JP4233059B2 - Silica glass crucible for pulling silicon single crystal and method for producing the same - Google Patents
Silica glass crucible for pulling silicon single crystal and method for producing the same Download PDFInfo
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- JP4233059B2 JP4233059B2 JP2005154088A JP2005154088A JP4233059B2 JP 4233059 B2 JP4233059 B2 JP 4233059B2 JP 2005154088 A JP2005154088 A JP 2005154088A JP 2005154088 A JP2005154088 A JP 2005154088A JP 4233059 B2 JP4233059 B2 JP 4233059B2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 173
- 239000013078 crystal Substances 0.000 title claims abstract description 81
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 73
- 239000010703 silicon Substances 0.000 title claims abstract description 73
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000011521 glass Substances 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims description 31
- 239000000377 silicon dioxide Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 23
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims 1
- 239000000155 melt Substances 0.000 abstract description 5
- 230000007774 longterm Effects 0.000 abstract description 2
- 238000010828 elution Methods 0.000 description 13
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/09—Other methods of shaping glass by fusing powdered glass in a shaping mould
- C03B19/095—Other methods of shaping glass by fusing powdered glass in a shaping mould by centrifuging, e.g. arc discharge in rotating mould
-
- 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
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
- C30B15/10—Crucibles or containers for supporting the melt
-
- 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
- C30B29/02—Elements
- C30B29/06—Silicon
Abstract
Description
本発明は、シリコン単結晶引上げ用石英ガラスルツボ及びその製造方法に関する。 The present invention relates to a quartz glass crucible for pulling a silicon single crystal and a method for manufacturing the same.
従来、シリコン単結晶の製造には、いわゆるチョクラルスキー法（ＣＺ法）と呼ばれる方法が広く採用されている。このＣＺ法は、石英ガラスで製造したルツボ内でシリコン多結晶を溶融し、このシリコン融液にシリコン単結晶の種結晶を浸漬し、ルツボを回転させながら種結晶を徐々に引上げ、シリコン単結晶を種結晶を核として成長させる方法である。前記ＣＺ法で製造される単結晶は、高純度であるとともにシリコンウェーハを歩留まりよく製造できることが必要で、その製造に使用される石英ガラスルツボとしては泡を含まない透明な内層と泡を含み不透明な外層からなる二層構造の石英ガラスルツボが一般的に用いられている。 Conventionally, a so-called Czochralski method (CZ method) has been widely used for the production of silicon single crystals. In this CZ method, a silicon polycrystal is melted in a crucible made of quartz glass, a silicon single crystal seed crystal is immersed in the silicon melt, and the seed crystal is gradually pulled up while rotating the crucible. Is grown using seed crystals as nuclei. The single crystal produced by the CZ method is required to have a high purity and to be able to produce a silicon wafer with a high yield. As a quartz glass crucible used for the production, a transparent inner layer containing no bubbles and an opaque containing bubbles In general, a quartz glass crucible having a two-layer structure composed of various outer layers is used.
近年、シリコン単結晶の大口径化に伴い、単結晶の引上げ作業が長時間化し１４００℃以上のシリコン融液に長時間接触するようになり、その内表面がシリコン融液と反応し、内表面の浅い層に結晶化が起こり、褐色のクリストバライトがリング状（以下ブラウンリングという）に現れることが起こる。前記ブラウンリング内はクリストバライト層がないか又はあっても大変薄い層であるが、操業時間の経過とともにブラウンリングはその面積を拡大し、互いに融合しながら成長を続け、遂にはその中心部が浸食され、不規則なガラス溶出面となる。このガラス溶出面が出現すると、シリコン単結晶に転位が起こり易くなり、単結晶引上げの歩留まりに支障をきたすことになる。特に、２００ｍｍ以上の大口径のウェーハを製造するシリコン単結晶を成長させるにはＣＺ法の操業を１００時間を超えて行う必要があり、前記ガラス溶出面の出現が顕著となる。 In recent years, with the increase in the diameter of silicon single crystals, the pulling operation of the single crystal has become longer, and has come into contact with a silicon melt at 1400 ° C. or higher for a long time. Crystallization occurs in the shallow layer of the crystal, and brown cristobalite appears in a ring shape (hereinafter referred to as a brown ring). The brown ring has a cristobalite layer with or without a cristobalite layer, but as the operating time elapses, the brown ring expands its area and continues to grow while fusing with each other. And an irregular glass elution surface. When this glass elution surface appears, dislocations are likely to occur in the silicon single crystal, which hinders the yield of single crystal pulling. In particular, in order to grow a silicon single crystal for producing a wafer having a large diameter of 200 mm or more, it is necessary to carry out the operation of the CZ method for more than 100 hours, and the appearance of the glass elution surface becomes remarkable.
上記ブラウンリングは、ガラス表面の微細な傷や原料粉の溶け残りである結晶質残留部分、ガラス構造の欠陥などを核として発生すると考えられており、その数を減らすには、ガラスの表面状態を良好に保ったり、結晶質残留成分をなくするために溶融時間を高温、長時間化したり、或いは特許文献１に示すように内表面を形成する原料粉として非晶質である合成粉を使用することが行われている。前記非晶質である合成粉からなる合成石英ガラスは、不純物の含有量が極めて少なく、ブラウンリングの発生を少なくできる利点がある。しかしながら、透明な内層が合成石英ガラスからなるルツボは、天然石英ガラスからなるルツボと比較してポリシリコンを溶融した際、その融液表面が振動し易い欠点もあった。この振動は特に種付けからショルダー形成時、単結晶ボディ部前半の初期の引上げ工程に多く見られ、種付け作業に時間を要したり、結晶が乱れ、溶かし直し、いわゆるメルトバックを引き起こしたりして生産性を低下させる場合があった。
上記欠点を解消すべく本発明者は鋭意研究を続けた結果、ＣＺ法においてルツボ内表面に発生するブラウンリングの発生数を減らすと、結晶の引上げ時にシリコン融液面が振動し易くなり、作業性が悪化する問題があった。その解決として、シリコン融液の初期湯面位置から単結晶引上げ後の残湯位置までの石英ガラスルツボの内表面に沿って測定した長さＭに対し単結晶引上げの初期湯面位置から０．３Ｍの範囲に発生するブラウンリングの数と引上げ後の残湯位置から０．３Ｍまでの範囲のブラウンリングの数の比を特定範囲以上とすると融液表面の振動がなくなり、単結晶引上げの歩留まりが高くなることがわかった。 As a result of continuous research conducted by the inventor in order to eliminate the above-described drawbacks, if the number of brown rings generated on the inner surface of the crucible in the CZ method is reduced, the silicon melt surface is likely to vibrate when the crystal is pulled up. There was a problem of worsening sex. As a solution to this, the length M measured along the inner surface of the quartz glass crucible from the initial molten metal position of the silicon melt to the remaining molten metal position after pulling the single crystal is 0. 0 from the initial molten metal position of the single crystal pulling. If the ratio of the number of brown rings generated in the range of 3M to the number of brown rings in the range from 0.3M to the remaining hot water position after pulling exceeds the specified range, the melt surface vibration will be lost and the yield of pulling up the single crystal will be reduced. Was found to be high.
したがって、本発明は、融液表面の振動の発生を抑え、かつ、長時間の操業においてもルツボ内表面において肌荒れ面の発生率が低く、安定にシリコン単結晶を引き上げることができるシリコン単結晶引上げ用石英ガラスルツボを提供することを目的とする。 Therefore, the present invention suppresses the occurrence of vibrations on the melt surface, has a low incidence of rough skin on the inner surface of the crucible even during long-time operation, and can pull up the silicon single crystal stably. An object of the present invention is to provide a quartz glass crucible for use.
また、本発明は、上記優れた特性を有するシリコン単結晶引上げ用石英ガラスルツボを低価格で製造できる方法を提供することを目的とする。 Another object of the present invention is to provide a method capable of producing a quartz glass crucible for pulling a silicon single crystal having the above-described excellent characteristics at a low cost.
本発明は、天然石英ガラスからなる不透明な外層と、その内側に形成した結晶化剤を含まない透明層を有するCZ法によるシリコン単結晶引上げで使用する石英ガラスルツボにおいて、シリコン融液の初期湯面位置から単結晶引上げ後の残湯位置までの石英ガラスルツボの内表面に沿って測定した長さＭに対し初期湯面位置から０．３Ｍの範囲の内表面を天然石英ガラスまたは天然合成混合石英ガラスからなる透明層で形成し、かつシリコン融液の初期湯面位置から単結晶引上げ後の残湯位置までの石英ガラスルツボの内表面に沿って測定した長さＭに対し前記天然石英ガラスまたは天然合成混合石英ガラスからなる透明層で観測されるブラウンリングの単位面積（ｃｍ２）当りの個数が、単結晶引上げ後の残湯位置上０．３Ｍまでの範囲の合成石英ガラスからなる透明層で観測されるブラウンリングの個数の１．８倍以上であることを特徴とするシリコン単結晶引上げ用石英ガラスルツボ及びその製造方法に関する。 The present invention relates to a silica glass crucible used for pulling a silicon single crystal by a CZ method, which has an opaque outer layer made of natural quartz glass and a transparent layer that does not contain a crystallizing agent formed on the inside thereof. Natural quartz glass or natural synthetic mixture is used for the inner surface in the range of 0.3M from the initial molten metal surface position to the length M measured along the inner surface of the quartz glass crucible from the surface position to the remaining molten metal position after pulling the single crystal. The natural quartz glass is formed of a transparent layer made of quartz glass and has a length M measured along the inner surface of the quartz glass crucible from the initial molten metal surface position of the silicon melt to the remaining molten metal position after pulling the single crystal. Or the number per unit area (cm 2 ) of the brown ring observed in the transparent layer made of natural synthetic mixed quartz glass is within the range up to 0.3M above the position of the remaining hot water after pulling the single crystal. The present invention relates to a quartz glass crucible for pulling a silicon single crystal characterized by being at least 1.8 times the number of brown rings observed in a transparent layer made of synthetic quartz glass, and a method for producing the same.
本発明の石英ガラスルツボは、上述のとおり天然石英ガラスからなる不透明な外層と、その内側に形成した透明層を有する石英ガラスルツボにおいて、シリコン融液の初期湯面位置から単結晶引上げ後の残湯位置までの石英ガラスルツボの内表面に沿って測定した長さＭに対し初期湯面位置から０．３Ｍの範囲で観測されるブラウンリングの単位面積（ｃｍ２）当りの個数が、残湯位置上０．３Ｍまでの範囲で観測されるブラウンリングの個数の１．８倍以上、好ましくは２．５倍以上であるシリコン単結晶引上げ用石英ガラスルツボである。前記ブラウンリングとは、前述のとおりクリストバライトの褐色のリングで、その発生初期には図３（ａ）に示すようにクリストバライト層がないか又はあっても大変薄い層である。このブラウンリングは単結晶引上げの操業時間の経過、即ちルツボがシリコン融液と接触する時間が増大するとその面積を増し、図３（ｂ）のように結晶化組織が現れる。さらに単結晶の引上げを続け、シリコン融液とルツボとの反応が進むと図３（ｃ）にみるように褐色に囲まれた部分が次第に侵食され荒れたガラス溶出面（非晶質）となる。図３において、１７はルツボ内表面、１８はブラウンリング、１９は結晶化組織、２０はガラス溶出面である。前記ガラス溶出面ができると、シリコン単結晶に転位が生じ易くなり、単結晶化率が低下する。 As described above, the quartz glass crucible of the present invention is a quartz glass crucible having an opaque outer layer made of natural quartz glass and a transparent layer formed on the inside thereof. The number of brown rings per unit area (cm 2 ) observed in the range of 0.3 M from the initial hot water surface position to the length M measured along the inner surface of the quartz glass crucible up to the hot water position is the remaining hot water. A quartz glass crucible for pulling a silicon single crystal that is 1.8 times or more, preferably 2.5 times or more the number of brown rings observed in a range of up to 0.3 M on the position. The brown ring is a brown ring of cristobalite as described above, and is a very thin layer even if there is no cristobalite layer as shown in FIG. This brown ring increases in area when the operation time for pulling the single crystal increases, that is, when the crucible contacts with the silicon melt, and a crystallized structure appears as shown in FIG. When the pulling of the single crystal is continued and the reaction between the silicon melt and the crucible proceeds, the portion surrounded by brown is gradually eroded and becomes a rough glass elution surface (amorphous) as shown in FIG. . In FIG. 3, 17 is a crucible inner surface, 18 is a brown ring, 19 is a crystallized structure, and 20 is a glass elution surface. When the glass elution surface is formed, dislocation is likely to occur in the silicon single crystal, and the single crystallization rate is reduced.
上記ブラウンリングの個数は、ルツボ円周方向において幅１０ｃｍの任意の３点において観測されるブラウンリングの数をカウントし、測定面積で割って算出した単位面積（ｃｍ２）当りの個数である。ルツボのシリコン融液との接触時間が長く、ブラウンリングが成長し易い残湯付近においてはブラウンリングが融合する場合があるが、この場合同測定範囲内に観測される単独のブラウンリングの平均径から１個当たりの面積を計算し、融合部分の面積を前記１個当たりの面積で割った値を融合部分のブラウンリングの個数とする。 The number of the brown rings is a number per unit area (cm 2 ) calculated by counting the number of brown rings observed at three arbitrary points having a width of 10 cm in the circumferential direction of the crucible and dividing by the measured area. The contact time of the crucible with the silicon melt is long, and the brown ring may fuse in the vicinity of the remaining hot water where the brown ring is likely to grow. In this case, the average diameter of the single brown ring observed within the same measurement range Then, the area per piece is calculated, and the value obtained by dividing the area of the fused portion by the area per piece is taken as the number of brown rings in the fused portion.
CＺ法で用いられる石英ガラスルツボにおいて、ＣＺ法中でのシリコン融液表面の振動は、融液表面の位置が初期湯面位置から０．３Ｍの範囲において特に多く発生するが、その範囲だけのブラウンリングの数を増やすことで前記シリコン融液表面の振動を抑えることができる。また、前記範囲は、シリコン融液との接触時間が短いため、ブラウンリングの径は小さく、図３（ａ）に示すような状態であり、ガラス溶出面は発生せず、ブラウンリングの数を増やしても、単結晶引上げ歩留まりに影響を及ぼすことがない。 In the quartz glass crucible to be used in the CZ method, vibration of the silicon melt surface in the CZ method, the position of the melt surface is particularly greatly occurs in the range of 0.3M from the initial melt surface position, its scope only By increasing the number of brown rings, vibration of the silicon melt surface can be suppressed. Further, in the above range, since the contact time with the silicon melt is short, the diameter of the brown ring is small, as shown in FIG. 3 (a), the glass elution surface is not generated, and the number of brown rings is set. Even if it increases, it does not affect the yield of single crystal pulling.
一方、シリコン単結晶の転位は、その殆どが残湯位置上０．３Ｍまでの範囲において発生するが、この範囲はシリコン融液との接触時間が長いことからブラウンリングが成長し図３（ｃ）に示すガラス溶出面が発生しやすい。そこで、この範囲のブラウンリングの数を減らすことでガラス溶出面の発生を抑えることができ、単結晶引上げの歩留まりを向上できる。また、この範囲のブラウンリングの数を減らしても、シリコン融液の振動に影響することがない。 On the other hand, dislocations in a silicon single crystal is mostly generated in the range up to 0.3M over the remaining hot water position, this range brown ring grows because longer contact time with the silicon melt Figure 3 (c The glass elution surface shown in FIG. Therefore, by reducing the number of brown rings in this range, the generation of the glass elution surface can be suppressed, and the yield of single crystal pulling can be improved. Further, even if the number of brown rings in this range is reduced, the vibration of the silicon melt is not affected.
ＣＺ法においては、同じルツボを使用しても単結晶の引き上げの条件によって、ブラウンリングの個数に多少の違いが見られるが、本発明にあってはブラウンリングの個数がシリコン融液の初期湯面位置から単結晶引上げ後の残湯位置までのルツボの内表面に沿って測定した長さＭに対し初期湯面位置から０．３Ｍの範囲までに観測される単位面積（ｃｍ２）当りの個数が残湯位置上０．３Ｍまでの範囲に観測される個数に対し１．８倍以上、好ましくは２．５倍以上である。これによりシリコン融液表面の振動が抑制でき、シリコン単結晶引上げの歩留まりを高くできる。特に初期湯面位置から０．３Ｍの範囲までに観測されるブラウンリングの個数が２．０〜５．０個／ｃｍ２であると、シリコン融液表面の振動を確実に抑制することができる。また、残湯位置上０．３Ｍまでの範囲までに観測されるブラウンリングの個数が０．０２〜０．９個／ｃｍ２以下であるとシリコン単結晶の歩留まりが高水準となる。さらに、シリコン単結晶引上げ工程の前半において、トラブルで単結晶に転位が生じた場合、結晶を溶かし直して引上げをやり直す、いわゆるメルトバックを行うことがあるが、このメルトバックを行ったり、または１個のルツボから数本の単結晶を引き上げるマルチ引上げを行うと、ブラウンリングの数は増え、ブラウンリング同士の融合が進み、個数の計算が困難となる。メルトバックを行わずに引上げを行った場合、またはマルチ引上げの１本目を引き上げた後の状態において、ブラウンリングの個数が上記の範囲内であるルツボを使用すれば、メルトバックを行った場合でも、或はマルチ引上げを行った場合でも、前記範囲外のルツボと比較し良好な引上げが達成できることから、個数の計算はメルトバックを行わず１本の単結晶を引き上げた後ルツボ内表面について行うものとする。 In the CZ method, even if the same crucible is used, there are some differences in the number of brown rings depending on the pulling conditions of the single crystal. In the present invention, the number of brown rings is the initial temperature of the silicon melt. Per unit area (cm 2 ) observed from the initial molten metal surface position to 0.3 M with respect to the length M measured along the inner surface of the crucible from the surface position to the remaining molten metal position after pulling the single crystal. The number is 1.8 times or more, preferably 2.5 times or more of the number observed in the range up to 0.3 M on the remaining hot water position. Thereby, the vibration of the silicon melt surface can be suppressed, and the yield of pulling the silicon single crystal can be increased. In particular, when the number of brown rings observed from the initial molten metal surface position to a range of 0.3 M is 2.0 to 5.0 / cm 2 , vibration of the silicon melt surface can be reliably suppressed. . Further, when the number of brown rings observed up to 0.3 M above the remaining hot water position is 0.02 to 0.9 pieces / cm 2 or less, the yield of silicon single crystals becomes a high level. Further, in the first half of the silicon single crystal pulling process, when dislocations occur in the single crystal due to a trouble, the so-called meltback may be performed in which the crystal is melted and the pulling is performed again. When multiple pulling is performed by pulling several single crystals from a single crucible, the number of brown rings increases, the fusion of the brown rings progresses, and the number calculation becomes difficult. Even when meltback is performed, if the crucible with the number of brown rings in the above range is used after pulling up without performing meltback or after pulling up the first multi-pull Or, even when multi-pulling is performed, it is possible to achieve better pulling compared to a crucible outside the above range. Therefore, the number is calculated on the inner surface of the crucible after pulling up a single crystal without melting back. Shall.
本発明のシリコン単結晶引上げ用石英ガラスルツボは、シリコン融液表面に振動がなく、ガラス溶出面の出現によるルツボ内表面の肌荒れがなく、長時間安定してシリコン単結晶を引き上げることができる。 The quartz glass crucible for pulling a silicon single crystal according to the present invention does not vibrate on the surface of the silicon melt, does not cause rough surface of the inner surface of the crucible due to the appearance of the glass elution surface, and can pull the silicon single crystal stably for a long time.
本発明をより詳細に説明するために添付図面に従ってこれを説明する。 図１、２において、１は石英ガラスルツボ、２はルツボの底部、３は直胴部、４は天然石英ガラスからなる不透明な外層、５は天然石英ガラスからなる透明層、６は合成石英ガラスからなる透明層である。本発明の石英ガラスルツボの１態様を図１に示す。図１に示すように本発明の石英ガラスルツボは、天然石英ガラスからなる不透明層とその内側に石英ガラスからなる透明層を有し、その初期湯面位置から０．３Ｍの範囲の内表面が天然石英ガラスまたは天然合成混合石英ガラスからなる透明層、残湯位置上０．３Ｍまでの範囲の内表面が合成石英ガラスからなる透明層、それ以外の範囲の内表面は天然、天然合成混合、合成のいずれからなる透明層で形成した石英ガラスルツボである。この石英ガラスルツボは、図２の装置を用いて製造される。すなわち、天然シリカ粉を回転する型７に導入し、ルツボ形状に成形したのち、その中にアーク電極１３を挿入し、ルツボ状成形体の開口部を板状の蓋体１０で覆い、アーク電極１３により該ルツボ状成形体の内部キャビティを高温雰囲気１５にして少なくとも部分的に溶融ガラス化して不透明なルツボ基体を形成し、続いて合成シリカ粉をシリカ粉供給手段１４から高温雰囲気１５に供給し、溶融ガラス化して合成石英ガラスからなる透明層６をルツボ内表面に形成する、または不透明なルツボ基体の形成後もしくは形成中にシリカ粉供給手段９から流量規制バルブ１１で供給量を調節しながら高純度の天然シリカ粉または天然合成混合シリカを高温雰囲気１５に供給し、溶融ガラス化して天然石英ガラスまたは天然合成混合石英ガラスからなる透明層５を少なくとも初期湯面位置から０．３Ｍの範囲までに形成し、さらに合成シリカ粉をシリカ粉供給手段１４から高温雰囲気１５に供給し、溶融ガラス化して合成石英ガラスからなる透明層６をルツボ内表面の初期湯面位置から０．３Ｍの範囲を除き少なくとも残湯位置上０．３Ｍまでの範囲に形成する方法で製造される。また、別の態様の石英ガラスルツボは、ルツボの内層全体を合成石英ガラスで構成し、そのルツボの初期湯面位置から０．３Ｍの範囲の内表面をエッチング処理またはサンドブラスト加工処理することで微細な傷をつけ、ブラウンリングの数を増やし、初期湯面位置から０．３Ｍの範囲のブラウンリングの個数と残湯位置上０．３Ｍまでのブラウンリングの個数の比を１．８倍以上、好ましくは２．５倍以上に調製する方法でも製造できる。 In order to explain the present invention in more detail, it will be described with reference to the accompanying drawings. 1 and 2, 1 is a quartz glass crucible, 2 is a bottom part of the crucible, 3 is a straight body part, 4 is an opaque outer layer made of natural quartz glass, 5 is a transparent layer made of natural quartz glass, and 6 is a synthetic quartz glass. It is a transparent layer consisting of One embodiment of the quartz glass crucible of the present invention is shown in FIG . As shown in FIG. 1, the quartz glass crucible of the present invention has an opaque layer made of natural quartz glass and a transparent layer made of quartz glass inside, and an inner surface within a range of 0.3 M from the initial molten metal surface position. Transparent layer made of natural quartz glass or natural synthetic mixed quartz glass, transparent layer made of synthetic quartz glass with an inner surface in the range of up to 0.3M above the remaining hot water position, natural and natural synthetic mixed, It is a quartz glass crucible formed with a transparent layer made of any of the synthetic materials. This quartz glass crucible is manufactured using the apparatus of FIG. That is, natural silica powder is introduced into a rotating mold 7 and molded into a crucible shape, and then an arc electrode 13 is inserted therein, and the opening of the crucible shaped body is covered with a plate-like lid body 10. 13, the crucible-shaped molded body is made into an opaque crucible base by at least partially melting and vitrifying the internal cavity of the crucible-shaped molded body 15, and then synthetic silica powder is supplied from the silica powder supply means 14 to the high-temperature atmosphere 15. Then, a transparent layer 6 made of synthetic quartz glass is formed on the inner surface of the crucible by melting into glass, or while the opaque crucible base is formed or during formation, while adjusting the supply amount by the flow rate regulating valve 11 from the silica powder supply means 9. Supply high-purity natural silica powder or natural synthetic mixed silica to the high-temperature atmosphere 15 and convert it into molten glass to form natural quartz glass or natural synthetic mixed silica glass. The transparent layer 5 is formed in a range of at least 0.3 M from the initial molten metal surface position, and further, the synthetic silica powder is supplied from the silica powder supply means 14 to the high temperature atmosphere 15 and melted into a glass to form a transparent layer made of synthetic quartz glass. 6 is manufactured in a way to form a range from the initial melt surface position of the inner surface of the crucible to at least the remaining hot water position on 0.3M except to the extent of 0.3M. In another aspect, the quartz glass crucible is made of synthetic quartz glass with the entire inner layer of the crucible, and the inner surface within a range of 0.3 M from the initial molten metal position of the crucible is etched or sandblasted. The number of brown rings in the range of 0.3M from the initial hot water surface position to the number of brown rings up to 0.3M above the remaining hot water position is more than 1.8 times, Preferably, it can also be produced by a method of preparing 2.5 times or more.
以下に実施例を挙げて本発明を更に具体的に説明するが、本発明はこれに限定されるものではない。 EXAMPLES The present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto.
実施例１
図２に示す装置を用い、回転する型７内に純化処理した高純度の天然シリカ粉を投入し、遠心力により石英ガラスルツボ状成形体８に形成し、その内にアーク電極１３を挿入し、開口部を板状の蓋体１０で覆い、アーク電極１３により内部キャビティ内を高温雰囲気とし、溶融ガラス化して不透明石英ガラス外層４を作成するとともに、シリカ粉供給手段９から天然シリカ粉を１００ｇ／ｍｉｎで供給し、不透明石英ガラス外層４の内表面に天然石英ガラスからなる透明層５を融合一体化した。次にシリカ粉供給手段１４から合成シリカ粉を１００ｇ／ｍｉｎで供給し、シリコン単結晶引上げの使用後において、シリコン融液の初期湯面位置から単結晶引上げ後の残湯位置までの石英ガラスルツボの内表面に沿って測定した長さＭに対し初期湯面位置から０．５〜１．０Ｍの範囲の内側に、合成石英ガラスからなる透明層６を融合一体化し、外径が２２インチの石英ガラスルツボを製造した。この石英ガラスルツボを用いてＣＺ法でシリコン単結晶の引上げを行った。シリコン単結晶の引上げ結果およびルツボ内表面におけるブラウンリングの個数の測定結果を表１に示す。
Example 1
Using the apparatus shown in FIG. 2, high purity natural silica powder is put into a rotating mold 7 and formed into a quartz glass crucible shaped body 8 by centrifugal force, and an arc electrode 13 is inserted therein. The opening is covered with a plate-like lid 10, the inside cavity is made into a high-temperature atmosphere by the arc electrode 13, and the glass is melted to form an opaque quartz glass outer layer 4, and 100 g of natural silica powder is supplied from the silica powder supply means 9. The transparent layer 5 made of natural quartz glass was fused and integrated with the inner surface of the opaque quartz glass outer layer 4. Next, synthetic silica powder is supplied from the silica powder supply means 14 at 100 g / min, and after using the silicon single crystal pulling, the quartz glass crucible from the initial molten metal surface position of the silicon melt to the remaining hot water position after the single crystal pulling is used. A transparent layer 6 made of synthetic quartz glass is fused and integrated on the inner side within a range of 0.5 to 1.0 M from the initial molten metal position with respect to the length M measured along the inner surface, and the outer diameter is 22 inches. A quartz glass crucible was manufactured. Using this quartz glass crucible, the silicon single crystal was pulled by the CZ method. Table 1 shows the results of pulling up the silicon single crystal and the results of measuring the number of brown rings on the inner surface of the crucible.
実施例２
図２に示す装置を用い、回転する型７内に純化処理した高純度の天然シリカ粉を投入し、遠心力によりルツボ状成形体８に形成し、その内にアーク電極１３を挿入し、開口部を板状の蓋体１０で覆い、アーク電極１３により内部キャビティ内を高温雰囲気とし、溶融ガラス化して不透明外層４を形成すると共に、シリカ粉供給手段１４から合成シリカ粉を１００ｇ／ｍｉｎで供給し、不透明外層４の内表面全体に合成石英ガラスからなる透明層を融合一体化した。次にシリカ粉供給手段９から天然シリカ粉を１００ｇ／ｍｉｎで供給し、シリコン単結晶引上げの使用後において、シリコン融液の初期湯面位置から単結晶引上げ後の残湯位置までの石英ガラスルツボの内表面に沿って測定した長さＭに対し初期湯面位置から０．４Ｍの範囲の内側に天然石英ガラスからなる透明層を融合一体化し、外径が２２インチの石英ガラスルツボを製造した。この石英ガラスルツボを用いてＣＺ法でシリコン単結晶の引上げを行った。シリコン単結晶の引上げ結果およびルツボ内表面におけるブラウンリングの個数の測定結果を表１に示す。
Example 2
Using the apparatus shown in FIG. 2, purified high-purity natural silica powder is put into a rotating mold 7, formed into a crucible-shaped molded body 8 by centrifugal force, an arc electrode 13 is inserted therein, an opening is formed The part is covered with a plate-like lid 10, the inside cavity is made into a high-temperature atmosphere by the arc electrode 13, and the glass is melted to form the opaque outer layer 4, and synthetic silica powder is supplied from the silica powder supply means 14 at 100 g / min. Then, a transparent layer made of synthetic quartz glass was fused and integrated on the entire inner surface of the opaque outer layer 4. Next, natural silica powder is supplied from the silica powder supply means 9 at 100 g / min, and after using the silicon single crystal pulling, the quartz glass crucible from the initial molten metal surface position of the silicon melt to the remaining hot water position after the single crystal pulling is used. A quartz glass crucible having an outer diameter of 22 inches was manufactured by fusing and integrating a transparent layer made of natural quartz glass on the inner side within a range of 0.4 M from the initial molten metal surface position with respect to the length M measured along the inner surface. . Using this quartz glass crucible, the silicon single crystal was pulled by the CZ method. Table 1 shows the results of pulling up the silicon single crystal and the results of measuring the number of brown rings on the inner surface of the crucible.
実施例３
図２に示す装置を用い、回転する型７内に純化処理した高純度の天然シリカ粉を投入し、遠心力によりルツボ状成形体８に形成し、その内にアーク電極１３を挿入し、開口部を板状の蓋体１０で覆い、アーク電極１３により内部キャビティ内を高温雰囲気とし、溶融ガラス化して不透明外層４を形成すると共に、シリカ粉供給手段１４から合成シリカ粉を１００ｇ／ｍｉｎで供給し、不透明外層４の内表面全体に合成石英ガラスからなる透明層を融合一体化し、外径が２２インチの石英ガラスルツボを製造した。さらに、前記ルツボの直胴部３上部であってシリコン融液の初期湯面位置から０．３５Ｍの範囲を通常のＨＦ洗浄に加え、５０％のＨＦで３０分間のエッチング処理を行った。この石英ガラスルツボを用いてＣＺ法でシリコン単結晶の引上げを行った。シリコン単結晶の引上げ結果およびルツボ内表面におけるブラウンリングの個数の測定結果を表１に示す。
Example 3
Using the apparatus shown in FIG. 2, purified high-purity natural silica powder is put into a rotating mold 7, formed into a crucible-shaped molded body 8 by centrifugal force, an arc electrode 13 is inserted therein, an opening is formed The part is covered with a plate-like lid 10, the inside cavity is made into a high-temperature atmosphere by the arc electrode 13, and the glass is melted to form the opaque outer layer 4, and synthetic silica powder is supplied from the silica powder supply means 14 at 100 g / min. Then, a transparent layer made of synthetic quartz glass was fused and integrated with the entire inner surface of the opaque outer layer 4 to produce a quartz glass crucible having an outer diameter of 22 inches. Furthermore, an area of 0.35 M from the position of the initial melt surface of the silicon melt at the upper part of the straight barrel portion 3 of the crucible was added to normal HF cleaning, and etching treatment was performed for 30 minutes with 50% HF. Using this quartz glass crucible, the silicon single crystal was pulled by the CZ method. Table 1 shows the results of pulling up the silicon single crystal and the results of measuring the number of brown rings on the inner surface of the crucible.
比較例１
図２に示す装置を用い、回転する型７内に純化処理した高純度の天然シリカ粉を投入し、遠心力によりルツボ状成形体８に形成し、その内にアーク電極１３を挿入し、開口部を板状の蓋体１０で覆い、アーク電極１３により内部キャビティ内を高温雰囲気とし、溶融ガラス化して不透明外層４を形成すると共に、シリカ粉供給手段１４から合成シリカ粉を１００ｇ／ｍｉｎで供給し、不透明外層４の内表面全体に合成石英ガラスからなる透明層を融合一体化し、外径が２２インチの石英ガラスルツボを製造した。この石英ガラスルツボを用いてＣＺ法でシリコン単結晶の引上げを行った。シリコン単結晶の引上げ結果およびルツボ内表面におけるブラウンリングの個数の測定結果を表１に示す。
Comparative Example 1
Using the apparatus shown in FIG. 2, purified high-purity natural silica powder is put into a rotating mold 7, formed into a crucible-shaped molded body 8 by centrifugal force, an arc electrode 13 is inserted therein, an opening is formed The part is covered with a plate-like lid 10, the inside cavity is made into a high-temperature atmosphere by the arc electrode 13, and the glass is melted to form the opaque outer layer 4, and synthetic silica powder is supplied from the silica powder supply means 14 at 100 g / min. Then, a transparent layer made of synthetic quartz glass was fused and integrated with the entire inner surface of the opaque outer layer 4 to produce a quartz glass crucible having an outer diameter of 22 inches. Using this quartz glass crucible, the silicon single crystal was pulled by the CZ method. Table 1 shows the results of pulling up the silicon single crystal and the results of measuring the number of brown rings on the inner surface of the crucible.
表１に示された結果から明らかなように、本発明の石英ガラスルツボはシリコン融液の振動がなく、もしあったとしても操業上問題がないレベルで、良好な単結晶化率であった。これに対し、比較例１に示す従来の石英ガラスルツボは、シリコン融液の振動により種付けやショルダー形成時に乱れが多発したため、メルトバックによる時間ロスが大きく、操業時間が長くなった。その結果、前記従来の石英ガラスルツボは、ブラウンリングの個数は少ないものの面積が大きくなり、ガラス溶出面の発生割合も増えたため、単結晶化率が低くなった。さらに、比較例２に示す天然石英ガラスからなる透明層を有すルツボは、シリコン融液の振動は起こらなかったが、残湯付近のブラウンリングの個数が多く、ガラス溶出面がかなりの割合で発生し、きわめて低い単結晶化率であった。 As is clear from the results shown in Table 1, the quartz glass crucible of the present invention has no vibration of the silicon melt and has a good single crystallization rate at a level where there is no operational problem if any. . On the other hand, the conventional quartz glass crucible shown in Comparative Example 1 was frequently disturbed during seeding and shoulder formation due to vibration of the silicon melt, so that the time loss due to meltback was large and the operation time was long. As a result, the conventional quartz glass crucible had a small number of brown rings, but the area was large and the generation rate of the glass elution surface was increased, so that the single crystallization rate was low. Furthermore, the crucible having a transparent layer made of natural quartz glass shown in Comparative Example 2 did not vibrate the silicon melt, but the number of brown rings near the remaining hot water was large, and the glass elution surface was a considerable proportion. It was generated and the single crystallization rate was extremely low.
以上のように本発明の石英ガラスルツボは、シリコン融液表面に振動がなく、かつ長時間の使用においても内表面の肌荒れがなく、長時間安定してシリコン単結晶を引き上げることができ、シリコン単結晶引上げ用石英ガラスルツボとして有用である。 As described above, the quartz glass crucible of the present invention has no vibration on the surface of the silicon melt, and there is no rough surface on the inner surface even after long-term use, and the silicon single crystal can be pulled up stably for a long time. It is useful as a quartz glass crucible for pulling single crystals.
１：石英ガラスルツボ
２：ルツボの底部
３：直胴部
４：天然石英ガラスからなる不透明な外層
５：天然石英ガラスからなる透明層
６：合成石英ガラスからなる透明層
７：回転する型
８：ルツボ状成形体
９、１４：シリカ粉供給手段
１０：板状の蓋体
１１：流量規制バルブ
１２：電源
１３：アーク電極
１５：高温雰囲気
１７：ルツボ内表面
１８：ブラウンリング
１９：結晶化組織
２０：ガラス溶出面
1: Quartz glass crucible 2: Bottom part of crucible 3: Straight body part 4: Opaque outer layer made of natural quartz glass 5: Transparent layer made of natural quartz glass 6: Transparent layer made of synthetic quartz glass 7: Rotating mold 8: Crucible shaped bodies 9, 14: Silica powder supply means 10: Plate-like lid body 11: Flow rate regulating valve 12: Power supply 13: Arc electrode 15: High temperature atmosphere 17: Crucible inner surface 18: Brown ring 19: Crystallized structure 20 : Glass elution surface
Claims (7)
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| WO2004097080A1 (en) * | 2003-05-01 | 2004-11-11 | Shin-Etsu Quartz Products Co., Ltd. | Quartz glass crucible for pulling up silicon single crystal and method for manufacture thereof |
| JP4671999B2 (en) | 2007-11-30 | 2011-04-20 | ジャパンスーパークォーツ株式会社 | Test method for quartz glass crucible |
| JP4995069B2 (en) | 2007-12-28 | 2012-08-08 | ジャパンスーパークォーツ株式会社 | Internal crystallization crucible and pulling method using the crucible |
| JP5008695B2 (en) | 2008-06-30 | 2012-08-22 | ジャパンスーパークォーツ株式会社 | Silica glass crucible and silicon single crystal pulling method using quartz glass crucible |
| JP5072933B2 (en) | 2008-10-31 | 2012-11-14 | ジャパンスーパークォーツ株式会社 | Silica glass crucible for pulling silicon single crystal, method for producing the same, and method for producing silicon single crystal |
| JP5042971B2 (en) | 2008-11-28 | 2012-10-03 | 株式会社Ｓｕｍｃｏ | Silica glass crucible for pulling silicon single crystal and manufacturing method thereof |
| JP5749147B2 (en) * | 2010-12-31 | 2015-07-15 | 株式会社Sumco | Method for producing silica glass crucible |
| US9932692B2 (en) * | 2013-06-30 | 2018-04-03 | Sumco Corporation | Vitreous silica crucible |
| WO2015001591A1 (en) | 2013-06-30 | 2015-01-08 | 株式会社Sumco | Method for inspecting silica glass crucible |
| WO2021131321A1 (en) | 2019-12-23 | 2021-07-01 | 株式会社Sumco | Quartz glass crucible and method for producing same |
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