JP2001226196A - Terbium aluminum garnet single crystal and its producing method - Google Patents
Terbium aluminum garnet single crystal and its producing methodInfo
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- JP2001226196A JP2001226196A JP2000039607A JP2000039607A JP2001226196A JP 2001226196 A JP2001226196 A JP 2001226196A JP 2000039607 A JP2000039607 A JP 2000039607A JP 2000039607 A JP2000039607 A JP 2000039607A JP 2001226196 A JP2001226196 A JP 2001226196A
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- crystal
- single crystal
- garnet single
- terbium
- aluminum garnet
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、光アイソレータ用
ファラデー回転子として好適な、テルビウム・アルミニ
ウム・ガーネット単結晶およびその製造方法に関するも
のである。The present invention relates to a terbium aluminum garnet single crystal suitable as a Faraday rotator for an optical isolator and a method for producing the same.
【０００２】[0002]
【従来の技術】テルビウム・アルミニウム・ガーネット
（略称：ＴＡＧ）単結晶の育成に関しては、過冷却状態
のルツボ内融液に基板結晶を着け、その表面に膜状に結
晶を成長させる溶液成長法（略称：ＬＰＥ法）での作製
が知られているが、実用的なバルク状結晶は作製されて
いなかった。2. Description of the Related Art With respect to the growth of terbium aluminum garnet (abbreviation: TAG) single crystal, a substrate crystal is attached to a melt in a crucible in a supercooled state, and a crystal is grown on the surface of the melt by a solution growth method ( Production by abbreviated name: LPE method) is known, but no practical bulk crystal has been produced.
【０００３】図２は、Ｔｂ２Ｏ３−Ａｌ２Ｏ３での状態
図である。図２のＴｂ２Ｏ３−Ａｌ ２Ｏ３での状態図か
らも、融液組成と同一の結晶組成を得ることの困難であ
ることが報告されている（参照；Cryst. Res. Techno
l., 34(1999)5-6, p 615-619）。[0003] FIG.2O3-Al2O3State in
FIG. Tb in FIG.2O3-Al 2O3The state diagram in
It is also difficult to obtain the same crystal composition as the melt composition.
(See; Cryst. Res. Techno
l., 34 (1999) 5-6, p 615-619).
【０００４】[0004]
【発明が解決しようとする課題】即ち、テルビウム・ア
ルミニウム・ガーネット単結晶の製造方法として最も一
般的に用いられている回転引き上げ法（略称：ＣＺ法）
では、結晶育成が進むに従って融液組成が変化し、結晶
の成長速度が小さくなることから、引き上げ速度を小さ
くすること及び融液の過冷却度を大きくすることが必要
である。That is, the rotation pulling method (abbreviation: CZ method) most commonly used as a method for producing a terbium aluminum garnet single crystal.
In this case, the melt composition changes as the crystal growth proceeds, and the crystal growth rate decreases. Therefore, it is necessary to reduce the pulling rate and increase the degree of supercooling of the melt.
【０００５】このことは、一定形状の良質結晶を安定に
育成することが困難な条件となる。通常、このような結
晶成長では、ルツボ内の融液の結晶化率が小さく、融液
の約３０％以下が結晶化できるに留まる。[0005] This is a condition under which it is difficult to stably grow a good quality crystal having a certain shape. Usually, in such crystal growth, the crystallization rate of the melt in the crucible is small, and only about 30% or less of the melt can be crystallized.
【０００６】従って、本発明の目的は、一定形状の良質
結晶であって、かつルツボ内の融液の結晶化率が大きい
状態で成長したテルビウム・アルミニウム・ガーネット
単結晶およびその製造方法を提供することである。Accordingly, an object of the present invention is to provide a terbium-aluminum-garnet single crystal which is a high-quality crystal having a uniform shape and which is grown with a high crystallization ratio of a melt in a crucible, and a method for producing the same. That is.
【０００７】[0007]
【課題を解決するための手段】本発明では、引き下げ法
によりテルビウム・アルミニウム・ガーネット単結晶を
製造している。引き下げ法とは、ルツボ底の中央にノズ
ルを設け、その先端から流出する融液に種結晶を着け、
ノズル先端の外形にほぼ等しい断面形状を持つファイバ
ー状の単結晶を得る方法である。According to the present invention, a terbium aluminum garnet single crystal is manufactured by a pulling-down method. With the lowering method, a nozzle is provided at the center of the bottom of the crucible, and a seed crystal is attached to the melt flowing out from the tip,
This is a method for obtaining a fiber-like single crystal having a cross-sectional shape substantially equal to the outer shape of the nozzle tip.
【０００８】結晶が細いことから、熱歪みの小さい良質
結晶が得易いこと、冷却速度が大きいことから添加物の
実効偏析係数が１に近いこと等の特徴から、現在、Ｎｄ
ドープＹ３Ａｌ５Ｏ１２（略称：ＹＡＧ）、Ａｌ２Ｏ３
/ＹＡＧ共晶体、シリコン等、多くの結晶作製に用いら
れている（参照；例１： 特願平１０−９８３２７号、
出願人、科学技術振興事業団、例２：J .of Crystal Gr
owth, 204(1999)155-162）。At present, Nd has been characterized by the fact that it is easy to obtain good-quality crystals with small thermal strain due to the small size of the crystal and that the effective segregation coefficient of the additive is close to 1 due to the high cooling rate.
Doped Y 3 Al 5 O 12 (abbreviation: YAG), Al 2 O 3
/ YAG eutectic, used for the production of many crystals such as silicon (see; Example 1: Japanese Patent Application No. 10-98327,
Applicant, Japan Science and Technology Agency, Example 2: J.of Crystal Gr
owth, 204 (1999) 155-262).
【０００９】引き下げ法において、ＴＡＧ融液からＴＡ
Ｇ単結晶を作製する場合、育成結晶の一部は、透明結晶
が得られるが、その他の部分は、結晶中にインクルージ
ョン等を含み、融液全体を単結晶育成することは困難で
あった。In the lowering method, the TA
In the case of producing a G single crystal, a part of the grown crystal can obtain a transparent crystal, but the other part contains inclusions and the like in the crystal, and it is difficult to grow the entire melt as a single crystal.
【００１０】融液各成分の実効偏析係数がほぼ１となる
引き下げ法を用いた場合でも、融液組成に一致した単結
晶作製が難しいことから、アルミニウムガーネット構造
においてＴｂが８配位の位置に安定に存在できないと考
えられる。そこで、結晶成長に伴って融液組成の変化し
ない融液を得る手段として、ＲＥ３Ａｌ５Ｏ１２融液
（ＲＥは希土類元素である）を加えて育成することを行
った。[0010] Even in the case of using the pulling-down method in which the effective segregation coefficient of each component of the melt is almost 1, it is difficult to produce a single crystal in accordance with the composition of the melt. It is thought that it cannot exist stably. Therefore, as means for obtaining a melt in which the melt composition does not change with the crystal growth, RE 3 Al 5 O 12 melt (RE is a rare earth element) was added and grown.
【００１１】希土類元素ＲＥとしてＬｕ、Ｙｂ、Ｔｍ、
Ｅｒのいずれか一つ以上を加えることで、アルミニウム
ガーネット結晶が安定成長することが分かった。なお、
各元素について添加量と結晶性の関係を調べ、各々に結
晶成長が安定し良質結晶が得られる適正値の存在するこ
とが分かった。Ｔｂ量に対するＬｕの適正添加量は４〜
１５％、Ｙｂについては７〜１６％、Ｔｍについては９
〜１８％、そしてＥｒについては１０〜２０％の範囲で
あることが、育成結晶の形状および結晶性の観察から判
断された。Lu, Yb, Tm, as rare earth elements RE
It was found that by adding any one or more of Er, the aluminum garnet crystal grew stably. In addition,
The relationship between the added amount and the crystallinity of each element was examined, and it was found that there was an appropriate value for stabilizing crystal growth and obtaining a good quality crystal for each element. The proper addition amount of Lu to the Tb amount is 4 to
15%, 7-16% for Yb, 9 for Tm
It was determined from the observation of the shape and crystallinity of the grown crystal that it was in the range of １８18% and Er in the range of 10-20%.
【００１２】アルミニウムガーネット構造を安定に保つ
のに、８配位原子のイオン半径の適正値が存在すると考
えられる。即ち、Ｔｂイオン半径（Ｒ８：約１００ｐ
ｍ）は、その適正値に比べ大きく、ガーネット構造が不
安定になると思われる。ガーネット構造において、イオ
ン半径の異なる８配位希土類元素の偏析係数は、そのイ
オン半径によって異なり、イオン半径に対する融液から
結晶中への各元素の偏析係数の関係は、上に凸の二次関
数に類似している（参照；Materials Science and Engi
neering,R20(1997)281-338）。It is considered that there is an appropriate value of the ionic radius of the eight-coordinate atom in order to keep the aluminum garnet structure stable. That is, the Tb ion radius (R8: about 100 p
m) is larger than its proper value, and it is considered that the garnet structure becomes unstable. In the garnet structure, the segregation coefficient of an eight-coordinate rare earth element having a different ionic radius depends on the ionic radius, and the relationship between the ionic radius and the segregation coefficient of each element from the melt to the crystal is a quadratic function having an upward convexity. (See Materials Science and Engi
neering, R20 (1997) 281-338).
【００１３】アルミニウムガーネット構造に対してＴｂ
イオンと同等の偏析係数を持ち、イオン半径がＴｂイオ
ンより小さい希土類元素ＲＥを選定し、Ｔｂ３Ａｌ５Ｏ
１２にＲＥ３Ａｌ５Ｏ１２を加えることで、アルミニウ
ムガーネット構造を安定に保つことが可能になると考え
られる。結果として、Ｌｕ、Ｙｂ、Ｔｍ、Ｅｒを選定
し、ＲＥ３Ａｌ５Ｏ１２の組成で適量を加えることで、
融液組成と同等の組成を持つ単結晶が得られ、実効偏析
係数１が実現された。Tb for aluminum garnet structure
A rare earth element RE having a segregation coefficient equivalent to that of an ion and having an ion radius smaller than that of a Tb ion is selected, and Tb 3 Al 5 O
By adding RE 3 Al 5 O 12 to 12, considered it is possible to keep the aluminum garnet structure stable. As a result, Lu, Yb, Tm, and Er are selected, and a proper amount is added by the composition of RE 3 Al 5 O 12 ,
A single crystal having a composition equivalent to the melt composition was obtained, and an effective segregation coefficient of 1 was realized.
【００１４】なお、各元素について添加量が適量に対し
て少ない場合は、ガーネット構造とペロブスカイト構造
の複数の結晶相の存在が確認され、また添加量が多い場
合は、結晶組成および格子定数が一定で無く、結晶形状
制御が不安定になり、良質単結晶を得ることが困難であ
った。When the added amount of each element is smaller than an appropriate amount, existence of a plurality of crystal phases having a garnet structure and a perovskite structure is confirmed. When the added amount is large, the crystal composition and the lattice constant are constant. However, the control of the crystal shape became unstable, and it was difficult to obtain a good quality single crystal.
【００１５】即ち、本発明は、化学式を（ＴｂＸ、ＲＥ
１−Ｘ ）３Ａｌ５Ｏ１２とし、前記化学式の中で、希
土類元素ＲＥをＬｕ、Ｙｂ、Ｔｍ、Ｅｒのいずれか一つ
以上であり、ｘの範囲を０.８≦ｘ≦０.９６とするテル
ビウム・アルミニウム・ガーネット単結晶である。That is, according to the present invention, the chemical formula is represented by (Tb X , RE
1-X ) 3 Al 5 O 12 , wherein in the above chemical formula, the rare earth element RE is at least one of Lu, Yb, Tm, and Er, and the range of x is 0.8 ≦ x ≦ 0.96. Terbium aluminum garnet single crystal.
【００１６】また、本発明は、前記テルビウム・アルミ
ニウム・ガーネット単結晶において、希土類元素ＲＥを
Ｌｕとし、化学式の中で、ｘの範囲を０.８５≦ｘ≦０.
９６とするテルビウム・アルミニウム・ガーネット単結
晶である。The present invention also relates to the terbium aluminum garnet single crystal, wherein the rare earth element RE is Lu, and the range of x in the chemical formula is 0.85 ≦ x ≦ 0.8.
96 is a terbium aluminum garnet single crystal.
【００１７】また、本発明は、前記テルビウム・アルミ
ニウム・ガーネット単結晶において、希土類元素ＲＥを
Ｙｂとし、化学式の中で、ｘの範囲を０.８５≦ｘ≦０.
９３とするテルビウム・アルミニウム・ガーネット単結
晶である。The present invention also relates to the terbium aluminum garnet single crystal, wherein the rare earth element RE is Yb, and in the chemical formula, the range of x is 0.85 ≦ x ≦ 0.8.
93 is a terbium aluminum garnet single crystal.
【００１８】また、本発明は、前記テルビウム・アルミ
ニウム・ガーネット単結晶において、希土類元素ＲＥを
Ｔｍとし、化学式の中で、ｘの範囲を０.８５≦ｘ≦０.
９１とするテルビウム・アルミニウム・ガーネット単結
晶である。The present invention also relates to the terbium aluminum garnet single crystal, wherein the rare earth element RE is Tm, and the range of x in the chemical formula is 0.85 ≦ x ≦ 0.8.
91 is a terbium aluminum garnet single crystal.
【００１９】また、本発明は、前記テルビウム・アルミ
ニウム・ガーネット単結晶において、希土類元素ＲＥを
Ｅｒとし、化学式の中で、ｘの範囲を０.８≦ｘ≦０.９
とするテルビウム・アルミニウム・ガーネット単結晶で
ある。The present invention also relates to the terbium aluminum garnet single crystal, wherein the rare earth element RE is Er, and in the chemical formula, the range of x is 0.8 ≦ x ≦ 0.9.
Terbium aluminum garnet single crystal.
【００２０】また、本発明は、ルツボ下端にノズルを設
けルツボ内の融液をノズル先端から引き下げ結晶化させ
るテルビウム・アルミニウム・ガーネット単結晶の製造
方法である。Further, the present invention is a method for producing a terbium-aluminum-garnet single crystal in which a nozzle is provided at a lower end of a crucible and a melt in the crucible is pulled down from the tip of the nozzle and crystallized.
【００２１】また、本発明は、先に記載したいずれかに
記載のテルビウム・アルミニウム・ガーネット単結晶を
主成分とする単結晶を製造するテルビウム・アルミニウ
ム・ガーネット単結晶の製造方法である。Further, the present invention is a method for producing a terbium-aluminum-garnet single crystal for producing a single crystal containing the above-mentioned terbium-aluminum-garnet single crystal as a main component.
【００２２】[0022]
【実施例】本発明の実施例によるテルビウム・アルミニ
ウム・ガーネット単結晶およびその製造方法について、
以下に説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS A terbium aluminum garnet single crystal and a method for producing the same according to an embodiment of the present invention will be described.
This will be described below.
【００２３】（実施例１）図１は、本発明の実施例によ
るテルビウム・アルミニウム・ガーネット単結晶の結晶
引き下げ法の説明図である。純度９９.９９％の酸化テ
ルビウム(化学式：Ｔｂ４Ｏ７)原料と、純度９９.９９
９％の酸化アルミニウム(化学式：Ａｌ２Ｏ ３)と純度９
９.９９％の酸化ルテチウム(化学式：Ｌｕ２Ｏ３)原料
を用い、Ｌｕ ２Ｏ３原料の添加量を０〜２０％の範囲で
各々の原料調合物を調整した。(Embodiment 1) FIG. 1 shows an embodiment of the present invention.
Terbium aluminum garnet single crystal
It is explanatory drawing of a reduction method. 99.99% pure oxide
Rubium (chemical formula: Tb4O7) Raw material and purity 99.99
9% aluminum oxide (chemical formula: Al2O 3) And purity 9
9.99% lutetium oxide (chemical formula: Lu2O3)material
Using Lu 2O3In the range of 0-20%
Each raw material formulation was prepared.
【００２４】この調合物を湿式混合し乾燥したものを最
終原料とし、Ｉｒルツボに投入し、図１に示すような通
常の結晶引下げ炉を用いてファイバー状結晶を育成し
た。ルツボ形状は、直径約１５ｍｍ、高さ約４５ｍｍ
で、ルツボ底の形状は約４５°傾斜しており、先端に５
００〜６００μｍのノズルが開いており、先端の平坦な
部分は約直径２ｍｍである。The resulting mixture was wet-mixed and dried to obtain a final raw material, which was then charged into an Ir crucible, and a fiber crystal was grown using an ordinary crystal pulling furnace as shown in FIG. Crucible shape is about 15mm in diameter and about 45mm in height
The shape of the crucible bottom is inclined about 45 °,
The nozzle of 00 to 600 μm is open, and the flat part at the tip is about 2 mm in diameter.
【００２５】即ち、ノズル先端から流出する融液に種結
晶先端を着け、種結晶を０.５〜１.０ｍｍ／ｍｉｎの速
度で引き下げながらファイバー状の結晶を育成した。育
成はＡｒ雰囲気で行い、ガス流量は０.００２ｍ３／ｍ
ｉｎとした。That is, the tip of the seed crystal was attached to the melt flowing out from the tip of the nozzle, and the seed crystal was grown at a rate of 0.5 to 1.0 mm / min while growing a fiber crystal. The growth was performed in an Ar atmosphere, and the gas flow rate was 0.002 m 3 / m
in.
【００２６】Ｌｕ２Ｏ３添加量では、４〜１５％の範囲
で良質の結晶を得ることができた。特に、７〜１２％の
範囲では、結晶形状制御性および結晶性ともに良質で、
ルツボ内の融液全体を結晶化でき、全体が透明な結晶が
得られた。With Lu 2 O 3 added, good quality crystals could be obtained in the range of 4 to 15%. In particular, in the range of 7 to 12%, both crystal shape controllability and crystallinity are good,
The entire melt in the crucible could be crystallized, and transparent crystals were obtained as a whole.
【００２７】Ｌｕ２Ｏ３添加量が４％未満の場合、結晶
外形の制御は安定するが、結晶は単一相でなく、不透明
となり、逆にＬｕ２Ｏ３添加量が１５％を超える場合
は、結晶形状が一定で無く、直径変動が大きく、透明な
部分は観察されなかった。When the added amount of Lu 2 O 3 is less than 4%, the control of the crystal shape is stable, but the crystal is not a single phase and becomes opaque, and conversely, when the added amount of Lu 2 O 3 exceeds 15%. The crystal shape was not constant, the diameter varied greatly, and no transparent portion was observed.
【００２８】（実施例２）純度９９.９９％の酸化テル
ビウム(化学式：Ｔｂ４Ｏ７)原料と、純度９９.９９９
％の酸化アルミニウム(化学式：Ａｌ２Ｏ３)と純度９
９.９９％の酸化イットリビウム(化学式：Ｙｂ２Ｏ３)
原料を用い、Ｙｂ２Ｏ３原料の添加量を０〜２５％の範
囲で各々の原料調合物を調整した。この調合物を湿式混
合し乾燥したものを最終原料とし、Ｉｒルツボに投入
し、実施例１と同様の手段および条件で結晶を育成し
た。(Example 2) A terbium oxide (chemical formula: Tb 4 O 7 ) raw material having a purity of 99.99% and a purity of 99.999
% Aluminum oxide (chemical formula: Al 2 O 3 ) and purity 9
9.99% yttrium oxide (chemical formula: Yb 2 O 3 )
Using the raw materials, each raw material mixture was adjusted in the range of 0 to 25% of the Yb 2 O 3 raw material added. The resulting mixture was wet-mixed and dried to obtain a final raw material, which was then charged into an Ir crucible, and crystals were grown under the same means and under the same conditions as in Example 1.
【００２９】Ｙｂ２Ｏ３添加量では、７〜１６％の範囲
で、ほぼ良質の結晶を得ることができた。特に、９〜１
４％の範囲では、結晶形状制御性および結晶性ともに良
質で、ルツボ内融液全体を結晶化でき、全体が透明な結
晶が得られた。With the addition amount of Yb 2 O 3 , almost good quality crystals could be obtained in the range of 7 to 16%. In particular, 9-1
In the range of 4%, both the crystal shape controllability and the crystallinity were good, the entire melt in the crucible could be crystallized, and transparent crystals were obtained as a whole.
【００３０】添加量と結晶育成状況の関係は、実施例１
のＬｕ２Ｏ３の場合と同様の傾向を示した。即ち、Ｙｂ
２Ｏ３添加量が７％未満の場合、結晶外形の制御は安定
するが、結晶は単一相でなく、不透明となり、逆にＹｂ
２Ｏ３添加量が１６％を超える場合は、結晶形状が一定
でなく、直径変動が大きく、透明な部分は観察されなか
った。Example 1 shows the relationship between the amount of addition and the state of crystal growth.
The same tendency as in the case of Lu 2 O 3 was shown. That is, Yb
When the added amount of 2 O 3 is less than 7%, the control of the crystal outer shape is stable, but the crystal is not a single phase and becomes opaque, and conversely, Yb
When the added amount of 2 O 3 exceeds 16%, the crystal shape was not constant, the diameter varied greatly, and no transparent portion was observed.
【００３１】（実施例３）直径純度９９.９９％の酸化
テルビウム(化学式：Ｔｂ４Ｏ７)原料と、純度９９.９
９９％の酸化アルミニウム(化学式：Ａｌ２Ｏ３)と純度
９９.９９％の酸化トリウム(化学式：Ｔｍ２Ｏ３)原料
を用い、Ｔｍ２Ｏ３原料の添加量を０〜２５％の範囲で
各々の原料調合物を調整した。この調合物を湿式混合し
乾燥したものを最終原料とし、Ｉｒルツボに投入し、実
施例１と同様の手段および条件で結晶を育成した。Example 3 Terbium oxide (Tb 4 O 7 ) raw material having a diameter purity of 99.99% and a purity of 99.9
Using 99% aluminum oxide (chemical formula: Al 2 O 3 ) and 99.99% pure thorium oxide (chemical formula: Tm 2 O 3 ) raw material, the addition amount of the Tm 2 O 3 raw material is in the range of 0 to 25%. Each raw material formulation was prepared. The resulting mixture was wet-mixed and dried to obtain a final raw material, which was then charged into an Ir crucible, and crystals were grown under the same means and under the same conditions as in Example 1.
【００３２】Ｔｍ２Ｏ３添加量では、９〜１８％の範囲
で、ほぼ良質の結晶を得ることができた。特に、１１〜
１６％の範囲では、結晶形状制御性および結晶性ともに
良質で、ルツボ内融液全体を結晶化でき、全体が透明な
結晶が得られた。With the added amount of Tm 2 O 3 , almost good quality crystals could be obtained in the range of 9 to 18%. In particular, 11-
In the range of 16%, both the crystal shape controllability and the crystallinity were good, the entire melt in the crucible could be crystallized, and crystals were entirely transparent.
【００３３】Ｔｍ２Ｏ３添加量と結晶育成状況の関係
は、実施例１のＬｕ２Ｏ３の場合と同様の傾向を示し
た。即ち、Ｔｍ２Ｏ３添加量が９％未満の場合、結晶外
形の制御は安定するが、結晶は単一相でなく、不透明と
なり、逆にＴｍ２Ｏ３添加量が１８％を超える場合は、
結晶形状が一定でなく、直径変動が大きく、透明な部分
は観察されなかった。The relationship between the amount of Tm 2 O 3 added and the state of crystal growth showed the same tendency as in the case of Lu 2 O 3 in Example 1. That is, when the added amount of Tm 2 O 3 is less than 9%, the control of the crystal shape is stable, but the crystal is not a single phase and becomes opaque. Conversely, when the added amount of Tm 2 O 3 exceeds 18%, ,
The crystal shape was not constant, the diameter varied greatly, and no transparent portion was observed.
【００３４】（実施例４）直径純度９９.９９％の酸化
テルビウム(化学式：Ｔｂ４Ｏ７)原料と、純度９９.９
９９％の酸化アルミニウム(化学式：Ａｌ２Ｏ３)と純度
９９.９９％の酸化エルビウム(化学式：Ｅｒ２Ｏ３)原
料を用い、Ｅｒ２Ｏ３原料の添加量を０〜２５％の範囲
で各々の原料調合物を調整した。この調合物を湿式混合
し乾燥したものを最終原料とし、Ｉｒルツボに投入し、
実施例１と同様の手段および条件で結晶を育成した。Example 4 Terbium oxide (chemical formula: Tb 4 O 7 ) raw material having a diameter purity of 99.99% and a purity of 99.9
Using 99% aluminum oxide (chemical formula: Al 2 O 3 ) and 99.99% pure erbium oxide (chemical formula: Er 2 O 3 ) raw material, the addition amount of the Er 2 O 3 raw material is in the range of 0 to 25%. Each raw material formulation was prepared. The resulting mixture was wet-mixed and dried to obtain a final raw material, which was then charged into an Ir crucible,
Crystals were grown by the same means and under the same conditions as in Example 1.
【００３５】Ｅｒ２Ｏ３添加量では、１０〜２０％の範
囲で、ほぼ良質の結晶を得ることができた。特に、１２
〜１８％の範囲では、結晶形状制御性および結晶性とも
に良質で、ルツボ内融液全体を結晶化でき、全体が透明
な結晶が得られた。Ｅｒ２Ｏ ３添加量と結晶育成状況の
関係は、実施例１のＬｕ２Ｏ３の場合と同様の傾向を示
した。Er2O3The amount of addition is in the range of 10 to 20%.
In the area, almost good quality crystals could be obtained. In particular, 12
In the range of １８18%, both crystal shape controllability and crystallinity
High quality, crystallizes the entire melt in the crucible and is entirely transparent
Crystal was obtained. Er2O 3Of the amount of addition and crystal growth
The relation is Lu of the first embodiment.2O3Shows the same tendency as
did.
【００３６】即ち、Ｅｒ２Ｏ３添加量が１０％未満の場
合、結晶外形の制御は安定するが、結晶は単一相でな
く、不透明となり、逆にＥｒ２Ｏ３添加量が２０％を超
える場合は、結晶形状が一定でなく、直径変動が大きく
透明な部分は観察されなかった。That is, when the added amount of Er 2 O 3 is less than 10%, the control of the crystal outer shape is stable, but the crystal is not a single phase and becomes opaque, and conversely, the added amount of Er 2 O 3 is 20%. If it exceeds, the crystal shape is not constant, the diameter variation is large, and no transparent part was observed.
【００３７】以上、説明したように、本発明によれば、
通常の育成方法では作製困難であったテルビウム・アル
ミニウム・ガーネット構造を持つアルミニウムガーネッ
ト単結晶の作製が可能となった。更に、可視光波長域光
アイソレータの回転子として特性の優れるＴＡＧ系単結
晶が比較的容易に得られることから、可視光波長域用の
アイソレータが実用化ができることが示された等、多く
の重大な効果が認められた。As described above, according to the present invention,
Aluminum garnet single crystals having a terbium-aluminum-garnet structure, which were difficult to produce by ordinary growing methods, can now be produced. Furthermore, since it is relatively easy to obtain a TAG-based single crystal having excellent characteristics as a rotator of a visible light wavelength range optical isolator, it has been shown that an isolator for the visible light wavelength range can be put into practical use, and many other important factors have been demonstrated. Effect was recognized.
【００３８】[0038]
【発明の効果】以上、本発明によれば、一定形状の良質
結晶であり、かつルツボ内の融液の結晶化率が大きい状
態で成長したテルビウム・アルミニウム・ガーネット単
結晶およびその製造方法を提供することができる。As described above, according to the present invention, there is provided a terbium-aluminum-garnet single crystal which is a high-quality crystal having a uniform shape and which is grown with a high crystallization ratio of a melt in a crucible, and a method for producing the same. can do.
【図１】本発明の実施例による結晶引き下げ法の説明
図。FIG. 1 is an explanatory diagram of a crystal pulling down method according to an embodiment of the present invention.
【図２】Ｔｂ２Ｏ３−Ａｌ２Ｏ３状態図。FIG. 2 is a Tb 2 O 3 —Al 2 O 3 phase diagram.
１ 石英管 ２ 保温筒 ３ ルツボ（Ｉｒ） ４ ルツボ支持治具 ５ 誘導加熱用コイル ６ 融液 ７ 育成結晶 ８ 矢印：結晶育成方向（引き下げ方向） DESCRIPTION OF SYMBOLS 1 Quartz tube 2 Insulation tube 3 Crucible (Ir) 4 Crucible support jig 5 Induction heating coil 6 Melt 7 Growing crystal 8 Arrow: Crystal growing direction (downward direction)
Claims (7)
ｌ５Ｏ１２とし、前記化学式の中の希土類元素ＲＥが、
Ｌｕ，Ｙｂ，Ｔｍ，Ｅｒのいずれか一つ以上であり、ｘ
の範囲を０.８≦ｘ≦０.９６とすることを特徴とするテ
ルビウム・アルミニウム・ガーネット単結晶。[Claim 1] The chemical formula is represented by (Tb X , RE 1-X ) 3 A
l 5 O 12 and the rare earth element RE in the above chemical formula is
At least one of Lu, Yb, Tm and Er, and x
Terbium aluminum garnet single crystal, wherein the range of 0.8 ≦ x ≦ 0.96 is satisfied.
ット単結晶において、希土類元素ＲＥをＬｕとし、化学
式の中で、ｘの範囲を０.８５≦ｘ≦０.９６とすること
を特徴とする請求項１記載のテルビウム・アルミニウム
・ガーネット単結晶。2. The terbium aluminum garnet single crystal according to claim 1, wherein the rare earth element RE is Lu, and in the chemical formula, the range of x is 0.85 ≦ x ≦ 0.96. The described terbium aluminum garnet single crystal.
ット単結晶において、希土類元素ＲＥをＹｂとし、化学
式の中で、ｘの範囲を０.８５≦ｘ≦０.９３とすること
を特徴とする請求項１記載のテルビウム・アルミニウム
・ガーネット単結晶。3. The terbium aluminum garnet single crystal according to claim 1, wherein the rare earth element RE is Yb, and in the chemical formula, the range of x is 0.85 ≦ x ≦ 0.93. The described terbium aluminum garnet single crystal.
ット単結晶において、希土類元素ＲＥをＴｍとし、化学
式の中で、ｘの範囲を０.８５≦ｘ≦０.９１とすること
を特徴とする請求項１記載のテルビウム・アルミニウム
・ガーネット単結晶。4. The terbium aluminum garnet single crystal according to claim 1, wherein the rare earth element RE is Tm, and in the chemical formula, the range of x is 0.85 ≦ x ≦ 0.91. The described terbium aluminum garnet single crystal.
ット単結晶において、希土類元素ＲＥをＥｒとし、化学
式の中で、ｘの範囲を０.８≦x≦０.９とすることを特
徴とする請求項１記載のテルビウム・アルミニウム・ガ
ーネット単結晶。5. The terbium aluminum garnet single crystal according to claim 1, wherein the rare earth element RE is Er, and in the chemical formula, the range of x is 0.8 ≦ x ≦ 0.9. The described terbium aluminum garnet single crystal.
液をノズル先端から引き下げ結晶化させることを特徴と
するテルビウム・アルミニウム・ガーネット単結晶の製
造方法。6. A method for producing a terbium-aluminum-garnet single crystal, wherein a nozzle is provided at a lower end of a crucible and a melt in the crucible is pulled down from a nozzle tip and crystallized.
ルビウム・アルミニウム・ガーネット単結晶を主成分と
する単結晶を製造することを特徴とする請求項６に記載
のテルビウム・アルミニウム・ガーネット単結晶の製造
方法。7. A terbium-aluminum-garnet single crystal according to claim 6, wherein a single crystal mainly comprising the terbium-aluminum-garnet single crystal according to any one of claims 1 to 5 is produced. Method for producing crystals.
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|---|---|---|---|
| JP2000039607A JP2001226196A (en) | 2000-02-17 | 2000-02-17 | Terbium aluminum garnet single crystal and its producing method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000039607A JP2001226196A (en) | 2000-02-17 | 2000-02-17 | Terbium aluminum garnet single crystal and its producing method |
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|---|---|
| JP2001226196A true JP2001226196A (en) | 2001-08-21 |
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ID=18563149
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