JPS61186298A - Production of single crystal - Google Patents
Production of single crystalInfo
- Publication number
- JPS61186298A JPS61186298A JP60027667A JP2766785A JPS61186298A JP S61186298 A JPS61186298 A JP S61186298A JP 60027667 A JP60027667 A JP 60027667A JP 2766785 A JP2766785 A JP 2766785A JP S61186298 A JPS61186298 A JP S61186298A
- Authority
- JP
- Japan
- Prior art keywords
- flux
- single crystal
- crystal
- pulling
- bi2o3
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B9/00—Single-crystal growth from melt solutions using molten solvents
- C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
- C30B9/08—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using other solvents
- C30B9/12—Salt solvents, e.g. flux growth
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
- C30B29/28—Complex oxides with formula A3Me5O12 wherein A is a rare earth metal and Me is Fe, Ga, Sc, Cr, Co or Al, e.g. garnets
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B9/00—Single-crystal growth from melt solutions using molten solvents
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、Ｙ ３．−ＸＢＴＸ １＋’ｅｓＯｔｚ
単結晶の製造方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention is directed to Y3. -XBTX 1+'esOtz
This invention relates to a method for producing a single crystal.
ｙ３ｒ８５ｏ１２ （以下Ｙ工Ｇと略す）は、近赤外領
域の光（波長１．５〜５μｍ）に対して吸収係数が０．
２６ ｄＢ／ｃｍ と小さく、比ファラデー回転能が
２７０°／ｃｆｎ と大きいことから光アイソレータ
等の光機能繁子に利用される。こｉ−気光学結晶である
Ｙ工ＧのＹ位置の一部を、Ｂ１で置換した結晶、Ｙ ３
−ｚＢｉＸ ？ ｅ ｓ Ｏ，ｘｚ （以下ＢｉＹ工
Ｇと略す）において比ファラデー回転能（偏光面の回転
角）の増加することが報告されている。（ａｔＴａｋｅ
ｕｃｈｊ、 ｅｔ ａｌ 、 ” Ｆａｒａｄａｙ ｒ
ｏｔａｔｉｏｎａｎｄ ｏｐｔｉｃａｌ ａｂｓｏｒｐ
ｔｉｏｎ ｏｆ ｉｈ−ｓｉｎｇｌｅｃｒｙｓｔａｌ
ｏｆ ｂｉｓｍｕｔｈ−ｓｕｂｓｔｉｔｕｔｅｄ ｇａ
ｄ。y3r85o12 (hereinafter abbreviated as Y-G) has an absorption coefficient of 0.0 for light in the near-infrared region (wavelength 1.5 to 5 μm).
Since it has a small specific Faraday rotation ability of 26 dB/cm and a large specific Faraday rotation of 270°/cfn, it is used for optical function components such as optical isolators. This is a crystal in which part of the Y position of Y-G, which is an optical crystal, is replaced with B1, Y3
-zBiX? It has been reported that the specific Faraday rotation power (rotation angle of the plane of polarization) increases in e s O,xz (hereinafter abbreviated as BiY-G). (atTake
uchj, et al, ” Faraday r
rotation and optical absorption
tion of ih-single crystal
of bismuth-substituted ga
d.
１１ｎ１．ｕｍｉｒｏｎ ｇａｒｈｅｔ”、Ｊ、Ａｐｉ
ｐｌ、Ｐｈｙｓ、 ４４゜一般に、望みのイオンを望み
の量で置換ができ、そのうえ良質な大型単結晶が得られ
るような製造方法としては、ひきあげ法が考えられる。11n1. umiron garhet”, J, Api
pl, Phys, 44° In general, the pulling method can be considered as a manufacturing method that allows replacement of desired ions in desired amounts and also provides high-quality large-sized single crystals.
しかしＢｉＹ工Ｇは十数百度で分解溶融するのでこのひ
きあげ法等の直接溶融法で製造するのは困難である。そ
のため単結晶の製造には、フラックス法が用いられる。However, since BiY-G decomposes and melts at a temperature of 10-100 degrees, it is difficult to produce it by a direct melting method such as the pulling method. Therefore, the flux method is used to manufacture single crystals.
しかし従来のフラックス法による単結晶の製造では、磁
性酸化物のかなり大きい単結晶が製造できるようになっ
た利点はあるが、■大型単結晶を得るのに長時間かかる
■単結晶育成後に方位を決定する操作が必要になる
という問題点があった。そこで本発明は、このような問
題点を解決するもので、その目的は、高品質の大型Ｂｉ
Ｙ工Ｇ単結晶を短時間に製造する方法を提供することに
ある。However, manufacturing single crystals using the conventional flux method has the advantage of being able to manufacture fairly large single crystals of magnetic oxide, but ■It takes a long time to obtain large single crystals.■It takes a long time to obtain large single crystals. Requires an operation to determine
There was a problem. The present invention is intended to solve these problems, and its purpose is to provide high-quality large-sized Bi
It is an object of the present invention to provide a method for manufacturing Y/G single crystal in a short time.
本発明は、ＢｉＹ工Ｇ単結晶の製造方法としてＢａＯ−
Ｂｉ２Ｏ３−Ｂ２Ｏ３系を用いたフラックスひきあげ法
を利用することを特徴とする。The present invention provides a method for producing a BiY engineered G single crystal.
It is characterized by utilizing a flux pulling method using the Bi2O3-B2O3 system.
本発明の上記の構成によれば種結晶の方位を任意に選ぶ
ことにより望みの方向の単結晶が得られ、また結晶径は
、ひきあげ速度と降温速度の調整により望みの大きさの
単結晶が得られる。一般のフラックスひきあげ法では、
ふたをすることができないため、フラックス法による磁
性酸化物単結晶の製造に最も使用されている、ＰｂＯお
よび（または） Ｐ ｂ Ｆ ２のような蒸気圧が高い
フラックスは、不適である。またｐｂｏｆｐｂ］ｌｒｚ
系を用いたフラックス法の場合には、ＰｂイオンがＦθ
イオンと一部置換してしまいＢｉＹ工Ｇ単結晶の光吸収
係数を劣化してしまう。According to the above configuration of the present invention, a single crystal in a desired direction can be obtained by arbitrarily selecting the orientation of the seed crystal, and the crystal diameter can be adjusted to a desired size by adjusting the pulling rate and cooling rate. can get. In the general flux pulling method,
Fluxes with high vapor pressure, such as PbO and/or PbF2, which are most used in the production of magnetic oxide single crystals by the flux method, are unsuitable because they cannot be capped. Also pbofpb]lrz
In the case of the flux method using a system, Pb ions are Fθ
This partially replaces the ions and deteriorates the optical absorption coefficient of the BiY-G single crystal.
一方、Ｂｉ２Ｏ３もフラックスとして利用されており、
Ｙ工Ｇの結晶合成も報告されている。On the other hand, Bi2O3 is also used as a flux.
Crystal synthesis of Y-G has also been reported.
（Ｊ 、Ｗ、Ｎ１ｅｌｓｅｎ：、Ｔ、Ａｐｐｌ、Ｐｈｙ
ｓ、 、 ２９ 、３９０（１９５Ｂ））
本発明は、ＢｉＹ工Ｇの製造を目的とするのであるから
このＢ’１２Ｏ３をフラックスとして用いるのが妥当で
あろう。(J, W, N1elsen:, T, Appl, Phy
s, , 29, 390 (195B)) Since the purpose of the present invention is to manufacture BiY-G, it would be appropriate to use this B'12O3 as a flux.
しかし、Ｂｉ２Ｏａのみを使用すると、このＢｉ２Ｏ３
は、容易に還元されて金属ビスマスとなり、るつぼの白
金と化合して低融点合金となる。つまり、るつぼを侵し
、しかもるつぼの成分が育成結晶中へ混入して吸収特性
を劣化してしまう。このるつぼに対する腐蝕性を改善す
るためには、Ｂｉ２Ｏ３のみの替りに本発明の上記の構
成で用いるＢａＯ−Ｂｉ２Ｏ３−Ｂ２Ｏ３系を利用する
のが最も適している。However, if only Bi2Oa is used, this Bi2O3
is easily reduced to metal bismuth, which combines with platinum in the crucible to form a low melting point alloy. In other words, the crucible is attacked, and the components of the crucible are mixed into the grown crystal, deteriorating the absorption properties. In order to improve the corrosivity of this crucible, it is most suitable to use the BaO-Bi2O3-B2O3 system used in the above configuration of the present invention instead of only Bi2O3.
またＢａＯ−Ｂｉ２Ｏ３−Ｂ２Ｏ３糸フラツクスは、ガ
ーネットと比重差が小さく、粘性も大きい。その上、不
揮発性であるので、ＢｉＹ工Ｇ単結晶のフラックスひき
あげ法による製造に最も適している。Moreover, the BaO-Bi2O3-B2O3 yarn flux has a small difference in specific gravity from garnet and has a high viscosity. Furthermore, since it is non-volatile, it is most suitable for producing BiY-G single crystals by the flux pulling method.
Ｙ２Ｏ３，Ｆｅ２Ｏ２をＹ３’Ｆθ５０１２ の組成比
となるよう秤量し、加剰Ｆｅ２Ｏ３をＹ工Ｇ： Ｆ ｅ
２Ｏ３” ５ ： １で加えたものを原料とした。フ
ラックスとしては、ＢａＯは水と反応して発熱したり、
空気中の炭酸ガスと化合したりするので安定なりａＯ０
３を用いてＢａＯ：Ｂｉ２Ｏ３：Ｂ２Ｏ３＝５０：１５
：３５となるよう秤量した。これらを７ラツクス：原料
＝６０：４０に充分混合した後、順次溶融しつつ白金る
つぼに充填し、種結晶を液面真上につむした後に１３０
０℃で２４時間保持した。Y2O3 and Fe2O2 are weighed to have a composition ratio of Y3'Fθ5012, and the excess Fe2O3 is
The raw material was 2O3" added at a ratio of 5:1. As a flux, BaO reacts with water to generate heat,
It is stable because it combines with carbon dioxide gas in the air.
3 using BaO:Bi2O3:B2O3=50:15
:35. After thoroughly mixing these at a ratio of 7 lac: raw material = 60:40, they were sequentially melted and filled into a platinum crucible, and seed crystals were placed directly above the liquid surface.
It was held at 0°C for 24 hours.
炉床部と炉上部で温度差を２５℃つけて徐冷し、１１５
０℃になったところで種結晶を１２５ ｒｐｍで回転し
つつ液面下はぼ５１Ｔｒｍの７ラツクス中へ入れ結晶径
が約１０閣になるまで１．２５ ｍｍ／ ｄａｙで育成
、ひきあげを行った。この時の成長固液界面の温度は、
約１１３０℃であった。１０３０℃までの徐冷が終了し
たらフラックスから単結晶を離し、熱衝撃を緩和するた
めに１００℃／ｈの速度で室温まで徐冷した。この育成
中に蒸発したフラックスの量は、約Ｚ５％であった。The temperature difference between the hearth and the upper part of the furnace is 25℃, and the temperature is gradually cooled to 115℃.
When the temperature reached 0° C., the seed crystal was placed in a 7-lux chamber with approximately 51 Trm below the liquid surface while rotating at 125 rpm, and was grown and pulled up at a rate of 1.25 mm/day until the crystal diameter reached approximately 10 mm. The temperature of the growing solid-liquid interface at this time is
The temperature was approximately 1130°C. After the slow cooling to 1030° C. was completed, the single crystal was separated from the flux and slowly cooled to room temperature at a rate of 100° C./h to alleviate thermal shock. The amount of flux evaporated during this growth was approximately Z5%.
スペクトル分析により、育成された単結晶への不純物の
混入量を調べたところ、［Ｌ００ｏ１〜Ｃ１，。When the amount of impurities mixed into the grown single crystal was investigated by spectral analysis, it was found that [L00o1~C1,.
０１％のＭｎ、Ｄｙ、Ｏｒ、Ｙｂ、Ｏｓ、Ａｌ。01% Mn, Dy, Or, Yb, Os, Al.
Ｂ 、 Ｓ ｉ 、 Ｏｕ 、 Ｔ ｉ 、 Ｍ ｇ
、 Ｍ Ｏが検出され、０、０００１％以下のＮｉ、Ｏ
ａ、Ｂａ、Ｓｒが検出された。、また育成された結晶中
のＹ、Ｂｉ。B, S i, Ou, T i, M g
, MO detected, less than 0,0001% Ni, O
a, Ba, and Sr were detected. , and Y and Bi in the grown crystal.
ｌｌ１ｅの組成分布をＥＭＸ （エレクトロン、マイク
ロプローブＸ線アナライザー）を使用して測定した。そ
の連続分析の結果、育成されたＢｉＹ工Ｇ単結晶の組成
分布は、底部から頂部に渡り均質であった。育成された
ＢｉＹ工Ｇ単結晶の成長面である（１１０）而の熱リン
酸及び希塩酸による腐食像を観察した。熱リン酸腐食の
場合、１ｏμ程度のエッチ、ビットが偏在し、そのエッ
チビット濃度の平均値は、１０３〜１０４個／ｃｄであ
った。希塩酸腐食の場合、１μ以下のエッチビットが１
０３〜１０４個／ｄの閾度で全体に平均してあった。The composition distribution of ll1e was measured using EMX (Electron, Microprobe X-ray analyzer). As a result of the continuous analysis, the composition distribution of the grown BiY-G single crystal was homogeneous from the bottom to the top. Corrosion images of the (110) growth surface of the grown BiY-G single crystal by hot phosphoric acid and dilute hydrochloric acid were observed. In the case of hot phosphoric acid corrosion, etch bits of about 1 μm were unevenly distributed, and the average value of the etch bit concentration was 10 3 to 10 4 bits/cd. In the case of dilute hydrochloric acid corrosion, the etch bit of 1μ or less is 1
The overall average was a threshold of 03 to 104 pieces/d.
マイクロ波用共鳴素子としての特性を確認するため、強
磁性共鳴吸収幅（以下ΔＨと記す）を測定した。この９
２Ｏ０ＭｂｚｃＸバンド２におけるΔＨはボンド法によ
り作製された約０．９ ｒｒｒｍφの球状結晶で１．２
Ｏｓ であった。また波長０．８μに対する吸収係数
は、９０ ｃｍ−”程度であった。組成比分析結果より
、育成されたＢｉＹ工Ｇ単結晶のＢｉ［換量Ｘは、Ｘ＝
１．０５で、この時のファラデー回転角（θＦ）は、波
長０．８μｍに対して８２Ｏ０ ｄｅｇ／ｌ：ｍ に達
していた。In order to confirm the characteristics as a microwave resonance element, the ferromagnetic resonance absorption width (hereinafter referred to as ΔH) was measured. This 9
ΔH in 2O0MbzcX band 2 is 1.2 for a spherical crystal of approximately 0.9 rrrmφ made by the bond method.
It was Os. In addition, the absorption coefficient at a wavelength of 0.8 μ was approximately 90 cm-”. From the composition ratio analysis results, the Bi[exchange amount
1.05, and the Faraday rotation angle (θF) at this time reached 82O0 deg/l:m for a wavelength of 0.8 μm.
以上述べたように本発明によればフラックスひきあげ法
においてフラックスとしてＢａＯ−Ｂｉ２Ｏ３−Ｂ２Ｏ
Ｓ系を用いることにより、高品質の大型ＢｉＹ工Ｇ単結
晶が短時間に製造できるという効果を有する。As described above, according to the present invention, BaO-Bi2O3-B2O is used as the flux in the flux pulling method.
The use of the S-based material has the effect that high-quality, large-sized BiY-G single crystals can be produced in a short time.
以上that's all
Claims (1)
がら単結晶を育成・ひきあげる、フラックスひきあげ法
によるＹ＿３＿−＿ＸＢＴＸ Ｆｅ５Ｏ１２単結晶の製
造方法において、フラックスとしてＢａＯ−ＢＴ２Ｏ３
−Ｂ２Ｏ３系を用いることを特徴とする単結晶の製造方
法。In the method for producing Y_3_-_XBTX Fe5O12 single crystal by the flux pulling method, which uses seed crystals from flux (fluxing agent) to grow and pull up single crystals while lowering the temperature, BaO-BT2O3 is used as the flux.
- A method for producing a single crystal, characterized by using a B2O3 system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60027667A JPS61186298A (en) | 1985-02-15 | 1985-02-15 | Production of single crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60027667A JPS61186298A (en) | 1985-02-15 | 1985-02-15 | Production of single crystal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS61186298A true JPS61186298A (en) | 1986-08-19 |
Family
ID=12227296
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60027667A Pending JPS61186298A (en) | 1985-02-15 | 1985-02-15 | Production of single crystal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61186298A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114182339A (en) * | 2021-10-29 | 2022-03-15 | 中国科学院福建物质结构研究所 | Method for growing rare earth doped yttrium iron garnet single crystal material |
-
1985
- 1985-02-15 JP JP60027667A patent/JPS61186298A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114182339A (en) * | 2021-10-29 | 2022-03-15 | 中国科学院福建物质结构研究所 | Method for growing rare earth doped yttrium iron garnet single crystal material |
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