JPH01294592A - Growth of single crystal - Google Patents
Growth of single crystalInfo
- Publication number
- JPH01294592A JPH01294592A JP12397788A JP12397788A JPH01294592A JP H01294592 A JPH01294592 A JP H01294592A JP 12397788 A JP12397788 A JP 12397788A JP 12397788 A JP12397788 A JP 12397788A JP H01294592 A JPH01294592 A JP H01294592A
- Authority
- JP
- Japan
- Prior art keywords
- coracle
- single crystal
- raw material
- diameter
- material melt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000013078 crystal Substances 0.000 title claims abstract description 39
- 239000002994 raw material Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 abstract description 11
- 230000007547 defect Effects 0.000 abstract description 3
- 239000000155 melt Substances 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000002109 crystal growth method Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- BSYNRYMUTXBXSQ-UHFFFAOYSA-N Aspirin Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O BSYNRYMUTXBXSQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910004606 CdTc Inorganic materials 0.000 description 1
- 229910004541 SiN Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
- Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、ＧａＡｓ、 ｌｎＰ等のｍ−ｖ族化合物半導
体、ＣｄＴｃ等のｎ−ｖｔ族化合物半導体、Ｓｉ、Ｇｅ
等の１１導体、１．１Ｎｂｏ、、Ｂ！ ＋ ｔｓｉｏｙ
ｏ等の酸化物単結晶をチョクラルスキー法で育成する方
法に関する。Detailed Description of the Invention (Industrial Application Field) The present invention is applicable to m-v group compound semiconductors such as GaAs and lnP, n-vt group compound semiconductors such as CdTc, Si, Ge
11 conductors such as 1.1Nbo,,B! + tsioy
This invention relates to a method for growing single crystals of oxides such as o by the Czochralski method.
（従来の技術）
第４図はコラクルを用いた従来の単結晶の育成方法（特
開昭６２−２８８１９３号公報）の説明図である。この
方法は、るつぼ１に収容した原料融液２の中に逆円錐形
のコラクル】３を浸漬させ、該コラクルの先端の小間口
１４より、原料融液４を流入させ、単結晶５を引き上げ
るもので、るつぼに対するコラクルの相対移動速度を変
化させて、各工程毎に適した過冷却領域を確保すること
により、デンドライト成長を含まない良質な単結晶を製
造しようとするものである。その際、コラクル内原料融
液表面はるつぼ内原料融液表面より８１以上低く維持さ
れている。(Prior Art) FIG. 4 is an explanatory diagram of a conventional single crystal growth method using a coracle (Japanese Patent Laid-Open No. 62-288193). In this method, an inverted conical coracle 3 is immersed in a raw material melt 2 housed in a crucible 1, and a raw material melt 4 is flowed in through a small opening 14 at the tip of the coracle to pull up a single crystal 5. This method attempts to produce high-quality single crystals that do not contain dendrite growth by changing the relative movement speed of the coracle with respect to the crucible to ensure an appropriate supercooling region for each step. At this time, the surface of the raw material melt in the coracle is maintained 81 or more lower than the surface of the raw material melt in the crucible.
（発明が解決しようとする課題）
Ｉ―記の方法では第３図の矢印１５のように、唯一の小
開口Ｉ４よりコラクル内に熱い原料セ液が導入され、成
長結晶５の中心部に当たってから周囲に広がるため、固
液界面は上に凸化し易く、多結晶化や高転位化などの結
晶欠陥を発生させることになる。なお、小開口の断面積
を小さくして、コラクル内の原料融液の対流を抑制する
ことも考えられるが、流入抵抗が大きくなり、特に、直
径の大きな単結晶を引き上げようとするときには、原料
融液の流入が追い付かなくなる。(Problem to be Solved by the Invention) In the method described in I-, hot raw material separator liquid is introduced into the coracle through the only small opening I4, as shown by arrow 15 in FIG. 3, and after hitting the center of the growing crystal 5, As it spreads around the surrounding area, the solid-liquid interface tends to convex upward, resulting in the occurrence of crystal defects such as polycrystalization and high dislocation. Although it is possible to suppress the convection of the raw material melt inside the coracle by reducing the cross-sectional area of the small opening, this increases the inflow resistance, and this is especially important when trying to pull a single crystal with a large diameter. The inflow of melt cannot keep up.
他方、原料融液に浸漬するコラクルの傾斜側面の融液表
面近くに、小開口を複数設けることにより、該小開口か
ら原料融液を流入させ、コラクル下端の小開口から流出
させて、半径方向の温度分布を平坦化させようとする装
置が、特願昭６１−２９０５４９号公報に記載されてい
るが、固液界面の外周部近くに原料融液流入用の小開口
があるため、その近傍の原料融液の温度が変動し易く、
安定した結晶成長を行うことが難しい。On the other hand, by providing a plurality of small openings near the melt surface on the inclined side surface of the coracle that is immersed in the raw material melt, the raw material melt flows in through the small openings and flows out through the small opening at the lower end of the coracle, so that the coracle is immersed in the raw material melt. A device for flattening the temperature distribution is described in Japanese Patent Application No. 61-290549. The temperature of the raw material melt fluctuates easily,
It is difficult to achieve stable crystal growth.
本発明は、上記の欠点を解消し、固液界面を常時平坦若
しくは下に僅かに凸にして安定した結晶成長を可能とす
る単結晶の育成方法を提供しようとするものである。The present invention aims to eliminate the above-mentioned drawbacks and provide a method for growing a single crystal in which the solid-liquid interface is always flat or slightly convex downward, thereby enabling stable crystal growth.
（課題を解決するための手段）
本発明は、逆円錐形の側壁を有するコラクルをるつぼ内
原料融液中に浸漬させ、コラクル内原料融液から単結晶
を引き上げる単結晶の育成方法において、引上結晶の直
胴部の直径Ｃに対して、
（＋／２）Ｃ≦Ｂ≦（３／４）Ｃ
の関係を満たすコラクル底部の直径Ｂの円周上に、１つ
以上の小開口出口をもうけたコラクルを用い、コラクル
内の原料融液深さＡについては、
（１／＋５）Ｂ≦Ａ≦（１／２） Ｂ
の関係を満たすように、コラクルを維持しながら単結晶
を引き上げることを特徴とする単結晶の育成方法である
。(Means for Solving the Problems) The present invention provides a single crystal growth method in which a coracle having an inverted conical side wall is immersed in a raw material melt in a crucible, and a single crystal is pulled from the raw material melt in the coracle. With respect to the diameter C of the straight body of the upper crystal, one or more small opening exits are provided on the circumference of the coracle bottom diameter B that satisfies the relationship (+/2)C≦B≦(3/4)C. The single crystal is pulled up while maintaining the coracle so that the depth A of the raw material melt inside the coracle satisfies the relationship (1/+5)B≦A≦(1/2)B. This is a single crystal growth method characterized by the following.
（作用）
第１図は、本発明を実施するための単結晶製造装置の説
明図である。この方法は、るつぼｌに原料融液２を収容
し、その中に逆円錐形のコラクル３を浸漬し、コラクル
内に導入された原料融液４から単結晶５を引き上げるも
ので、コラクル３は、逆円錐部６の上端周囲に原料融液
を覆う環状板７が設けてあり、下端底部８には原料融液
を導入する小間口９が複数設けられている。その際、引
上結晶の直胴部の直径Ｃに対して、
（１／２）Ｃ≦Ｂ≦（３／４） Ｃ
の関係を満たすコラクル底部の直径Ｂの円周上に、小間
口９の出口を設けることにより、原料融液の流れを、図
中の矢印１０のように、まず引上結晶の周囲に当て、そ
れから中心に向かわせることにより、コラクルの逆傾斜
部の冷却を回避して、固液界面の周囲温度を上昇させる
。(Function) FIG. 1 is an explanatory diagram of a single crystal manufacturing apparatus for carrying out the present invention. In this method, a raw material melt 2 is placed in a crucible l, an inverted cone-shaped coracle 3 is immersed therein, and a single crystal 5 is pulled up from the raw material melt 4 introduced into the coracle. An annular plate 7 is provided around the upper end of the inverted conical portion 6 to cover the raw material melt, and a plurality of small openings 9 for introducing the raw material melt are provided at the lower end bottom portion 8. At that time, with respect to the diameter C of the straight body of the pulled crystal, a small frontage 9 is placed on the circumference of the diameter B of the bottom of the coracle that satisfies the relationship (1/2)C≦B≦(3/4)C. By providing an outlet, the flow of the raw material melt is first applied to the periphery of the pulled crystal and then directed to the center, as shown by arrow 10 in the figure, thereby avoiding cooling of the reversely inclined part of the coracle. This increases the ambient temperature at the solid-liquid interface.
また、コラクル内の原料融液深さＡについては、（１／
１５） Ｂ≦Ａ≦（１／２）Ｂ
の関係を満たすようにして、原料融液深さＡを制限する
ことにより、固液界面の中心部の熱をコラクルを介して
雰囲気ガス中に放散させ、該中心部の温度を相対的に低
下させる。その結果、コラクル内原料融液の半径方向の
温度分布を平準化若しくは中心部の温度が若干低い温度
分布とすることができ、固液界面の形状を平坦化若しく
は下に凸化することができるようになった。Furthermore, the depth A of the raw material melt in the coracle is (1/
15) Heat in the center of the solid-liquid interface is dissipated into the atmospheric gas through the coracle by limiting the depth A of the raw material melt so that the relationship B≦A≦(1/2)B is satisfied. to relatively lower the temperature at the center. As a result, the temperature distribution in the radial direction of the raw material melt in the coracle can be leveled or the temperature at the center can be made slightly lower, and the shape of the solid-liquid interface can be flattened or convexed downward. It became so.
なお、コラクルの材質は、石英、ｐＢＮＳＢＮ。The material of the coracle is quartz and pBNSBN.
カーボン、＾１，０５、ＡＩＮ、 ＳｉＣ，マグネシア
、ジルコニア、ベリリア、ＳｉＮ、、Ｍｏ、 ｆ、 Ｔ
ａ及びこれらの複合体などを用いることができる。Carbon, ^1,05, AIN, SiC, magnesia, zirconia, beryllia, SiN, Mo, f, T
a, complexes thereof, and the like can be used.
第２図は、本発明で使用する別のコラクルの断面図であ
り、コラクル１１内の原料融液深さ八を小さく、小開口
の入口から融液表面までの距ｆＩＩＤを太き（とるため
に、コラクルの底１２を厚くしたものである。FIG. 2 is a cross-sectional view of another coracle used in the present invention. In addition, the bottom 12 of the coracle is made thicker.
（実施例） 第１図の装置を用いてＧａＡｓ単結晶を育成した。(Example) A GaAs single crystal was grown using the apparatus shown in FIG.
コラクルは、傾斜角４５°で高さが２０ＩＩ１１の逆円
錐部と、該逆円錐部上端に接続する、外径が１４５＋Ｉ
１ｍ、内径が８０ＩＩ１１の環状板と、内径が４０＋ｓ
ｓの底面を有し、肉厚５ｍｍのＢＮ製であり、該底面の
直径Ｂが４０１の円周上に直径５ｎ＋ＴＩの小開口を３
つ設けたものを用いた。そして、直径１５０ｍｍのｐｔ
３Ｎ製のる−） ｉ：１’ １．： ハ、ＧａＡｓ原料
を４Ｋｇチャージして、加熱溶融した後、上記のコラク
ルを浮が６たとこる・コラクル内の原料融液の深さΔは
Ｉ ５ｍｍでありた〇次いで、引上速度をＩＯ＋ａｍ／
ｈｒとして直径Ｃが７５ＩＩＩｌｌ（７）ＧａＡｓ１１
結晶を引き」Ｚげたところ、＝Ｆ川な固液界面を維持し
ながら、安定して引き−１−げることかできた。得られ
た単結晶は、単結晶化率が９５％以上であった。The coracle has an inverted conical part with an inclination angle of 45° and a height of 20II11, and an outer diameter of 145+I connected to the upper end of the inverted conical part.
1m, annular plate with inner diameter of 80II11 and inner diameter of 40+s
It has a bottom surface of s and is made of BN with a wall thickness of 5 mm, and the diameter B of the bottom surface is 3 small openings of diameter 5n + TI on the circumference of 401.
I used one provided with one. And a pt with a diameter of 150mm
3N glue) i:1' 1. : After charging 4 kg of GaAs raw material and heating and melting it, the above coracle was lifted up by 6 times.・The depth Δ of the raw material melt in the coracle was I 5 mm.〇Then, the pulling speed was adjusted to IO+am/
Diameter C as hr is 75IIIll (7) GaAs11
When the crystal was pulled and pulled, it was possible to pull it stably while maintaining the =F solid-liquid interface. The single crystal obtained had a single crystallization rate of 95% or more.
比較のために、第３図のコラクルを用いて、上記の実施
例と同様にＧａＡｓ単結晶を引き上げた。For comparison, a GaAs single crystal was pulled using the coracle shown in FIG. 3 in the same manner as in the above example.
このコラクルは内径１００ｍｍの円筒部と、先端に直径
４■の小開口を有し、傾斜角３０°の逆円錐部を有する
ものである。引き上げ操作は、引上結晶の直径が５０５
ｍまでは比較的安定して引き上げることができたが、固
液界面の形状は中央部に同化がみられ、多結晶が一部発
生していた。また、引上結晶の直径を７５ｍｍにしよう
とすると、直径の急激な減少や切断が発生した。This coracle has a cylindrical part with an inner diameter of 100 mm, a small opening with a diameter of 4 cm at the tip, and an inverted conical part with an inclination angle of 30 degrees. The pulling operation is performed when the diameter of the pulled crystal is 505 mm.
Although the material could be pulled up relatively stably up to m, the shape of the solid-liquid interface was assimilated in the center, and some polycrystals were generated. Further, when trying to increase the diameter of the pulled crystal to 75 mm, a sudden decrease in diameter or cutting occurred.
（発明の効果）
本発明は上記の構成を採用することにより、原料融液を
コラクルの傾斜側面に沿って流入させ、固液界面の周囲
より中央に向かって流すようにして、コラクル内の半径
方向の原料融液温度分布を平準化させ若しくは中心部の
温度を下げ、引上結晶の固液界面の形状を平坦若しくは
下に凸にすることができ、引上結晶の形状制御を容易に
し、結晶欠陥の少ない高品質な単結晶を安定して育成す
ることができるようになった。(Effects of the Invention) By adopting the above configuration, the present invention allows the raw material melt to flow along the inclined side surfaces of the coracle, and flows from the periphery of the solid-liquid interface toward the center, thereby allowing the raw material melt to flow within the radius within the coracle. By leveling the temperature distribution of the raw material melt in the direction or lowering the temperature at the center, the shape of the solid-liquid interface of the pulled crystal can be flattened or convex downward, making it easier to control the shape of the pulled crystal. It has become possible to stably grow high-quality single crystals with few crystal defects.
第１図は本発明を実施するための単結晶育成装置の１具
体例を示したもので、熱の流れを説明するための説明図
、第２図は本発明の他のコラクルの断面図、第３図は従
来の単結晶育成装置における熱の流れを説明するための
説明図である。
第１図FIG. 1 shows a specific example of a single crystal growth apparatus for carrying out the present invention, and is an explanatory diagram for explaining the flow of heat, and FIG. 2 is a cross-sectional view of another coracle of the present invention. FIG. 3 is an explanatory diagram for explaining the flow of heat in a conventional single crystal growth apparatus. Figure 1
Claims (1)
中に浸漬させ、コラクル内原料融液から単結晶を引き上
げる単結晶の育成方法において、引上結晶の直胴部の直
径Ｃに対して、 （１／２）Ｃ≦Ｂ≦（３／４）Ｃ の関係を満たすコラクル底部の直径Ｂの円周上に、１つ
以上の小開口出口をもうけたコラクルを用い、コラクル
内の原料融液深さＡについては、 （１／１５）Ｂ≦Ａ≦（１／２）Ｂ の関係を満たすように、コラクルを維持しながら単結晶
を引き上げることを特徴とする単結晶の育成方法。[Claims] In a single crystal growing method in which a coracle having an inverted conical side wall is immersed in a raw material melt in a crucible and a single crystal is pulled from the raw material melt in the coracle, Using a coracle that has one or more small openings on the circumference of the coracle bottom with a diameter B that satisfies the relationship (1/2)C≦B≦(3/4)C with respect to the diameter C, The single crystal is characterized in that the single crystal is pulled up while maintaining the coracle so that the depth A of the raw material melt in the coracle satisfies the following relationship: (1/15)B≦A≦(1/2)B How to cultivate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12397788A JPH01294592A (en) | 1988-05-23 | 1988-05-23 | Growth of single crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12397788A JPH01294592A (en) | 1988-05-23 | 1988-05-23 | Growth of single crystal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01294592A true JPH01294592A (en) | 1989-11-28 |
Family
ID=14873992
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12397788A Pending JPH01294592A (en) | 1988-05-23 | 1988-05-23 | Growth of single crystal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01294592A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006199577A (en) * | 2004-12-22 | 2006-08-03 | Tokuyama Corp | Pulling apparatus for producing metal fluoride single crystal and method for producing metal fluoride single crystal using the apparatus |
| JP2007106662A (en) * | 2005-09-14 | 2007-04-26 | Tokuyama Corp | Metal fluoride single crystal pulling apparatus and method for producing metal fluoride single crystal using the apparatus |
| US7229494B2 (en) | 2002-02-13 | 2007-06-12 | Nippon Mining & Metals Co., Ltd. | Production method for compound semiconductor single crystal |
| US8016942B2 (en) | 2004-12-22 | 2011-09-13 | Tokuyama Corporation | Process for producing metal fluoride single crystal |
-
1988
- 1988-05-23 JP JP12397788A patent/JPH01294592A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7229494B2 (en) | 2002-02-13 | 2007-06-12 | Nippon Mining & Metals Co., Ltd. | Production method for compound semiconductor single crystal |
| JP2006199577A (en) * | 2004-12-22 | 2006-08-03 | Tokuyama Corp | Pulling apparatus for producing metal fluoride single crystal and method for producing metal fluoride single crystal using the apparatus |
| US8016942B2 (en) | 2004-12-22 | 2011-09-13 | Tokuyama Corporation | Process for producing metal fluoride single crystal |
| JP2007106662A (en) * | 2005-09-14 | 2007-04-26 | Tokuyama Corp | Metal fluoride single crystal pulling apparatus and method for producing metal fluoride single crystal using the apparatus |
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