 and the raw material rod 1 relatively downward with respect to the melting zone, single crystal growth can be performed.
【００２７】以下、各実施例は図２に示した単結晶製造
装置を用いてなされている。Hereinafter, each embodiment is performed using the single crystal manufacturing apparatus shown in FIG.
【００２８】実施例１ ＹＢａ2 Ｃｕ3 Ｏy 単結晶をフローティングゾーン法に
よって製造した。Example 1 A YBa 2 Cu 3 O y single crystal was produced by a floating zone method.
【００２９】（結晶化原料棒の製造）Ｙ2 Ｏ3 とＢａＣ
Ｏ3 とＣｕＯを元素比にして１：２：３に混合した粉末
を８８０℃で１５時間焼成し、その粉末を加圧成形器で
直径６ｍｍ、長さ７ｃｍの丸棒状にして９５０℃で１５
時間均質に焼成してＹＢａ2 Ｃｕ3 Ｏy 原料棒１とす
る。(Production of raw material rod for crystallization) Y 2 O 3 and BaC
A powder obtained by mixing O 3 and CuO in an elemental ratio of 1: 2: 3 is baked at 880 ° C. for 15 hours, and the powder is formed into a round bar having a diameter of 6 mm and a length of 7 cm by a pressure molding machine at 950 ° C. for 15 hours.
It is fired uniformly for a time to obtain a YBa 2 Cu 3 O y raw material rod 1.
【００３０】同様に、Ｙ2 Ｏ3 とＢａＣＯ3 とＣｕＯを
Ｙ：Ｂａ：Ｃｕの元素比にして１：２９：６６で混合し
た粉末を８８０℃で１５時間焼成し、その粉末を加圧成
形器で直径６ｍｍの丸棒状にして９００℃で１５時間均
質に焼成して溶媒とする。しかるのち、この円柱棒状の
溶媒を径方向に切断し円盤状にしてＹＢａ2 Ｃｕ3 Ｏy
原料棒１に融着させる。Similarly, a powder obtained by mixing Y 2 O 3 , BaCO 3 and CuO at an element ratio of Y: Ba: Cu of 1:29:66 is baked at 880 ° C. for 15 hours, and the powder is subjected to pressure molding. The mixture is made into a round bar having a diameter of 6 mm in a vessel and homogeneously baked at 900 ° C. for 15 hours to obtain a solvent. Thereafter, the cylindrical rod-shaped solvent is cut in the radial direction to form a disk, and YBa 2 Cu 3 O y
The material rod 1 is fused.
【００３１】このようにＹＢａ2 Ｃｕ3 Ｏ7 原料棒１の
先端に溶媒を融着した円柱棒状試料を、赤外線加熱方式
を採用したフローティングゾーン法単結晶製造装置の上
部試料回転軸４に固定し、同様に下部回転軸５に種結晶
２としてＹＢａ2 Ｃｕ3 Ｏy焼成棒を固定する。なお、
この場合種結晶２と溶媒をつけたＹＢａ2 Ｃｕ3 Ｏy原
料棒１が回転軸に対して偏心しないように設定する。そ
してハロゲンランプ７を用い赤外線を使用して上記溶媒
を加熱溶解したのちに種結晶を溶媒に接触させ、液体の
表面張力により原料棒と種結晶の間に溶融溶媒を保持さ
せる。しかる後に原料棒と種結晶とを互いに反対方向に
３０ｒｐｍで回転させる。The cylindrical rod-shaped sample obtained by fusing the solvent to the tip of the YBa 2 Cu 3 O 7 raw material rod 1 is fixed to the upper sample rotating shaft 4 of the floating zone single crystal manufacturing apparatus employing the infrared heating method. Similarly, a YBa 2 Cu 3 O y firing rod is fixed to the lower rotating shaft 5 as the seed crystal 2. In addition,
In this case species YBa 2 Cu 3 O y feed rod 1 with a crystal 2 and the solvent is set so as not to eccentrically with respect to the rotation axis. Then, after the solvent is heated and dissolved using infrared rays using a halogen lamp 7, the seed crystal is brought into contact with the solvent, and the molten solvent is held between the raw material rod and the seed crystal by the surface tension of the liquid. Thereafter, the raw material rod and the seed crystal are rotated at 30 rpm in directions opposite to each other.
【００３２】さらに、この浮遊溶融帯を５ｍｍ／ｈｒの
速度で原料棒側、すなわち上方に移動させて種結晶にＹ
Ｂａ2 Ｃｕ3 Ｏy 結晶化原料棒を作成する。なお、石英
管６内の雰囲気を０．１％の酸素を含むアルゴンガスと
した。Further, the floating molten zone is moved at a speed of 5 mm / hr to the raw material rod side, that is, upward, so that the seed crystal becomes Y
A Ba 2 Cu 3 O y crystallization raw material rod is prepared. The atmosphere in the quartz tube 6 was argon gas containing 0.1% oxygen.
【００３３】原料棒１がほぼ消費されたときに作成した
結晶化原料棒と原料棒とを切り離して室温まで冷却し
た。ここまでが結晶化原料棒の作成工程である。When the raw material rod 1 was almost consumed, the crystallization raw material rod and the raw material rod were cut off and cooled to room temperature. The process up to this point is the preparation process of the raw material rod for crystallization.
【００３４】（単結晶の製造）次に、種結晶２としてＹ
Ｂａ2 Ｃｕ3 Ｏy 単結晶を下部回転軸５に、上部回転軸
４に溶媒をつけた結晶化原料棒を固定し、再び上記と同
様な方法と操作で融けた溶媒、すなわち浮遊溶融帯を
０．５ｍｍ／ｈｒで結晶化原料棒側に移動させ、種結晶
に 単結晶を育成させた。なお、石英管６内の雰囲気を
０．１％の酸素を含むアルゴンガスとした。この結果、
直径４ｍｍ、長さ７ｍｍの円柱状の棒体が得られた。こ
れをＸ線背面ラウエ解析により単結晶であることを確認
し、さらにこの単結晶を粉末にしてＸ線回折によりＹＢ
ａ2 Ｃｕ3 Ｏy 相であることを確認した。(Preparation of Single Crystal) Next, Y as a seed crystal 2
A Ba 2 Cu 3 O y single crystal is fixed to the lower rotating shaft 5 and a crystallization raw material rod having a solvent attached to the upper rotating shaft 4 is fixed. It was moved to the raw material rod side at 0.5 mm / hr to grow a single crystal as a seed crystal. The atmosphere in the quartz tube 6 was argon gas containing 0.1% oxygen. As a result,
A cylindrical rod having a diameter of 4 mm and a length of 7 mm was obtained. This was confirmed to be a single crystal by X-ray backside Laue analysis, and this single crystal was powdered to obtain YB by X-ray diffraction.
It was confirmed that it was an a 2 Cu 3 O y phase.
【００３５】しかる後、５００℃で２５時間、４００℃
で６０時間酸素中で熱処理をして磁化測定により超伝導
転移温度９１．５Ｋの超伝導体であることを確認した。Thereafter, at 500 ° C. for 25 hours, 400 ° C.
And heat treatment in oxygen for 60 hours, and it was confirmed by magnetization measurement that the superconductor had a superconducting transition temperature of 91.5K.
【００３６】実施例２ ＬａＢａ2 Ｃｕ3 Ｏy 単結晶をフローティングゾーン法
によって製造した。[0036] was prepared according to Example 2 LaBa 2 Cu 3 O y single crystal floating zone method.
【００３７】（結晶化原料棒の製造）Ｌａ2 Ｏ3 とＢａ
ＣＯ3 とＣｕＯを元素比にして１：２：３に混合した粉
末を８８０℃で１５時間焼成し、その粉末を加圧成形器
で直径６ｍｍ、長さ７ｃｍの丸棒状にして１０３０℃で
１５時間均質に焼成してＬａＢａ2 Ｃｕ3 Ｏy 原料棒１
とする。(Production of raw material rod for crystallization) La 2 O 3 and Ba
A powder obtained by mixing CO 3 and CuO in an elemental ratio of 1: 2: 3 is calcined at 880 ° C. for 15 hours, and the powder is formed into a round bar having a diameter of 6 mm and a length of 7 cm using a pressure molding machine at 1530 ° C. LaBa 2 Cu 3 O y raw material rod 1
And
【００３８】同様に、Ｌａ2 Ｏ3 とＢａＣＯ3 とＣｕＯ
をＬａ：Ｂａ：Ｃｕの元素比にして１：４：６に混合し
た粉末を８８０℃で１５時間焼成し、その粉末を加圧成
形器で直径６ｍｍの丸棒状にして９００℃で１５時間均
質に焼成して溶媒とする。しかるのち、実施例１と同様
の装置と操作で溶媒を１５ｍｍ／ｈｒの速度で原料棒側
に移動させて結晶化原料棒を作成する。なお、石英管６
内の雰囲気を０．１％の酸素を含むアルゴンガスとし
た。Similarly, La 2 O 3 , BaCO 3 and CuO
Was mixed at an elemental ratio of La: Ba: Cu of 1: 4: 6, and calcined at 880 ° C. for 15 hours, and the powder was formed into a round bar having a diameter of 6 mm with a press and homogenized at 900 ° C. for 15 hours. Into a solvent. Thereafter, the crystallization raw material rod is prepared by moving the solvent to the raw material rod side at a speed of 15 mm / hr by the same apparatus and operation as in Example 1. The quartz tube 6
The inside atmosphere was an argon gas containing 0.1% oxygen.
【００３９】（単結晶の製造）しかる後、この結晶化原
料棒を用いて実施例１と同様の装置と操作で融けた溶媒
を０．５ｍｍ／ｈｒの速度で結晶化原料棒側に移動させ
て種結晶にＬａＢａ2Ｃｕ3 Ｏy 単結晶を育成させる。
なお、石英管６内の雰囲気を０．１％の酸素を含むアル
ゴンガスとした。この結果、直径５ｍｍ、長さ４０ｍｍ
の円柱状の棒体が得られた。これをＸ線背面ラウエ解析
により単結晶であることを確認し、さらにこの単結晶を
粉末にしてＸ線回折によりＬａＢａ2 Ｃｕ3 Ｏy 相であ
ることを確認したしかる後、５００℃で２５時間、４０
０℃で６０時間酸素中で熱処理をして磁化測定により超
伝導転移温度９０Ｋの超伝導体であることを確認した。(Preparation of Single Crystal) Thereafter, using the raw material rod for crystallization, the solvent melted by the same apparatus and operation as in Example 1 was moved to the raw material rod side at a rate of 0.5 mm / hr. Then, a LaBa 2 Cu 3 O y single crystal is grown on the seed crystal.
The atmosphere in the quartz tube 6 was argon gas containing 0.1% oxygen. As a result, a diameter of 5 mm and a length of 40 mm
Was obtained. This was confirmed to be a single crystal by X-ray backside Laue analysis, and this single crystal was powdered to confirm that it was a LaBa 2 Cu 3 O y phase by X-ray diffraction. , 40
Heat treatment was performed in oxygen at 0 ° C. for 60 hours, and magnetization measurement confirmed that the superconductor had a superconducting transition temperature of 90K.
【００４０】実施例３ ＰｒＢａ2 Ｃｕ3 Ｏy 単結晶をフローティングゾーン法
によって製造した。[0040] was prepared according to Example 3 PrBa 2 Cu 3 O y single crystal floating zone method.
【００４１】（結晶化原料棒の製造）Ｐｒ6 Ｏ11とＢａ
ＣＯ3 とＣｕＯを元素比にして１：２：３に混合した粉
末を８８０℃で１５時間焼成し、その粉末を加圧成形器
で直径６ｍｍ、長さ７ｃｍの丸棒状にして９５０℃で１
５時間均質に焼成してＰｒＢａ2 Ｃｕ3 Ｏy 原料棒１と
する。(Production of raw material rod for crystallization) Pr 6 O 11 and Ba
A powder obtained by mixing CO 3 and CuO at an elemental ratio of 1: 2: 3 was calcined at 880 ° C. for 15 hours, and the powder was formed into a round bar having a diameter of 6 mm and a length of 7 cm using a pressure molding machine at 950 ° C. for 1 hour.
It is baked uniformly for 5 hours to obtain PrBa 2 Cu 3 O y raw material rod 1.
【００４２】同様に、Ｐｒ6 Ｏ11とＢａＣＯ3 とＣｕＯ
をＰｒ：Ｂａ：Ｃｕの元素比にして１：６：１３に混合
した粉末を８８０℃で１５時間焼成し、その粉末を加圧
成形器で直径６ｍｍの丸棒状にして９２０℃で１５時間
均質に焼成して溶媒とする。しかるのち、実施例１と同
様の装置と操作で融けた溶媒、すなわち浮遊溶融帯を１
０ｍｍ／ｈｒの速度で原料棒側に移動させて結晶化原料
棒を作成する。なお、石英管６内の雰囲気を０．１％の
酸素を含むアルゴンガスとした。Similarly, Pr 6 O 11 , BaCO 3 and CuO
Was mixed at an elemental ratio of Pr: Ba: Cu of 1: 6: 13, and calcined at 880 ° C. for 15 hours. The powder was formed into a round bar having a diameter of 6 mm with a pressure molding machine and homogenized at 920 ° C. for 15 hours. Into a solvent. Thereafter, the solvent melted by the same apparatus and operation as in Example 1, that is, the suspended
The crystallization raw material rod is prepared by moving the raw material rod side at a speed of 0 mm / hr. The atmosphere in the quartz tube 6 was argon gas containing 0.1% oxygen.
【００４３】（単結晶の製造）しかる後、この結晶化原
料棒を用いて実施例１と同様の装置と操作で溶媒を０．
５ｍｍ／ｈｒの速度で結晶化原料棒側に移動させて種結
晶にＰｒＢａ2 Ｃｕ3Ｏy 単結晶を育成させる。なお、
石英管６内の雰囲気を０．１％の酸素を含むアルゴンガ
スとした。この結果、直径５ｍｍ、長さ３０ｍｍの円柱
状の棒体が得られた。これをＸ線背面ラウエ解析により
単結晶であることを確認し、さらにこの単結晶を粉末に
してＸ線回折によりＰｒＢａ2 Ｃｕ3 Ｏy 相であること
を確認した。(Preparation of Single Crystal) Thereafter, using the raw material rod for crystallization, the solvent was reduced to 0.1 using the same apparatus and operation as in Example 1.
The seed crystal is moved at a speed of 5 mm / hr to the crystallization raw material rod side to grow a single crystal of PrBa 2 Cu 3 O y . In addition,
The atmosphere in the quartz tube 6 was argon gas containing 0.1% oxygen. As a result, a cylindrical rod having a diameter of 5 mm and a length of 30 mm was obtained. This was confirmed to be a single crystal by X-ray back Laue analysis, it was confirmed that the addition PrBa 2 Cu 3 O y phase by X-ray diffraction by the single-crystal powder.
【００４４】しかる後、５００℃で２５時間、４００℃
で６０時間酸素中で熱処理をした。この物質は、超伝導
体とならないことで知られている。Thereafter, at 500 ° C. for 25 hours, 400 ° C.
For 60 hours in oxygen. This material is known not to be a superconductor.
【００４５】実施例４ ＮｄＢａ2 Ｃｕ3 Ｏy 単結晶をフローティングゾーン法
によって製造した。[0045] was prepared according to Example 4 NdBa 2 Cu 3 O y single crystal floating zone method.
【００４６】（結晶化原料棒の製造）Ｎｄ2 Ｏ3 とＢａ
ＣＯ3 とＣｕＯを元素比にして１：２：３に混合した粉
末を８８０℃で１５時間焼成し、その粉末を加圧成形器
で直径６ｍｍ、長さ７ｃｍの丸棒状にして９５０℃で１
５時間均質に焼成してＮｄＢａ2 Ｃｕ3 Ｏy 原料棒１と
する。(Manufacture of raw material rod for crystallization) Nd 2 O 3 and Ba
A powder obtained by mixing CO 3 and CuO at an elemental ratio of 1: 2: 3 was calcined at 880 ° C. for 15 hours, and the powder was formed into a round bar having a diameter of 6 mm and a length of 7 cm using a pressure molding machine at 950 ° C. for 1 hour.
It is baked uniformly for 5 hours to obtain NdBa 2 Cu 3 O y raw material rod 1.
【００４７】同様に、Ｎｄ2 Ｏ3 とＢａＣＯ3 とＣｕＯ
をＮｄ：Ｂａ：Ｃｕの元素比にして１：１３：２１．３
に混合した粉末を８８０℃で１５時間焼成し、その粉末
を加圧成形器で直径６ｍｍの丸棒状にして９００℃で１
５時間均質に焼成して溶媒とする。しかるのち、実施例
１と同様の装置と操作で溶媒を５ｍｍ／ｈｒの速度で原
料棒側に移動させて結晶化原料棒を作成する。なお、石
英管６内の雰囲気を０．１％の酸素を含むアルゴンガス
とした。Similarly, Nd 2 O 3 , BaCO 3 and CuO
With the element ratio of Nd: Ba: Cu being 1: 13: 21.3
The powder mixed in the above was calcined at 880 ° C. for 15 hours, and the powder was formed into a round bar having a diameter of 6 mm with a pressure molding machine at 900 ° C. for 1 hour.
Bake homogeneously for 5 hours to obtain a solvent. Thereafter, the crystallization raw material rod is prepared by moving the solvent to the raw material rod side at a speed of 5 mm / hr by the same apparatus and operation as in Example 1. The atmosphere in the quartz tube 6 was argon gas containing 0.1% oxygen.
【００４８】（単結晶の製造）しかる後、この結晶化原
料棒を用いて実施例１と同様の装置と操作で溶媒を０．
５ｍｍ／ｈｒの速度で結晶化原料棒側に移動させて種結
晶にＮｄＢａ2 Ｃｕ3Ｏy 単結晶を育成させる。なお、
石英管６内の雰囲気を０．１％の酸素を含むアルゴンガ
スとした。この結果、直径４ｍｍ、長さ２５ｍｍの円柱
状の棒体が得られた。これをＸ線背面ラウエ解析により
単結晶であることを確認し、さらにこの単結晶を粉末に
してＸ線回折によりＮｄＢａ2 Ｃｕ3 Ｏy 相であること
を確認した。(Preparation of Single Crystal) Thereafter, using the raw material rod for crystallization, the solvent was reduced to 0.1 using the same apparatus and operation as in Example 1.
The seed crystal is moved at a speed of 5 mm / hr to the crystallization raw material rod side to grow a single crystal of NdBa 2 Cu 3 O y . In addition,
The atmosphere in the quartz tube 6 was argon gas containing 0.1% oxygen. As a result, a cylindrical rod having a diameter of 4 mm and a length of 25 mm was obtained. This was confirmed to be a single crystal by X-ray back Laue analysis, and this single crystal was powdered to confirm that it was a NdBa 2 Cu 3 O y phase by X-ray diffraction.
【００４９】しかる後、５００℃で２５時間、４００℃
で６０時間酸素中で熱処理をして磁化測定により超伝導
転移温度９１Ｋの超伝導体であることを確認した。Thereafter, at 500 ° C. for 25 hours, 400 ° C.
And heat treatment in oxygen for 60 hours, and it was confirmed by measurement of magnetization that the superconductor had a superconducting transition temperature of 91K.
【００５０】実施例５ ＳｍＢａ2 Ｃｕ3 Ｏy 単結晶をフローティングゾーン法
によって製造した。[0050] was prepared according to Example 5 SmBa 2 Cu 3 O y single crystal floating zone method.
【００５１】（結晶化原料棒の製造）Ｓｍ2 Ｏ3 とＢａ
ＣＯ3 とＣｕＯを元素比にして１：２：３に混合した粉
末を８８０℃で１５時間焼成し、その粉末を加圧成形器
で直径６ｍｍ、長さ７ｃｍの丸棒状にして１０８０℃で
２時間均質に焼成してＳｍＢａ2 Ｃｕ3 Ｏy 原料棒１と
する。(Production of raw material rod for crystallization) Sm 2 O 3 and Ba
A powder obtained by mixing CO 3 and CuO at an elemental ratio of 1: 2: 3 is baked at 880 ° C. for 15 hours, and the powder is formed into a round bar having a diameter of 6 mm and a length of 7 cm by a pressure molding machine at 1080 ° C. for 2 hours. and time homogeneously firing a SmBa 2 Cu 3 O y feed rod 1.
【００５２】同様に、Ｓｍ2 Ｏ3 とＢａＣＯ3 とＣｕＯ
をＳｍ：Ｂａ：Ｃｕの元素比にして１：１９．４：３
１．７に混合した粉末を８８０℃で１５時間焼成し、そ
の粉末を加圧成形器で直径６ｍｍの丸棒状にして９００
℃で１５時間均質に焼成して溶媒とする。しかるのち、
実施例１と同様の装置と操作で溶媒を５，ｍｍ／ｈｒの
速度で原料棒側に移動させて結晶化原料棒を作成する。
なお、石英管６内の雰囲気を０．１％の酸素を含むアル
ゴンガスとした。Similarly, Sm 2 O 3 , BaCO 3 and CuO
In the element ratio of Sm: Ba: Cu is 1: 19.4: 3
The powder mixed in 1.7 was calcined at 880 ° C. for 15 hours, and the powder was formed into a round bar having a diameter of 6 mm using a pressure molding machine.
Bake homogeneously at 15 ° C for 15 hours to obtain a solvent. After a while
A crystallization raw material rod is prepared by moving the solvent to the raw material rod side at a speed of 5 mm / hr by the same apparatus and operation as in Example 1.
The atmosphere in the quartz tube 6 was argon gas containing 0.1% oxygen.
【００５３】（単結晶の製造）しかる後、この結晶化原
料棒を用いて実施例１と同様の装置と操作で溶媒を０．
５ｍｍ／ｈｒの速度で結晶化原料棒側に移動させて種結
晶にＳｍＢａ2 Ｃｕ3Ｏy 単結晶を育成させる。なお、
石英管６内の雰囲気を０．１％の酸素を含むアルゴンガ
スとした。この結果、直径４ｍｍ、長さ２４ｍｍの円柱
状の棒体が得られた。これをＸ線背面ラウエ解析により
単結晶であることを確認し、さらにこの単結晶を粉末に
してＸ線回折によりＳｍＢａ2 Ｃｕ3 Ｏy 相であること
を確認した。(Preparation of Single Crystal) Thereafter, using the raw material rod for crystallization, the solvent was reduced to 0.1 using the same apparatus and operation as in Example 1.
The SmBa 2 Cu 3 O y single crystal is grown as a seed crystal by moving the crystallization raw material rod side at a speed of 5 mm / hr. In addition,
The atmosphere in the quartz tube 6 was argon gas containing 0.1% oxygen. As a result, a cylindrical rod having a diameter of 4 mm and a length of 24 mm was obtained. This was confirmed to be a single crystal by X-ray back Laue analysis, it was confirmed that the addition SmBa 2 Cu 3 O y phase by X-ray diffraction by the single-crystal powder.
【００５４】しかる後、５００℃で２５時間、４００℃
で６０時間酸素中で熱処理をして磁化測定により超伝導
転移温度９４Ｋの超伝導体であることを確認した。Then, at 500 ° C. for 25 hours, 400 ° C.
And heat treatment in oxygen for 60 hours, and it was confirmed by magnetization measurement that the superconductor had a superconducting transition temperature of 94K.
【００５５】なお、上記結晶化原料棒の製造において、
溶媒の組成をＳｍ2 Ｏ3 とＢａＣＯ3 とＣｕＯをＳｍ：
Ｂａ：Ｃｕの元素比にして１：１４．７：２３．８とし
てもよく、また１：１６．８：２７．４としてもよい。
これらの場合にも、優れた超伝導特性を示すＳｍＢａ2
Ｃｕ3 Ｏy 単結晶が得られた。In the production of the crystallization raw material rod,
The composition of the solvent is Sm 2 O 3 , BaCO 3 and CuO are Sm:
The element ratio of Ba: Cu may be 1: 14.7: 23.8, or may be 1: 16.8: 27.4.
Also in these cases, SmBa 2 having excellent superconducting properties
A Cu 3 O y single crystal was obtained.
【００５６】また、結晶化原料棒および単結晶の製造時
における石英管６内の雰囲気を空気としたときは、良質
の単結晶が得られなかった。さらに、７％の酸素を含む
アルゴンガス雰囲気とした場合も、同様に良質の単結晶
が得られなかった。Further, when the atmosphere in the quartz tube 6 during the production of the crystallization raw material rod and the single crystal was air, no good single crystal was obtained. Furthermore, when an argon gas atmosphere containing 7% oxygen was used, a high-quality single crystal was not obtained.
【００５７】さらに、結晶化原料棒および単結晶の製造
時における石英管６内の雰囲気を０．１％の酸素を含む
窒化ガスとした場合でも良質の単結晶を得ることができ
た。また、アルゴンガスまたは窒化ガスのみの雰囲気で
も良質の単結晶を得ることができた。Further, even when the atmosphere in the quartz tube 6 during the production of the crystallization raw material rod and the single crystal was a nitriding gas containing 0.1% of oxygen, a high-quality single crystal could be obtained. In addition, a high-quality single crystal could be obtained even in an atmosphere containing only argon gas or nitriding gas.
【００５８】[0058]
【発明の効果】以上説明したように、本発明によれば、
比較的短時間に種結晶によって任意の結晶軸方向に良質
なＲＢａ2 Ｃｕ3 Ｏy 単結晶を製造することができる。
しかも製造に使用する効果な原料の大部分を単結晶化で
きるので、フラックス法や容積引上げ法に比較し、原料
コストの節約が可能である。As described above, according to the present invention,
A high-quality RBa 2 Cu 3 O y single crystal can be produced in an arbitrary crystal axis direction by a seed crystal in a relatively short time.
In addition, since most of the effective raw materials used in the production can be single-crystallized, the raw material cost can be saved as compared with the flux method or the volume raising method.
【図１】本発明の原理を説明するためのＹＢａ2 Ｃｕ3
Ｏ7 −Ｂａ3 Ｃｕ7 Ｏ10系の相平衡図である。FIG. 1 shows YBa 2 Cu 3 for explaining the principle of the present invention.
O 7 -Ba a phase diagram of the 3 Cu 7 O 10 system.
【図２】フローティングゾーン単結晶製造装置の断面図
である。FIG. 2 is a sectional view of a floating zone single crystal manufacturing apparatus.
【符号の説明】 １ 原料棒 ２ 種結晶 ３ 溶融帯域（溶媒） ４，５ 回転軸 ６ 石英管 ７ ハロゲンランプ ８ 回転楕円鏡 ９ 観察窓 １０ レンズ １１ 観察用スクリーン[Description of Signs] 1 Raw material rod 2 Seed crystal 3 Melting zone (solvent) 4,5 Rotation axis 6 Quartz tube 7 Halogen lamp 8 Spheroid mirror 9 Observation window 10 Lens 11 Observation screen
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平２−275800（ＪＰ，Ａ) 特開 平２−275776（ＪＰ，Ａ) 特開 平１−179790（ＪＰ，Ａ) 特開 平３−279286（ＪＰ，Ａ) ＪＰＮ．Ｊ．ＡＰＰＬ．ＰＨＹＳ．27 〜６！（1988−６）ＰＰ．Ｌ1065−Ｌ 1067 Ｊ．ＣＲＹＳＴ．ＧＲＯＷＴＨ 99 （1990）Ｐ．922−924 Ｊ．ＣＲＹＳＴ．ＧＲＯＷＴＨ 130 （1993）Ｐ．389−393 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-2-275800 (JP, A) JP-A-2-275776 (JP, A) JP-A-1-179790 (JP, A) JP-A-3-275 279286 (JP, A) JPN. J. APPL. PHYS. 27 to 6! (1988-6) PP. L1065-L1067J. CRYST. GROWTH 99 (1990) p. 922-924 J.C. CRYST. GROWTH 130 (1993) p. 389-393
Claims (5)
溶媒を加熱溶融して溶融帯を形成し、前記原料棒を下方
向に移動させることにより前記溶融帯を移動させて前記
種結晶上に単結晶を析出させるフローティングゾーン法
による希土類元素含有単結晶の製造方法において、 前記原料棒として、ＲＢａ2 Ｃｕ3 Ｏy （Ｒは、Ｙ，Ｌ
ａ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅｕ，Ｇｄ，Ｔｂ，Ｄｙ，Ｈ
ｏ，Ｅｒ，Ｔｍ，Ｙｂからなる希土類元素群から選択さ
れた一元素を表し、ｙは６．０〜７．０である。）から
なり、前記溶融帯を２〜１５ｍｍ／ｈｒの速度で移動さ
せて作成した結晶化原料棒を用い、前記結晶化原料棒を
構成する希土類元素の酸化物と、酸化バリウムあるいは
炭酸バリウムのうち少なくとも一種と、酸化銅とを元素
比にして１：４：６〜１：２９：６６の範囲で配合した
混合物で構成した溶媒であって、前記結晶化原料棒と前
記種結晶との間に設けたものからなる溶融帯を０．１〜
１．０ｍｍ／ｈｒの速度で移動させるとともに、該溶媒
の加熱温度を９２０〜１１００℃の範囲とし、少なくと
も前記溶媒の加熱雰囲気を５％以下の酸素を含む不活性
ガスとし、該不活性ガスはアルゴンガスまたは窒素ガス
のうち少なくとも１種のガスであることを特徴とする希
土類元素含有単結晶の製造方法。1. A solvent is provided between a raw material rod and a seed crystal, and the solvent is heated and melted to form a molten zone, and the raw material rod is moved downward to move the molten zone, In the method for producing a rare-earth element-containing single crystal by a floating zone method in which a single crystal is deposited on a seed crystal , RBa 2 Cu 3 O y (R is Y, L
a, Pr, Nd, Sm, Eu, Gd, Tb, Dy, H
represents one element selected from the group of rare earth elements consisting of o, Er, Tm, and Yb, and y is 6.0 to 7.0. ), The molten zone is moved at a speed of 2 to 15 mm / hr.
Using a crystallization raw material rod prepared by the above method, an oxide of a rare earth element constituting the crystallization raw material rod, at least one of barium oxide or barium carbonate, and copper oxide in an element ratio of 1: 4: 6. A solvent composed of a mixture blended in the range of １ ： 1: 29: 66 , wherein the solvent is
The molten zone formed between the seed crystal and the
Is moved at a speed of 1.0 mm / hr, the heating temperature of the solvent in the range of 920-1,100 ° C., less the
Also the heating atmosphere of the solvent is inert containing less than 5% oxygen
Gas and the inert gas is argon gas or nitrogen gas
A method for producing a rare earth element-containing single crystal , which is at least one gas selected from the group consisting of:
製造方法によって得られた単結晶を酸素雰囲気中で熱処
理することを特徴とする超伝導体の製造方法。 2. The rare-earth element-containing single crystal according to claim 1,
The single crystal obtained by the manufacturing method is heat-treated in an oxygen atmosphere.
A method of manufacturing a superconductor.
いて、前記熱処理は、２段階で行われることを特徴とす
る超伝導体の製造方法。 3. The method for manufacturing a superconductor according to claim 2, wherein
Wherein the heat treatment is performed in two stages.
Manufacturing method of superconductor.
いて、前記熱処理の第１段階は５００℃で２５時間行う
ものであることを特徴とする超伝導体の製造方法。 4. A method for manufacturing a superconductor according to claim 3, wherein
And the first stage of the heat treatment is performed at 500 ° C. for 25 hours.
A method for producing a superconductor, comprising:
造方法において、前記熱処理の第２段階は４００℃で６
０時間行うものであることを特徴とする超伝導体の製造
方法。 5. A method for producing a superconductor according to claim 3 or 4.
In the fabrication method, the second stage of the heat treatment is performed at 400 ° C. for 6 hours.
Manufacture of superconductor characterized by being performed for 0 hours
Method.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6053172A JP2733197B2 (en) | 1994-02-25 | 1994-02-25 | Method for producing rare earth element-containing single crystal |
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| Publication Number | Publication Date |
|---|---|
| JPH07237991A JPH07237991A (en) | 1995-09-12 |
| JP2733197B2 true JP2733197B2 (en) | 1998-03-30 |
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| JPH01179790A (en) * | 1988-01-12 | 1989-07-17 | Ube Ind Ltd | Production of single crystal of high temperature superconductor |
| JP2822451B2 (en) * | 1988-06-02 | 1998-11-11 | 住友電気工業株式会社 | Superconductor manufacturing method |
| JP2684432B2 (en) * | 1988-12-29 | 1997-12-03 | 弘直 兒嶋 | Superconducting oxide single crystal and method for producing the same |
| JPH03279286A (en) * | 1990-03-27 | 1991-12-10 | Kobe Steel Ltd | Preparation of raw material bar for producing single crystal of oxide superconductor |
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| Title |
|---|
| Ｊ．ＣＲＹＳＴ．ＧＲＯＷＴＨ １３０（１９９３）Ｐ．３８９−３９３ |
| Ｊ．ＣＲＹＳＴ．ＧＲＯＷＴＨ ９９（１９９０）Ｐ．９２２−９２４ |
| ＪＰＮ．Ｊ．ＡＰＰＬ．ＰＨＹＳ．２７〜６！（１９８８−６）ＰＰ．Ｌ１０６５−Ｌ１０６７ |
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