JP2005257184A - Crucible for high purity silicon melt casting - Google Patents
Crucible for high purity silicon melt casting Download PDFInfo
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- JP2005257184A JP2005257184A JP2004070053A JP2004070053A JP2005257184A JP 2005257184 A JP2005257184 A JP 2005257184A JP 2004070053 A JP2004070053 A JP 2004070053A JP 2004070053 A JP2004070053 A JP 2004070053A JP 2005257184 A JP2005257184 A JP 2005257184A
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 51
- 239000010703 silicon Substances 0.000 title claims abstract description 51
- 238000005266 casting Methods 0.000 title claims abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 143
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 45
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 45
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052796 boron Inorganic materials 0.000 claims abstract description 32
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 26
- 238000002844 melting Methods 0.000 claims abstract description 25
- 230000008018 melting Effects 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 23
- 239000005350 fused silica glass Substances 0.000 claims description 27
- 239000002994 raw material Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002210 silicon-based material Substances 0.000 abstract 2
- 239000002002 slurry Substances 0.000 description 45
- 239000002245 particle Substances 0.000 description 23
- 239000004576 sand Substances 0.000 description 23
- 239000008119 colloidal silica Substances 0.000 description 20
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 20
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 6
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 6
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 5
- 229910000018 strontium carbonate Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003438 strontium compounds Chemical class 0.000 description 1
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Abstract
Description
この発明は、シリコン原料を溶解し鋳造して高純度のシリコンインゴットを製造するためのるつぼに関するものである。 The present invention relates to a crucible for producing a high-purity silicon ingot by melting and casting a silicon raw material.
シリコン原料を溶解し鋳造してシリコンインゴットを製造するためのるつぼの一つとして、石英ガラス又は黒鉛からなるるつぼの内側に５０〜３００μｍの微細溶融シリカ砂をシリカで結合してなる内層が被覆された構造を有するシリコンインゴット鋳造用るつぼが知られている。この微細溶融シリカ砂をシリカで結合してなる内層は、るつぼの内壁から剥離しやすいところから、シリコン原料をるつぼ内で溶解し凝固させてシリコンインゴットを作製する際に、シリコン溶湯が凝固時に収縮しシリコンインゴットの外周がるつぼ内壁面に引っ張られる現象が発生しても、前記内層はるつぼ内面から剥離し、それによってシリコンインゴットに内部応力が残留せず、従って、シリコンインゴット製造時の内部応力割れが発生することはないので歩留まりが向上し、さらにこの内部応力残留の少ない径の大きな優れたシリコンインゴットを作製することができるとされている。 As an example of a crucible for melting and casting silicon raw material to produce a silicon ingot, an inner layer made of silica fused with 50-300 μm fine fused silica sand is coated inside a crucible made of quartz glass or graphite. A crucible for casting a silicon ingot having a different structure is known. The inner layer formed by combining the fine fused silica sand with silica is easy to peel off from the inner wall of the crucible. When the silicon raw material is melted and solidified in the crucible to produce a silicon ingot, the molten silicon shrinks during solidification. Even if the outer periphery of the silicon ingot is pulled to the inner wall of the crucible, the inner layer is peeled off from the inner surface of the crucible, so that no internal stress remains in the silicon ingot. It is said that an excellent silicon ingot having a large diameter with little residual internal stress can be produced because no occurrence of slag occurs.
そして、この石英ガラス又は黒鉛からなるるつぼの内側に５０〜３００μｍの微細溶融シリカ砂をシリカで結合してなる内層が被覆された構造を有するシリコン溶解鋳造用るつぼは、コロイダルシリカに０．２〜４．０μｍの超微細な溶融シリカ粉末を混合して得られたスラリーをるつぼの内側に塗布または吹き付けてスラリー層を形成し、このスラリー層の表面に５０〜３００μｍの微細溶融シリカ砂を散布してスタッコ層を形成し、このスタッコ層の上にさらにスラリーを塗布または吹き付けて最表面スラリー層を形成し、ついで、乾燥し焼成することにより製造することも知られている。そして、このスラリー層の表面に５０〜３００μｍの微細溶融シリカ砂を散布してスタッコ層を形成する操作は複数回繰り返し施してもよいとされている（特許文献１参照）。
しかし、前記溶融シリカ砂をシリカで結合してなる内層を石英ガラス又は黒鉛からなるるつぼの内側に形成した従来のシリコン溶解鋳造用るつぼは、シリカおよび溶融シリカ砂に０．２ｐｐｍ程度の微量のボロンが不可避不純物として含まれているために、この従来の内層を有する石英ガラス又は黒鉛からなるるつぼを用いてシリコン原料を溶解し鋳造してシリコンインゴットを製造すると、内層のシリカおよび溶融シリカ砂に含まれるボロンが溶解中にシリコンに混入し、そのためボロンドープ量の少ない高抵抗の高純度シリコンインゴットを作製することは難しかった。 However, the conventional silicon melting and casting crucible in which the inner layer formed by combining the fused silica sand with silica is formed inside the crucible made of quartz glass or graphite is a small amount of boron of about 0.2 ppm in silica and fused silica sand. Is contained as an inevitable impurity, so when a silicon ingot is produced by melting and casting a silicon raw material using a crucible made of quartz glass or graphite having this conventional inner layer, it is contained in the inner layer silica and fused silica sand. Boron mixed into silicon during melting, it was difficult to produce a high-resistance high-purity silicon ingot with a small boron doping amount.
そこで、本発明者らは、前記シリカおよび溶融シリカ砂を主体とした内層を石英ガラス又は黒鉛からなるるつぼの内側に形成したるつぼを用いてもボロンドープ量の少ないシリコンインゴットを製造すべく研究を行なった結果、
（ａ）石英ガラス又は黒鉛からなるるつぼの内側に、微細溶融シリカ砂をシリカで結合してなりかつストロンチウムを含有した内層を形成したるつぼを作製し、このるつぼにシリコン原料を充填し溶解し鋳造して得られたシリコンインゴットは、前記内層のシリカおよび微細溶融シリカ砂に不可避不純物として含まれるボロンをストロンチウムが固定し、内層に含まれるボロンが溶解シリコンに混入することがない、
（ｂ）前記ボロンはストロンチウムと主としてＳｒＢ６の形の化合物として固定されると考えられるので、内層のシリカおよび微細溶融シリカ砂に不可避不純物として含まれるボロンをあらかじめ原子％で測定しておき、その測定値（原子％）の少なくとも１／６の量のストロンチウムを含有させる必要があるが、内層にストロンチウムが多く入りすぎるとストロンチウムそのものがコンタミになる可能性があるところから、その上限は、内層を構成するシリカに対し０．１％であることが好ましい、という研究結果が得られたのである。
Therefore, the present inventors have conducted research to produce a silicon ingot with a small boron doping amount even when a crucible in which an inner layer mainly composed of silica and fused silica sand is formed inside a crucible made of quartz glass or graphite is used. As a result,
(A) A crucible in which a fine fused silica sand is bonded with silica and an inner layer containing strontium is formed inside a crucible made of quartz glass or graphite, and a silicon raw material is filled in the crucible and melted and cast. In the silicon ingot obtained, boron contained as an unavoidable impurity in the silica and fine fused silica sand of the inner layer is fixed by strontium, and boron contained in the inner layer is not mixed into the dissolved silicon,
(B) Since boron is considered to be fixed as a compound of strontium and mainly in the form of SrB 6 , boron contained as an inevitable impurity in the inner layer silica and fine fused silica sand is measured in advance in atomic percent, Although it is necessary to contain strontium in an amount of at least 1/6 of the measured value (atomic%), if too much strontium enters the inner layer, strontium itself may become contaminated. The research result that 0.1% is preferable with respect to the silica to comprise was obtained.
この発明は、係る研究結果に基づいて成されたものであって、
（１）るつぼの内面に、溶融シリカ粉末がシリカによって結合された内層を形成した構造を有するシリコン原料を溶解し鋳造してシリコンインゴットを製造するためのるつぼにおいて、前記内層はストロンチウムを含む高純度シリコン溶解鋳造用るつぼ、
（２）前記シリコン溶解鋳造用るつぼの内面に形成された内層に含まれるストロンチウムの量は、前記内層に含まれるボロン含有量の１／６以上、内層を構成するシリカに対し０．１原子％以下となるように含まれる前記（１）記載の高純度シリコン溶解鋳造用るつぼ、に特徴を有するものである。
The present invention was made based on the research results, and
(1) In a crucible for producing a silicon ingot by melting and casting a silicon raw material having a structure in which an inner layer in which fused silica powder is bonded by silica is formed on the inner surface of a crucible, the inner layer has a high purity containing strontium Crucible for silicon melting casting,
(2) The amount of strontium contained in the inner layer formed on the inner surface of the silicon melting and casting crucible is 1/6 or more of the boron content contained in the inner layer and 0.1 atomic% relative to the silica constituting the inner layer. The crucible for high-purity silicon melting and casting described in the above (1), which is included so as to be as follows, is characterized.
この発明の高純度シリコン溶解鋳造用るつぼの製造方法を以下に説明する。まず、石英ガラス又は黒鉛からなるるつぼの内側にコロイダルシリカに０．２〜４．０μｍの超微細な溶融シリカ粉末および０．２〜４．０μｍの超微細な酸化ストロンチウム粉末を混合して得られた酸化ストロンチウム粉末を含むストロンチウム含有スラリーをるつぼの内側に塗布または吹き付けてストロンチウム含有スラリー層を形成する。さらに、このストロンチウム含有スラリー層の表面に５０〜３００μｍの微細溶融シリカ砂および５０〜３００μｍの微細酸化ストロンチウム粉末を散布してストロンチウム含有スタッコ層を形成し、このストロンチウム含有スタッコ層の上にさらに前記酸化ストロンチウム粉末を含むスラリーを塗布または吹き付けて最表面スラリー層を形成してもよい。この内側にストロンチウム含有スラリー層、またはストロンチウム含有スラリー層およびストロンチウム含有スタッコ層を形成したるつぼを乾燥し焼成することによりこの発明の高純度シリコン溶解鋳造用るつぼを製造することができる。そして、この酸化ストロンチウム粉末を含むストロンチウム含有スラリー層の表面に５０〜３００μｍの微細溶融シリカ砂および５０〜３００μｍの微細酸化ストロンチウム粉末を散布して酸化ストロンチウム含有スタッコ層を形成する操作は複数回繰り返し施してもよい。 A method for producing a crucible for high purity silicon melting and casting according to the present invention will be described below. First, it is obtained by mixing colloidal silica with ultrafine fused silica powder of 0.2-4.0 μm and ultrafine strontium oxide powder of 0.2-4.0 μm inside a crucible made of quartz glass or graphite. A strontium-containing slurry containing strontium oxide powder is applied or sprayed on the inside of the crucible to form a strontium-containing slurry layer. Further, 50-300 μm fine fused silica sand and 50-300 μm fine strontium oxide powder are dispersed on the surface of the strontium-containing slurry layer to form a strontium-containing stucco layer, and the strontium-containing stucco layer is further oxidized on the strontium-containing stucco layer. A slurry containing strontium powder may be applied or sprayed to form the outermost slurry layer. The crucible for melting high-purity silicon of the present invention can be manufactured by drying and firing the crucible in which the strontium-containing slurry layer or the strontium-containing slurry layer and the strontium-containing stucco layer are formed. The operation of forming a strontium oxide-containing stucco layer by spraying 50 to 300 μm fine fused silica sand and 50 to 300 μm fine strontium oxide powder on the surface of the strontium-containing slurry layer containing the strontium oxide powder was repeated several times. May be.
ストロンチウムをスラリーに含有させる方法として、酸化ストロンチウム粉末を使用することが最も好ましいが、これに限定されるものではなく、融点、沸点が高く、焼成中や溶解中に揮発しないストロンチウム化合物として添加することができ、スラリー中に水酸化ストロンチウム、硝酸ストロンチウム、炭酸ストロンチウムの溶液として添加することができる。しかし、純ストロンチウムは融点、沸点が低いため、純ストロンチウムの添加は好ましくない。
前記酸化ストロンチウム、水酸化ストロンチウム、硝酸ストロンチウム、炭酸ストロンチウムの内層に添加する添加量は、ストロンチウム換算で内層に含まれるボロン含有量の１／６以上、内層を構成するシリカに対し０．１原子％以下となるように添加する。
As a method of incorporating strontium into the slurry, it is most preferable to use strontium oxide powder, but it is not limited to this, and it is added as a strontium compound that has a high melting point and boiling point and does not volatilize during firing or dissolution. And can be added to the slurry as a solution of strontium hydroxide, strontium nitrate, and strontium carbonate. However, since pure strontium has a low melting point and boiling point, addition of pure strontium is not preferable.
The amount of strontium oxide, strontium hydroxide, strontium nitrate, and strontium carbonate added to the inner layer is at least 1/6 of the boron content contained in the inner layer in terms of strontium, and 0.1 atomic% relative to the silica constituting the inner layer. Add as follows.
従来の内層を有するシリコン溶解鋳造用るつぼに比べて、ボロン混入量の少ないシリコンインゴットを製造することができる。 Compared to a conventional silicon melting and casting crucible having an inner layer, a silicon ingot with less boron content can be manufactured.
実施例１
内径：１７０ｍｍ、外径：１９０ｍｍ、深さ：１５０ｍｍの寸法を有する石英ガラスるつぼを用意した。
さらに、市販の平均粒径：１．０μｍの超微粉シリカ粉末（ボロン含有量：０．２３ｐｐｍ）、平均粒径：１５０μｍの微細溶融シリカ砂（ボロン含有量：０．２１ｐｐｍ）および平均粒径：１．０μｍの超微粉酸化ストロンチウム粉末を用意した。
さらに平均粒径：１０ｎｍ以下のコロイド状シリカ：３０容量％を含有し、残部：水からなるコロイダルシリカを用意し、このコロイダルシリカに対して前記用意した平均粒径：１．０μｍの超微粉シリカ粉末：６０％を添加混合してスラリーを作製した。このスラリーに含まれるボロンは０．２ｐｐｍであったので、このスラリーにさらに先に用意した平均粒径：１．０μｍの超微粉酸化ストロンチウム粉末：０．２ｐｐｍ（スラリーに含まれるボロン量の１／１に相当）を添加することによりストロンチウム含有スラリーを作製した。
前記ストロンチウム含有スラリーを前記石英ガラスるつぼの内側に塗布してスラリー層を形成し、このスラリー層の表面に平均粒径：１５０μｍの微細溶融シリカ砂を散布してストロンチウム含有スタッコ層を形成した。この操作を３回繰り返したのち、最後にストロンチウム含有スラリー層を形成し、ついで大気雰囲気中、温度：１０００℃で２時間加熱保持して乾燥し焼成することにより石英ガラスるつぼの内側に、合計厚さが３ｍｍを有する内層を形成し、本発明シリコン溶解鋳造用るつぼ（以下、本発明るつぼという）１を作製した。
Example 1
A quartz glass crucible having an inner diameter of 170 mm, an outer diameter of 190 mm, and a depth of 150 mm was prepared.
Furthermore, commercially available average particle size: 1.0 μm ultrafine silica powder (boron content: 0.23 ppm), average particle size: 150 μm fine fused silica sand (boron content: 0.21 ppm) and average particle size: A 1.0 μm ultrafine strontium oxide powder was prepared.
Further, colloidal silica containing 30% by volume of colloidal silica having an average particle size of 10 nm or less and the balance: water is prepared. Powder: 60% was added and mixed to prepare a slurry. Since the boron contained in this slurry was 0.2 ppm, the average particle diameter prepared earlier in this slurry: ultrafine strontium oxide powder of 1.0 μm: 0.2 ppm (1 / of the amount of boron contained in the slurry) Was added) to prepare a strontium-containing slurry.
The strontium-containing slurry was applied to the inside of the quartz glass crucible to form a slurry layer, and finely fused silica sand having an average particle size of 150 μm was sprayed on the surface of the slurry layer to form a strontium-containing stucco layer. After repeating this operation three times, finally, a strontium-containing slurry layer is formed, and then heated and held in an air atmosphere at a temperature of 1000 ° C. for 2 hours, dried and fired to obtain a total thickness inside the quartz glass crucible. An inner layer having a thickness of 3 mm was formed to produce a crucible for melting and casting silicon (hereinafter referred to as a crucible of the present invention) 1 of the present invention.
実施例２
内径：１７０ｍｍ、外径：１９０ｍｍ、深さ：１５０ｍｍの寸法を有する石英ガラスるつぼを用意した。
さらに、市販の平均粒径：１．０μｍの超微粉シリカ粉末（ボロン含有量：０．２３ｐｐｍ）、平均粒径：１５０μｍの微細溶融シリカ砂（ボロン含有量：０．２１ｐｐｍ）および炭酸ストロンチウムを用意した。
さらに平均粒径：１０ｎｍ以下のコロイド状シリカ：３０容量％を含有し、残部：水からなるコロイダルシリカを用意し、このコロイダルシリカに前記用意した炭酸ストロンチウムを１００ｐｐｍ（ｗｔ換算）溶解することにより炭酸ストロンチウム含有コロイダルシリカを作製した。この炭酸ストロンチウム含有コロイダルシリカ：３０容量％に対して平均粒径：１．０μｍの超微粉シリカ粉末：６０容量％を添加混合しストロンチウム含有スラリーを作製した。
前記ストロンチウム含有スラリーを前記石英ガラスるつぼの内側に塗布してスラリー層を形成し、このスラリー層の表面に平均粒径：１５０μｍの微細溶融シリカ砂を散布してストロンチウム含有スタッコ層を形成した。この操作を３回繰り返したのち、最後にストロンチウム含有スラリー層を形成し、ついで大気雰囲気中、温度：１０００℃で２時間加熱保持して乾燥し焼成することにより石英ガラスるつぼの内側に、合計厚さが３ｍｍを有する内層を形成し、本発明るつぼ２を作製した。
Example 2
A quartz glass crucible having an inner diameter of 170 mm, an outer diameter of 190 mm, and a depth of 150 mm was prepared.
Furthermore, commercially available average particle size: 1.0 μm ultrafine silica powder (boron content: 0.23 ppm), average particle size: 150 μm fine fused silica sand (boron content: 0.21 ppm) and strontium carbonate are prepared did.
Further, colloidal silica containing 30% by volume of colloidal silica having an average particle size of 10 nm or less and the balance: water is prepared, and carbon dioxide is prepared by dissolving 100 ppm (in terms of wt) of the prepared strontium carbonate in this colloidal silica. Strontium-containing colloidal silica was prepared. The strontium carbonate-containing colloidal silica: 30% by volume was added and mixed with 60% by volume of ultrafine silica powder having an average particle size of 1.0 μm to prepare a strontium-containing slurry.
The strontium-containing slurry was applied to the inside of the quartz glass crucible to form a slurry layer, and finely fused silica sand having an average particle size of 150 μm was sprayed on the surface of the slurry layer to form a strontium-containing stucco layer. After repeating this operation three times, finally, a strontium-containing slurry layer is formed, and then heated and held in an air atmosphere at a temperature of 1000 ° C. for 2 hours, dried and fired to obtain a total thickness inside the quartz glass crucible. An inner layer having a thickness of 3 mm was formed to produce the crucible 2 of the present invention.
実施例３
内径：１７０ｍｍ、外径：１９０ｍｍ、深さ：１５０ｍｍの寸法を有する石英ガラスるつぼを用意した。
さらに、市販の平均粒径：１．０μｍの超微粉シリカ粉末（ボロン含有量：０．２３ｐｐｍ）、平均粒径：１５０μｍの微細溶融シリカ砂（ボロン含有量：０．２１ｐｐｍ）および硝酸ストロンチウムを用意した。
さらに平均粒径：１０ｎｍ以下のコロイド状シリカ：３０容量％を含有し、残部：水からなるコロイダルシリカを用意し、このコロイダルシリカに前記用意した硝酸ストロンチウムを１００ｐｐｍ（ｗｔ換算）溶解することにより硝酸ストロンチウム含有コロイダルシリカを作製した。この硝酸ストロンチウム含有コロイダルシリカ：３０容量％に対して平均粒径：１．０μｍの超微粉シリカ粉末：６０容量％を添加混合しストロンチウム含有スラリーを作製した。
前記ストロンチウム含有スラリーを前記石英ガラスるつぼの内側に塗布してスラリー層を形成し、このスラリー層の表面に平均粒径：１５０μｍの微細溶融シリカ砂を散布してストロンチウム含有スタッコ層を形成した。この操作を３回繰り返したのち、最後にストロンチウム含有スラリー層を形成し、ついで大気雰囲気中、温度：１０００℃で２時間加熱保持して乾燥し焼成することにより石英ガラスるつぼの内側に、合計厚さが３ｍｍを有する内層を形成し、本発明るつぼ３を作製した。
Example 3
A quartz glass crucible having an inner diameter of 170 mm, an outer diameter of 190 mm, and a depth of 150 mm was prepared.
Furthermore, commercially available average particle size: 1.0 μm ultrafine silica powder (boron content: 0.23 ppm), average particle size: 150 μm fine fused silica sand (boron content: 0.21 ppm) and strontium nitrate did.
Furthermore, colloidal silica containing 30% by volume of colloidal silica having an average particle size of 10 nm or less and the balance: water is prepared, and nitric acid is prepared by dissolving 100 ppm (in terms of wt) of the prepared strontium nitrate in the colloidal silica. Strontium-containing colloidal silica was prepared. A strontium-containing slurry was prepared by adding and mixing 60% by volume of ultrafine silica powder having an average particle size of 1.0 μm to 30% by volume of this strontium nitrate-containing colloidal silica.
The strontium-containing slurry was applied to the inside of the quartz glass crucible to form a slurry layer, and finely fused silica sand having an average particle size of 150 μm was sprayed on the surface of the slurry layer to form a strontium-containing stucco layer. After repeating this operation three times, finally, a strontium-containing slurry layer is formed, and then heated and held in an air atmosphere at a temperature of 1000 ° C. for 2 hours, dried and fired to obtain a total thickness inside the quartz glass crucible. An inner layer having a thickness of 3 mm was formed to produce the crucible 3 of the present invention.
実施例４
内径：１７０ｍｍ、外径：１９０ｍｍ、深さ：１５０ｍｍの寸法を有する石英ガラスるつぼを用意した。
さらに、市販の平均粒径：１．０μｍの超微粉シリカ粉末（ボロン含有量：０．２３ｐｐｍ）、平均粒径：１５０μｍの微細溶融シリカ砂（ボロン含有量：０．２１ｐｐｍ）および水酸化ストロンチウムを用意した。
さらに平均粒径：１０ｎｍ以下のコロイド状シリカ：３０容量％を含有し、残部：水からなるコロイダルシリカを用意し、このコロイダルシリカに前記用意した水酸化ストロンチウムを１００ｐｐｍ（ｗｔ換算）溶解することにより水酸化ストロンチウム含有コロイダルシリカを作製した。この水酸化ストロンチウム含有コロイダルシリカ：３０容量％に対して平均粒径：１．０μｍの超微粉シリカ粉末：６０容量％を添加混合しストロンチウム含有スラリーを作製した。
前記ストロンチウム含有スラリーを前記石英ガラスるつぼの内側に塗布してスラリー層を形成し、このスラリー層の表面に平均粒径：１５０μｍの微細溶融シリカ砂を散布してストロンチウム含有スタッコ層を形成した。この操作を３回繰り返したのち、最後にストロンチウム含有スラリー層を形成し、ついで大気雰囲気中、温度：１０００℃で２時間加熱保持して乾燥し焼成することにより石英ガラスるつぼの内側に、合計厚さが３ｍｍを有する内層を形成し、本発明るつぼ４を作製した。
Example 4
A quartz glass crucible having an inner diameter of 170 mm, an outer diameter of 190 mm, and a depth of 150 mm was prepared.
Furthermore, commercially available average particle size: 1.0 μm ultrafine silica powder (boron content: 0.23 ppm), average particle size: 150 μm fine fused silica sand (boron content: 0.21 ppm) and strontium hydroxide Prepared.
Further, colloidal silica containing 30% by volume of colloidal silica having an average particle size of 10 nm or less and the balance: water is prepared, and the prepared strontium hydroxide is dissolved in 100 ppm (in terms of wt) in this colloidal silica. Colloidal silica containing strontium hydroxide was produced. This strontium hydroxide-containing colloidal silica: 30% by volume was added and mixed with 60% by volume of ultrafine silica powder having an average particle size of 1.0 μm to prepare a strontium-containing slurry.
The strontium-containing slurry was applied to the inside of the quartz glass crucible to form a slurry layer, and finely fused silica sand having an average particle size of 150 μm was sprayed on the surface of the slurry layer to form a strontium-containing stucco layer. After repeating this operation three times, finally, a strontium-containing slurry layer is formed, and then heated and held in an air atmosphere at a temperature of 1000 ° C. for 2 hours, dried and fired to obtain a total thickness inside the quartz glass crucible. An inner layer having a thickness of 3 mm was formed to produce the crucible 4 of the present invention.
従来例
実施例で用意したコロイダルシリカに対して前記用意した平均粒径：１．０μｍの超微粉シリカ粉末：６０％を添加混合してスラリーを作製し、前記スラリーを前記石英ガラスるつぼの内側に塗布してスラリー層を形成し、このスラリー層の表面に平均粒径：１５０μｍの微細溶融シリカ砂を散布してストロンチウム含有スタッコ層を形成し、この操作を３回繰り返したのち、最後にスラリー層を形成し、ついで大気雰囲気中、温度：１０００℃で２時間加熱保持して乾燥し焼成することにより石英ガラスるつぼの内側に、合計厚さが３ｍｍを有する内層を形成し、従来シリコン溶解鋳造用るつぼ（以下、従来るつぼという）を作製した。
To the colloidal silica prepared in the conventional example, the prepared ultrafine silica powder having an average particle diameter of 1.0 μm: 60% was added and mixed to prepare a slurry, and the slurry was placed inside the quartz glass crucible. A slurry layer is formed by coating, and finely fused silica sand having an average particle diameter of 150 μm is sprayed on the surface of the slurry layer to form a strontium-containing stucco layer. This operation is repeated three times, and finally the slurry layer Next, in an air atmosphere, the temperature is kept at 1000 ° C. for 2 hours, dried and fired to form an inner layer having a total thickness of 3 mm inside the quartz glass crucible. A crucible (hereinafter referred to as a conventional crucible) was produced.
このようにして作製した本発明るつぼ１〜４および従来るつぼに、ボロン含有量：０．０１ｐｐｍ未満、抵抗値：２００Ωｍのシリコン原料を装入し、溶解鋳造してシリコンインゴットを作製した。この作製したシリコンインゴットの抵抗値およびシリコンインゴットに含まれるボロン量をＩＣＰ法により測定し、その結果を表１に示した。 A silicon raw material having a boron content of less than 0.01 ppm and a resistance value of 200 Ωm was charged into the crucibles 1 to 4 of the present invention and the conventional crucible thus produced, and melt-cast to prepare a silicon ingot. The resistance value of this produced silicon ingot and the amount of boron contained in the silicon ingot were measured by the ICP method, and the results are shown in Table 1.
表１に示される結果から、本発明るつぼ１〜４を用いて作製したシリコンインゴットは、従来るつぼを用いて作製したシリコンインゴットに比べてボロン濃度の増加が見られないところから、本発明るつぼ１〜４は、溶解鋳造時のボロンによる汚染が少ないことが分かる。 From the results shown in Table 1, the silicon ingot produced using the crucibles 1 to 4 of the present invention shows no increase in boron concentration compared to the silicon ingot produced using the conventional crucible. As for -4, it turns out that there is little contamination by the boron at the time of melt | dissolution casting.
さらに、溶解鋳造して作製したシリコンインゴットの表面に付着している本発明るつぼ１〜４および従来るつぼの内層に含まれるボロン量をＩＣＰ法により測定し、溶解前後の内層に含まれるボロン量を表２に示した。 Furthermore, the amount of boron contained in the inner layer of the crucibles 1 to 4 of the present invention and the conventional crucible adhering to the surface of the silicon ingot produced by melt casting was measured by the ICP method, and the amount of boron contained in the inner layer before and after melting was determined. It is shown in Table 2.
表２に示される結果から、本発明るつぼ１〜４によるシリコン原料溶解鋳造後の本発明るつぼ１〜４の内層に含まれるボロン量は、溶解鋳造前と比較して大きな変化が見られないが、従来るつぼによるシリコン原料溶解鋳造後の従来るつぼの内層に含まれるボロン量は、溶解鋳造前と比較して大きく減少するところから、本発明るつぼは従来るつぼに比べてシリコン原料の溶解鋳造時に内層から溶け出すボロン量が極めて少ないことがわかる。 From the results shown in Table 2, the amount of boron contained in the inner layer of the crucibles 1 to 4 of the present invention after the silicon raw material melt casting by the crucibles 1 to 4 of the present invention is not significantly changed compared to that before the melting casting. Since the amount of boron contained in the inner layer of the conventional crucible after the silicon raw material melt casting by the conventional crucible is greatly reduced as compared with that before the melt casting, the crucible of the present invention is the inner layer at the time of melting and casting the silicon raw material compared to the conventional crucible. It can be seen that the amount of boron that dissolves from the reactor is extremely small.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007131512A (en) * | 2005-08-09 | 2007-05-31 | Mitsubishi Materials Corp | Crucible for high purity silicon melt casting |
| JP2007130687A (en) * | 2005-08-09 | 2007-05-31 | Mitsubishi Materials Corp | Crucible for melt-casting high purity silicon |
| JP2007210860A (en) * | 2006-02-10 | 2007-08-23 | Nippon Steel Materials Co Ltd | Casting mold for producing polycrystalline silicon cast piece |
| JP7383103B1 (en) | 2022-10-28 | 2023-11-17 | 株式会社ヨータイ | Castable dry sprayed material and its construction method |
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2004
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007131512A (en) * | 2005-08-09 | 2007-05-31 | Mitsubishi Materials Corp | Crucible for high purity silicon melt casting |
| JP2007130687A (en) * | 2005-08-09 | 2007-05-31 | Mitsubishi Materials Corp | Crucible for melt-casting high purity silicon |
| JP2007210860A (en) * | 2006-02-10 | 2007-08-23 | Nippon Steel Materials Co Ltd | Casting mold for producing polycrystalline silicon cast piece |
| JP7383103B1 (en) | 2022-10-28 | 2023-11-17 | 株式会社ヨータイ | Castable dry sprayed material and its construction method |
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