JPH09202697A - Production of bismuth-substituted type garnet - Google Patents
Production of bismuth-substituted type garnetInfo
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- JPH09202697A JPH09202697A JP791496A JP791496A JPH09202697A JP H09202697 A JPH09202697 A JP H09202697A JP 791496 A JP791496 A JP 791496A JP 791496 A JP791496 A JP 791496A JP H09202697 A JPH09202697 A JP H09202697A
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- garnet
- heat treatment
- insertion loss
- composition
- producing
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は，ファラデー効果を
有する光学用ガーネット材料の中でも，特にビスマス
（Ｂｉ）置換型ガーネットの製造方法に関し，液相成長
法（ＬＰＥ法）にて育成したＧｄＢｉ系ガーネット及び
ＴｂＢｉ系ガーネット単結晶厚膜の製造方法の改良に関
する。TECHNICAL FIELD The present invention relates to a method for producing a bismuth (Bi) substitution type garnet among optical garnet materials having a Faraday effect, and relates to a GdBi garnet grown by a liquid phase growth method (LPE method). And an improvement in a method for producing a TbBi-based garnet single crystal thick film.
【０００２】[0002]
【従来の技術】従来，光通信において，ファラデー回転
を応用したデバイスが開発，実用化されている。また，
光通信の中でも半導体レーザを使用した光通信におい
て，光ファイバーケーブルやコネクタなどからの反射光
が半導体レーザ等に戻ると発信が不安定となる。この不
安定性を防止するために，光アイソレータが使用されて
いる。2. Description of the Related Art Conventionally, in optical communication, devices applying Faraday rotation have been developed and put into practical use. Also,
Among optical communications, in optical communications using a semiconductor laser, when light reflected from an optical fiber cable, connector, etc. returns to the semiconductor laser or the like, transmission becomes unstable. Optical isolators are used to prevent this instability.
【０００３】大きなファラデー回転を持つＢｉ置換型希
土類鉄ガーネットは，ＬＰＥ法，フラックス法等で育成
され，近赤外領域での光アイソレータに使用されてい
る。特にＬＰＥ法で育成されるガーネット厚膜は，生産
性に優れているので，低価格で光アイソレータ材料の供
給を可能としている。Bi-substitution type rare earth iron garnet having a large Faraday rotation is grown by the LPE method, the flux method or the like and used for an optical isolator in the near infrared region. In particular, the garnet thick film grown by the LPE method has excellent productivity, and therefore it is possible to supply the optical isolator material at a low cost.
【０００４】ところで，光アイソレータは，順方向の光
に対してはより高い透過率を示し，逆方向の光に対して
はより低い透過率を示すことが望ましい。したがって，
それに使用されるガーネット材料は，ファラデー回転係
数が約１０００ｄｅｇ／ｃｍ2 以上と大きく，光透過率
の高い，即ち，光吸収損失が０．３ｄＢ以下であること
が要求される。このような光アイソレータ材料に用いら
れるＢｉ置換型ガーネット液相成長法は次のようにして
行われている。By the way, it is desirable that the optical isolator has a higher transmittance for light in the forward direction and a lower transmittance for light in the reverse direction. Therefore,
The garnet material used for it is required to have a large Faraday rotation coefficient of about 1000 deg / cm 2 or more and a high light transmittance, that is, a light absorption loss of 0.3 dB or less. The Bi substitution type garnet liquid phase growth method used for such an optical isolator material is performed as follows.
【０００５】白金るつぼの中に，ＰｂＯ，Ｂｉ2 Ｏ3 ，
Ｂ2 Ｏ3 をフラックス成分とし，ガーネット育成成分
（Ｇｄ2 Ｏ3 ，Ｔｂ2 Ｏ3 ，Ｆｅ2 Ｏ3 ，Ａｌ2 Ｏ3 ，
Ｇａ2Ｏ3 等）を約１０００℃にて溶解して成長用溶液
を作製した後，降温して過飽和状態とする。その溶液中
に，ガーネット基板を浸漬し，長時間回転させながら，
Ｂｉ置換型ガーネット結晶厚膜を育成する。Ｂｉ置換型
ガーネットの中でも，ＧｄＢｉ系ガーネット，ＴｂＢｉ
系ガーネットは印加磁界が約１０００Ｏｅ以下と小さ
く，小型の永久磁石を印加磁場用として利用できる特徴
がある。In a platinum crucible, PbO, Bi 2 O 3 ,
B 2 O 3 was used as a flux component, and garnet growth components (Gd 2 O 3 , Tb 2 O 3 , Fe 2 O 3 , Al 2 O 3 ,
Ga 2 O 3 etc.) is melted at about 1000 ° C. to prepare a growth solution, and then the temperature is lowered to a supersaturated state. Immerse the garnet substrate in the solution and rotate it for a long time,
A Bi substitution type garnet crystal thick film is grown. Among the Bi substitution type garnets, GdBi type garnet, TbBi
The system garnet has a small applied magnetic field of about 1000 Oe or less, and is characterized in that a small permanent magnet can be used for the applied magnetic field.
【０００６】[0006]
【発明が解決しようとする課題】光アイソレータに使用
されるＢｉ置換型ガーネットは，低い挿入損失であるこ
とが必須となり，一般には，０．３ｄＢ以下が必要とさ
れる。更に，高性能な光アイソレータには，挿入損失が
０．１ｄＢ以下のガーネット材料が要求される方向にあ
る。The Bi substitution type garnet used for the optical isolator must have a low insertion loss, and generally 0.3 dB or less is required. Furthermore, a garnet material with an insertion loss of 0.1 dB or less is required for a high performance optical isolator.
【０００７】また，ＬＰＥ法によってＢｉ置換型ガーネ
ットを工業的に安価に安定して製造できるようになり，
光学用アイソレータ材料として使用されるに至ってい
る。Further, the LPE method makes it possible to stably produce Bi substitutional garnet at low cost industrially,
It has come to be used as an optical isolator material.
【０００８】ところで，前述したＬＰＥ法は溶液中の過
飽和成分により，Ｂｉ置換型ガーネットを析出育成する
ものであり，過飽和成分の濃度管理が極めて重要とな
り，溶液の温度や流動状態によって育成ガーネットの組
成が変化し，材料特性も変化することになる。このＬＰ
Ｅ法の現状は，溶液の温度制御や基板の回転数制御等を
実施することにより，結晶育成状態を管理している。By the way, the above-mentioned LPE method deposits and grows Bi-substituted garnet by supersaturated components in the solution, and it is extremely important to control the concentration of the supersaturated components, and the composition of the grown garnet depends on the temperature and the flow state of the solution. Changes, and the material properties also change. This LP
In the present state of the E method, the crystal growth state is managed by controlling the temperature of the solution, controlling the rotation speed of the substrate, and the like.
【０００９】しかしながら，析出するガーネット組成を
十分に制御できる状態には至っていない。したがって，
特性のバラツキを生じ，光の透過率が小さくなったり，
バラツキが生じ，挿入損失を増大させることになる。However, the composition of the precipitated garnet has not been sufficiently controlled. Therefore,
There are variations in the characteristics, the light transmittance decreases,
Variations will occur and increase the insertion loss.
【００１０】そこで，本発明の技術的課題は，ＬＰＥ法
によってＢｉ2 Ｏ3 成分を多量に含有する溶液からＢｉ
2 Ｏ3 を主成分とするＢｉ置換型ガーネットを析出させ
る方法において，材料特性に大きく影響する組成のバラ
ツキを抑制し挿入損失を低減するＢｉ置換型ガーネット
の製造方法を提供することにある。Therefore, the technical problem of the present invention is to use a solution containing a large amount of Bi 2 O 3 component by the LPE method to obtain Bi.
It is an object of the present invention to provide a method for producing a Bi-substituted garnet, which suppresses variation in composition that greatly affects material properties and reduces insertion loss in the method of depositing Bi-substituted garnet containing 2 O 3 as a main component.
【００１１】[0011]
【課題を解決するための手段】本発明によれば，ガーネ
ット基板上に，液相成長法によりＧｄＢｉ系ガーネット
単結晶またはＴｂＢｉ系ガーネット単結晶からなるＢｉ
置換型ガーネットを育成して光学用ガーネット材料を製
造する方法において，前記Ｂｉ置換型ガーネットを育成
後，熱処理によりＢｉ2 Ｏ3 組成値を０．０５〜１．２
５ｗｔ％減少させることを特徴とするＢｉ置換型ガーネ
ットの製造方法が得られる。According to the present invention, on a garnet substrate, a Bi crystal composed of a GdBi-based garnet single crystal or a TbBi-based garnet single crystal is formed by a liquid phase growth method.
In a method of growing a substitutional garnet to manufacture an optical garnet material, after growing the Bi substitutional garnet, a Bi 2 O 3 composition value is 0.05 to 1.2 by heat treatment.
A method for producing a Bi-substituted garnet is obtained which is characterized by reducing the amount by 5 wt%.
【００１２】ここで，本発明において，Ｂｉ置換型ガー
ネット材料に含有している局部的なＢｉ2 Ｏ3 過剰成分
を熱処理することにより除去し，熱的に平衡状態に組成
を近づけ，均質化を進行させ，同時に結晶格子の規則性
を向上させることにより，ガーネット材の挿入損失の低
減を実現するものである。本発明において，この熱処理
によるＢｉ2 Ｏ3 組成値の減少量０．０５〜１．２５ｗ
ｔ％の範囲と限定したのは，０．０５ｗｔ％以上で，挿
入損失の低減が顕著となり，１．２５ｗｔ％以上では，
挿入損失の増大が顕著となるからである。Here, in the present invention, the local Bi 2 O 3 excess component contained in the Bi-substituted garnet material is removed by heat treatment to bring the composition into a state of thermal equilibrium to homogenize it. By advancing it and improving the regularity of the crystal lattice at the same time, the insertion loss of the garnet material is reduced. In the present invention, the decrease in Bi 2 O 3 composition value due to this heat treatment is 0.05 to 1.25w.
The range of t% is limited to 0.05 wt% or more, the insertion loss is significantly reduced, and 1.25 wt% or more,
This is because the insertion loss is significantly increased.
【００１３】また，本発明によれば，前記Ｂｉ置換型ガ
ーネットの製造方法において，前記熱処理温度が，１０
３０〜１１９０℃の範囲にあることを特徴とするＢｉ置
換型ガーネットの製造方法が得られる。Further, according to the present invention, in the method for manufacturing the Bi substitution type garnet, the heat treatment temperature is 10
A method for producing a Bi-substituted garnet characterized by being in the range of 30 to 1190 ° C is obtained.
【００１４】ここで，本発明において，熱処理は，Ｂｉ
2 Ｏ3 の減少量と組成の均質化，結晶格子の規則性向上
させる。本発明において，この熱処理温度を１０３０〜
１１９０℃の範囲と限定したのは，１０３０℃以上で，
挿入損失の低減が顕著になると判断できるからであり，
また，１１９０℃以上で，挿入損失の増大が顕著になる
と判断できるからである。In the present invention, the heat treatment is Bi
It reduces the amount of 2 O 3 , homogenizes the composition, and improves the regularity of the crystal lattice. In the present invention, this heat treatment temperature is 1030 to
The range of 1190 ℃ is limited to 1030 ℃ or more,
This is because it can be judged that the reduction in insertion loss will be significant.
Also, it can be judged that the increase in insertion loss becomes remarkable at 1190 ° C. or higher.
【００１５】また，本発明によれば，前記した内のいず
れかのＢｉ置換型ガーネットの製造方法において，前記
熱処理における保持時間が０．５〜４０時間の範囲内に
あることを特徴とするＢｉ置換型ガーネットの製造方法
が得られる。Further, according to the present invention, in any one of the above-mentioned methods for producing a Bi-substituted garnet, the holding time in the heat treatment is in the range of 0.5 to 40 hours. A method for manufacturing a substitutional garnet is obtained.
【００１６】ここで，本発明において，熱処理における
保持時間は，Ｂｉ2 Ｏ3 の減少量にも寄与するが，主に
組成の均質化，結晶格子規則性向上させる。本発明にお
いて，熱処理温度の保持時間０．５〜４０時間の範囲内
であると限定した理由は，０．５時間以上で，挿入損失
の低減が顕著になるからであり，４０時間以上は，長時
間となり，工業的に不利益となるからである。Here, in the present invention, the holding time in the heat treatment contributes to the reduction amount of Bi 2 O 3 , but mainly improves the homogenization of the composition and the crystal lattice regularity. In the present invention, the reason why the holding time of the heat treatment temperature is limited to be within the range of 0.5 to 40 hours is that the reduction of the insertion loss becomes remarkable when the time is 0.5 hours or more. This is because it takes a long time and is industrially disadvantageous.
【００１７】また，本発明によれば，前記した内のいず
れかのＢｉ置換型ガーネットの製造方法において，前記
熱処理における雰囲気の酸素濃度が２〜１００％の範囲
にあることを特徴とするＢｉ置換型ガーネットの製造方
法が得られる。According to the present invention, in any one of the above-mentioned methods for producing a Bi-substituted garnet, the oxygen concentration of the atmosphere in the heat treatment is in the range of 2 to 100%. A method of manufacturing a mold garnet is obtained.
【００１８】ここで，本発明において，熱処理雰囲気は
主に酸素の空格子に関係し，主に結晶格子の規則性向上
させるのに効果がある。本発明において，熱処理雰囲気
の酸素濃度２〜１００％の範囲内と限定したのは，２％
以上で挿入損失の低減が顕著となるからである。Here, in the present invention, the heat treatment atmosphere mainly relates to the oxygen vacancies, and is effective in mainly improving the regularity of the crystal lattice. In the present invention, the oxygen concentration of the heat treatment atmosphere is limited to the range of 2 to 100% is 2%.
This is because the insertion loss is significantly reduced as described above.
【００１９】したがって，本発明においては，光アイソ
レータ等に使用されるＢｉ置換型ガーネットの挿入損失
の低減が，容易に実現できる。Therefore, in the present invention, the reduction of the insertion loss of the Bi substitution type garnet used for the optical isolator or the like can be easily realized.
【００２０】[0020]
【発明の実施の形態】以下，本発明の実施の形態につい
て図面を参照して説明する。Embodiments of the present invention will be described below with reference to the drawings.
【００２１】（第１の実施の形態）高純度（９９．９％
以上）の酸化ガドリニウム（Ｇｄ2 Ｏ3 ），酸化第２鉄
（Ｆｅ2 Ｏ3 ），酸化アルミニウム（Ａｌ2 Ｏ3 ），酸
化ガリウム（Ｇａ2 Ｏ3 ），酸化ビスマス（Ｂｉ
2 Ｏ3 ），酸化鉛（ＰｂＯ）及び酸化ホウ素（Ｂ
2 Ｏ3 ）の粉末を原料として使用し，フラックスとして
ＰｂＯ−Ｂｉ2 Ｏ3 −Ｂ2 Ｏ3 系を使用して，ＬＰＥ法
により（ＧｄＢｉ）3 （ＦｅＧａＡｌ）5 Ｏ12系ガーネ
ットを育成した。この時使用した基板はＮｄ3 Ｇａ5 Ｏ
12単結晶であり，格子定数は１２，５０９Å，基板の方
位は＜１１１＞である。また結晶育成は約７５０℃の融
液中で，上記基板を回転して行ない，厚さ約５００μｍ
のＧｄ2.1 Ｂｉ0.9Ｆｅ4.6 Ｇａ0.2 Ａｌ0.2 Ｏ12なる
組成を有するＧｄＢｉ系ガーネット厚膜単結晶を得た。(First Embodiment) High purity (99.9%)
Gadolinium oxide (Gd 2 O 3 ), ferric oxide (Fe 2 O 3 ), aluminum oxide (Al 2 O 3 ), gallium oxide (Ga 2 O 3 ), bismuth oxide (Bi)
2 O 3 ), lead oxide (PbO) and boron oxide (B
2 O 3 ) powder was used as the raw material and PbO-Bi 2 O 3 -B 2 O 3 system was used as the flux to grow (GdBi) 3 (FeGaAl) 5 O 12 system garnet by the LPE method. The substrate used at this time is Nd 3 Ga 5 O
It is a 12 single crystal, has a lattice constant of 12,509Å, and has a substrate orientation of <111>. Crystal growth was carried out by rotating the above substrate in a melt at about 750 ° C., and the thickness was about 500 μm.
A GdBi-based garnet thick film single crystal having a composition of Gd 2.1 Bi 0.9 Fe 4.6 Ga 0.2 Al 0.2 O 12 was obtained.
【００２２】次に，この試料の基板を除去した後，大気
中，１０５０〜１１５０℃で０〜１００時間保持した。
次に，これらＧｄＢｉ系ガーネット試料の両面を研磨
し，厚さ約３５０μｍの試料板とした。Next, after removing the substrate of this sample, it was held in the atmosphere at 1050-1150 ° C. for 0-100 hours.
Next, both surfaces of these GdBi-based garnet samples were polished to form a sample plate having a thickness of about 350 μm.
【００２３】次に，これら試料板の両面について５点ず
つＥＰＭＡ分析を行ない計１０点の平均値をＢｉ2 Ｏ3
組成値とした。Next, 5 points of EPMA analysis were performed on each of the two surfaces of these sample plates, and the average value of 10 points in total was Bi 2 O 3
The composition value was used.
【００２４】次に，これら試料板にＳｉＯ2 膜による無
反射被覆処理を行なった後，約１ＫＯｅの磁界を印加
し，波長１．３μｍにおける挿入損失を測定した。Next, these sample plates were subjected to antireflection coating with a SiO 2 film, and then a magnetic field of about 1 KOe was applied to measure the insertion loss at a wavelength of 1.3 μm.
【００２５】図１はガーネット厚膜結晶のＢｉ2 Ｏ3 組
成減少値と挿入損失の関係を示す図である。ここで，ガ
ーネット厚膜結晶のＢｉ2 Ｏ3 組成減少値とは，非熱処
理試料に対し，熱処理により変動したＢｉ2 Ｏ3 組成値
を表している。図１からわかるように，Ｂｉ2 Ｏ3 の組
成減少量が０．０５ｗｔ％以上では挿入損失が顕著に低
下し，一方１．２５ｗｔ％以上では挿入損失が顕著に増
大している。したがって，ＧｄＢｉ系ガーネット厚膜に
おいては，そのＢｉ2 Ｏ3 組成減少値が０．０５〜１．
２５ｗｔ％となる様に熱処理することにより，挿入損失
は著しく改善されることが分かる。FIG. 1 is a graph showing the relationship between the Bi 2 O 3 composition reduction value and the insertion loss of a garnet thick film crystal. Herein, the Bi 2 O 3 composition reduction value garnet thick film crystals, relative to non-heat samples represent Bi 2 O 3 composition value varied by heat treatment. As can be seen from FIG. 1, when the composition reduction amount of Bi 2 O 3 is 0.05 wt% or more, the insertion loss is remarkably reduced, while when it is 1.25 wt% or more, the insertion loss is remarkably increased. Therefore, in the GdBi-based garnet thick film, the Bi 2 O 3 composition reduction value is 0.05 to 1.
It can be seen that the insertion loss is remarkably improved by performing the heat treatment so as to be 25 wt%.
【００２６】（第２の実施の形態）第１の実施の形態と
同様にして，ＧｄＢｉ系ガーネット厚膜単結晶を育成，
基板除去後，１０００〜１２００℃で１０時間熱処理，
研磨して試料を得た後，ＥＰＭＡ分析によりＧｄＢｉ系
ガーネットのＢｉ2 Ｏ3 組成を測定し，熱処理によるＢ
ｉ2 Ｏ3 組成減少値を求めた。(Second Embodiment) In the same manner as in the first embodiment, a GdBi-based garnet thick film single crystal is grown.
After removing the substrate, heat treatment at 1000 ~ 1200 ℃ for 10 hours,
After polishing and obtaining a sample, the Bi 2 O 3 composition of the GdBi garnet was measured by EPMA analysis, and B by heat treatment was measured.
The i 2 O 3 composition reduction value was determined.
【００２７】図２は熱処理温度とＧｄＢｉ系ガーネット
のＢｉ2 Ｏ3 組成減少値を示す図である。熱処理温度が
１０３０℃以上でＢｉ2 Ｏ3 組成減少値が０．０５ｗｔ
％以上となり，１１９０℃以下で１．２５ｗｔ％以下と
なる。したがって，実施例１の結果と合わせて判断する
と，挿入損失が顕著に減少する熱処理温度は１０３０〜
１１９０℃となり，この温度範囲が有用となる。FIG. 2 is a graph showing the heat treatment temperature and the Bi 2 O 3 composition reduction value of the GdBi garnet. When the heat treatment temperature is 1030 ° C or higher, the Bi 2 O 3 composition reduction value is 0.05 wt.
% Or more and 1.25 wt% or less at 1190 ° C. or less. Therefore, judging from the results of Example 1, the heat treatment temperature at which the insertion loss is significantly reduced is 1030 to
It becomes 1190 ° C, and this temperature range becomes useful.
【００２８】（第３の実施の形態）第１の実施の形態と
同様にして，ＧｄＢｉ系ガーネット厚膜単結晶を育成，
基板除去後，１１００℃で０〜４０時間熱処理，研磨し
た後，無反射被覆処理をした後，波長１．３μｍにおけ
る各試料の挿入損失を測定した。(Third Embodiment) In the same manner as the first embodiment, a GdBi-based garnet thick film single crystal is grown.
After removing the substrate, the sample was heat-treated at 1100 ° C. for 0 to 40 hours, polished, and subjected to antireflection coating, and then the insertion loss of each sample at a wavelength of 1.3 μm was measured.
【００２９】図３は１１００℃における熱処理の保持温
度と挿入損失の関係を示す図である。保持時間が０．５
時間以上で，挿入損失の著しい減少が認められる。工業
上は，１１００℃で４０時間保持とすると，１回の熱処
理に約２日を要することになり，それ以上の長時間保持
は特策とはいえない。したがって，保持時間は０．５〜
４０時間が工業上有用な範囲とした。FIG. 3 is a diagram showing the relationship between the holding temperature of heat treatment at 1100 ° C. and the insertion loss. Retention time 0.5
A significant decrease in insertion loss is observed over time. Industrially, if the temperature is maintained at 1100 ° C. for 40 hours, one heat treatment requires about 2 days, and holding for a longer time cannot be said to be a special measure. Therefore, the holding time is 0.5 ~
40 hours was set to a range that is industrially useful.
【００３０】（第４の実施の形態）第１の実施の形態と
同様にして，ＧｄＢｉ系ガーネット厚膜単結晶を育成，
基板除去後，窒素中雰囲気，酸素混入雰囲気，酸素中雰
囲気にて，１１００℃で１０時間熱処理した後，研磨，
無反射被覆処理をした後，１．３μｍにおける各試料の
挿入損失を測定した。(Fourth Embodiment) A GdBi-based garnet thick film single crystal is grown in the same manner as in the first embodiment.
After removing the substrate, heat treatment at 1100 ° C. for 10 hours in a nitrogen atmosphere, an oxygen mixed atmosphere, or an oxygen atmosphere, followed by polishing,
After the antireflection coating treatment, the insertion loss of each sample at 1.3 μm was measured.
【００３１】図４は１１００℃における熱処理雰囲気の
酸素濃度と挿入損失の関係を示す図である。酸素濃度を
２％以上とすることで，挿入損失が著しく低減する。し
たがって，熱処理雰囲気の酸素濃度は２〜１００％が有
用となる。FIG. 4 is a graph showing the relationship between the oxygen concentration in the heat treatment atmosphere at 1100 ° C. and the insertion loss. By setting the oxygen concentration to 2% or more, the insertion loss is significantly reduced. Therefore, it is useful that the oxygen concentration of the heat treatment atmosphere is 2 to 100%.
【００３２】（第５の実施の形態）高純度（９９．９％
以上）の酸化テルビニウム（Ｔｂ2 Ｏ3 ），酸化ガドリ
ニウム（Ｇｄ2 Ｏ3 ），酸化第２鉄（Ｆｅ2 Ｏ3 ），酸
化アルミニウム（Ａｌ2 Ｏ3 ），酸化ビスマス（Ｂｉ2
Ｏ3 ），酸化鉛（ＰｂＯ）及び酸化ホウ素（Ｂ2 Ｏ3 ）
の粉末を原料として使用し，（ＧｄＣａ）3 （ＧａＭｇ
Ｚｒ）5 Ｏ15基板（格子定数１２，４９０Å，基板方位
＜１１１＞）上に，第１の実施の形態と同様にして，Ｔ
ｂ2.1 Ｂｉ0.9 Ｆｅ5 Ｏ12なる組成のＴｂＢｉ系ガーネ
ット厚膜（約５００μｍ厚）と，Ｔｂ2.0 Ｇｄ0.1 Ｂｉ
0.9 Ｆｅ4.6 Ｇａ0.2 Ａｌ0.2 Ｏ12なる組成のＴｂＢｉ
ガーネット厚膜（約４５０μｍ厚）を，第１の実施の形
態と同様にして，ＬＰＥ法にて作製した。(Fifth Embodiment) High purity (99.9%)
Terbium oxide (Tb 2 O 3 ), gadolinium oxide (Gd 2 O 3 ), ferric oxide (Fe 2 O 3 ), aluminum oxide (Al 2 O 3 ), bismuth oxide (Bi 2)
O 3 ), lead oxide (PbO) and boron oxide (B 2 O 3 ).
Powder of (GdCa) 3 (GaMg)
On a Zr) 5 O 15 substrate (lattice constant 12,490Å, substrate orientation <111>), as in the first embodiment, T
b 2.1 Bi 0.9 Fe 5 O 12 TbBi-based garnet thick film (about 500 μm thick) and Tb 2.0 Gd 0.1 Bi
TbBi having a composition of 0.9 Fe 4.6 Ga 0.2 Al 0.2 O 12
A garnet thick film (about 450 μm thick) was produced by the LPE method in the same manner as in the first embodiment.
【００３３】次に，第１の実施の形態と同様にして基板
除去後，空気中１１００℃で５時間熱処理した後，研
磨，無反射被覆処理した後，波長１．３μｍにおける各
試料の挿入損失を測定した。その結果を下記表１に示
す。Next, as in the first embodiment, after removing the substrate, heat-treating in air at 1100 ° C. for 5 hours, polishing, and antireflection coating, and then the insertion loss of each sample at a wavelength of 1.3 μm. Was measured. The results are shown in Table 1 below.
【００３４】[0034]
【表１】 [Table 1]
【００３５】尚，熱処理によるＢｉ2 Ｏ3 組成減少値は
０．１５〜０．２ｗｔ％の範囲であった。熱処理によ
り，挿入損失が著しく低減し，熱処理はＴｂＢｉガーネ
ットにおいても，ＧａＢｉ系ガーネットと同様に有用で
あることがわかる。The Bi 2 O 3 composition reduction value due to the heat treatment was in the range of 0.15 to 0.2 wt%. It can be seen that the heat treatment significantly reduces the insertion loss, and that the heat treatment is as effective for the TbBi garnet as for the GaBi garnet.
【００３６】また，本発明は上記実施の形態の組成，波
長にとどまるものではなく，ＬＰＥ法で作製されたＧｄ
Ｂｉ系ガーネット，ＴｂＢｉ系ガーネットに適用するこ
とができる。測定波長がガーネットの吸収スペクトルに
対応していない。Further, the present invention is not limited to the composition and wavelength of the above-mentioned embodiment, but Gd produced by the LPE method.
It can be applied to Bi type garnet and TbBi type garnet. The measured wavelength does not correspond to the absorption spectrum of garnet.
【００３７】上記実施の形態に示したガーネットのその
他の特性は，波長１．３μｍにおけるファラデー回転係
数は約１３００ｄｅｇ／ｃｍ以上であり，飽和磁化は，
ＧｄＢｉ系ガーネットが約２００Ｇ，ＴｂＢｉ系ガーネ
ットが約６００〜８００Ｇであり，ファラデー回転素子
例えば光アイソレータ用としては実用できる特性を示し
ている。Other characteristics of the garnet shown in the above embodiment are that the Faraday rotation coefficient at a wavelength of 1.3 μm is about 1300 deg / cm and the saturation magnetization is
The GdBi-based garnet is about 200 G, and the TbBi-based garnet is about 600 to 800 G, which shows characteristics that can be practically used for a Faraday rotation element such as an optical isolator.
【００３８】[0038]
【発明の効果】以上，説明したように，本発明によれ
ば，ＬＰＥ法によってＢｉ2 Ｏ3 成分を多量に含有する
溶液からＢｉ2 Ｏ3 を主成分とするＢｉ置換型ガーネッ
トを析出させる方法において，材料特性に大きく影響す
る組成のバラツキを抑制し挿入損失を低減するＢｉ置換
型ガーネット材料の製造方法を提供することにある。As described above, according to the present invention, a method for precipitating a Bi-substituted garnet containing Bi 2 O 3 as a main component from a solution containing a large amount of Bi 2 O 3 component by the LPE method. In view of the above, it is another object of the present invention to provide a method for producing a Bi-substitution type garnet material, which suppresses variation in composition that greatly affects material properties and reduces insertion loss.
【図１】第１の実施の形態において，ＧｄＢｉ系ガーネ
ット材の熱処理におけるＢｉ2Ｏ3 組成減少値と波長
１．３μｍにおける挿入損失の関係を示す図である。FIG. 1 is a diagram showing a relationship between a reduction value of Bi 2 O 3 composition in a heat treatment of a GdBi-based garnet material and an insertion loss at a wavelength of 1.3 μm in the first embodiment.
【図２】第２の実施の形態において，ＧｄＢｉ系ガーネ
ット材の熱処理におけるＢｉ2Ｏ3 組成減少値と熱処理
温度との関係を示す図である。FIG. 2 is a diagram showing a relationship between a heat treatment temperature and a Bi 2 O 3 composition reduction value in heat treatment of a GdBi-based garnet material in the second embodiment.
【図３】第３の実施の形態において，ＧｄＢｉ系ガーネ
ット材の熱処理における保持時間と挿入損失の関係を示
す図である。FIG. 3 is a diagram showing a relationship between a holding time and an insertion loss in heat treatment of a GdBi-based garnet material in the third embodiment.
【図４】第４の実施の形態において，ＧｄＢｉ系ガーネ
ット材の熱処理における雰囲気の酸素濃度と挿入損失の
関係を示す図である。FIG. 4 is a diagram showing the relationship between the oxygen concentration in the atmosphere and the insertion loss during heat treatment of a GdBi-based garnet material in the fourth embodiment.
Claims (4)
ＧｄＢｉ系ガーネット単結晶またはＴｂＢｉ系ガーネッ
ト単結晶からなるＢｉ置換型ガーネットを育成して光学
用ガーネット材料を製造する方法において，前記Ｂｉ置
換型ガーネットを育成後，熱処理によりＢｉ2 Ｏ3 組成
値を０．０５〜１．２５ｗｔ％減少させることを特徴と
するＢｉ置換型ガーネットの製造方法。1. A method for producing an optical garnet material by growing a Bi substitution type garnet composed of a GdBi type garnet single crystal or a TbBi type garnet single crystal on a garnet substrate by a liquid phase growth method, wherein the Bi substitution type garnet material is manufactured. A method for producing a Bi-substituted garnet, which comprises reducing the Bi 2 O 3 composition value by 0.05 to 1.25 wt% by heat treatment after growing the garnet.
製造方法において，前記熱処理温度が，１０３０〜１１
９０℃の範囲にあることを特徴とするＢｉ置換型ガーネ
ットの製造方法。2. The method for producing a Bi-substituted garnet according to claim 1, wherein the heat treatment temperature is 1030 to 11
A method for producing a Bi-substituted garnet, which is in the range of 90 ° C.
ットの製造方法において，前記熱処理における保持時間
が０．５〜４０時間の範囲内にあることを特徴とするＢ
ｉ置換型ガーネットの製造方法。3. The method for producing a Bi-substituted garnet according to claim 1 or 2, wherein a holding time in the heat treatment is within a range of 0.5 to 40 hours.
Method for manufacturing i-substitution garnet.
のＢｉ置換型ガーネットの製造方法において，前記熱処
理における雰囲気の酸素濃度が２〜１００％の範囲にあ
ることを特徴とするＢｉ置換型ガーネットの製造方法。4. The method for producing a Bi-substituted garnet according to claim 1, wherein the oxygen concentration of the atmosphere in the heat treatment is in the range of 2 to 100%. Type garnet manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP791496A JPH09202697A (en) | 1996-01-19 | 1996-01-19 | Production of bismuth-substituted type garnet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP791496A JPH09202697A (en) | 1996-01-19 | 1996-01-19 | Production of bismuth-substituted type garnet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09202697A true JPH09202697A (en) | 1997-08-05 |
Family
ID=11678816
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP791496A Withdrawn JPH09202697A (en) | 1996-01-19 | 1996-01-19 | Production of bismuth-substituted type garnet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09202697A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7133189B2 (en) * | 2002-02-22 | 2006-11-07 | Tdk Corporation | Magnetic garnet material, faraday rotator, optical device, bismuth-substituted rare earth-iron-garnet single-crystal film and method for producing the same and crucible for producing the same |
| US7695562B2 (en) | 2006-01-10 | 2010-04-13 | Tdk Corporation | Magnetic garnet single crystal and method for producing the same as well as optical element using the same |
| US7758766B2 (en) | 2007-09-17 | 2010-07-20 | Tdk Corporation | Magnetic garnet single crystal and Faraday rotator using the same |
| US7811465B2 (en) | 2004-11-19 | 2010-10-12 | Tdk Corporation | Magnetic garnet single crystal and optical element using same as well as method of producing single crystal |
| US7828895B2 (en) | 2006-01-27 | 2010-11-09 | Tdk Corporation | Method of producing optical element |
| US8142676B2 (en) | 2006-02-20 | 2012-03-27 | Tdk Corporation | Magnetic garnet single crystal and optical element using the same |
-
1996
- 1996-01-19 JP JP791496A patent/JPH09202697A/en not_active Withdrawn
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7133189B2 (en) * | 2002-02-22 | 2006-11-07 | Tdk Corporation | Magnetic garnet material, faraday rotator, optical device, bismuth-substituted rare earth-iron-garnet single-crystal film and method for producing the same and crucible for producing the same |
| US7333261B2 (en) | 2002-02-22 | 2008-02-19 | Tdk Corporation | Magnetic garnet material, faraday rotator, optical device, bismuth-substituted rare earth-iron-garnet single-crystal film and method for producing the same crucible for producing the same |
| US7517406B2 (en) | 2002-02-22 | 2009-04-14 | Tdk Corporation | Magnetic garnet material, faraday rotator, optical device, bismuth-substituted rare earth-iron-garnet single-crystal film and method for producing the same and crucible for producing the same |
| US7811465B2 (en) | 2004-11-19 | 2010-10-12 | Tdk Corporation | Magnetic garnet single crystal and optical element using same as well as method of producing single crystal |
| US8815011B2 (en) | 2004-11-19 | 2014-08-26 | Tdk Corporation | Magnetic garnet single crystal and optical element using same as well as method of producing single crystal |
| US7695562B2 (en) | 2006-01-10 | 2010-04-13 | Tdk Corporation | Magnetic garnet single crystal and method for producing the same as well as optical element using the same |
| US7828895B2 (en) | 2006-01-27 | 2010-11-09 | Tdk Corporation | Method of producing optical element |
| US8142676B2 (en) | 2006-02-20 | 2012-03-27 | Tdk Corporation | Magnetic garnet single crystal and optical element using the same |
| US7758766B2 (en) | 2007-09-17 | 2010-07-20 | Tdk Corporation | Magnetic garnet single crystal and Faraday rotator using the same |
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