JPH029783A - Quartz crucible - Google Patents
Quartz crucibleInfo
- Publication number
- JPH029783A JPH029783A JP15960788A JP15960788A JPH029783A JP H029783 A JPH029783 A JP H029783A JP 15960788 A JP15960788 A JP 15960788A JP 15960788 A JP15960788 A JP 15960788A JP H029783 A JPH029783 A JP H029783A
- Authority
- JP
- Japan
- Prior art keywords
- crucible
- cristobalite
- single crystal
- sol
- quartz glass
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000010453 quartz Substances 0.000 title abstract description 4
- 239000000843 powder Substances 0.000 claims abstract description 26
- 229910021493 α-cristobalite Inorganic materials 0.000 claims abstract description 17
- 238000002844 melting Methods 0.000 claims abstract description 15
- 230000008018 melting Effects 0.000 claims abstract description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 9
- 238000003980 solgel method Methods 0.000 claims abstract description 8
- 239000013078 crystal Substances 0.000 abstract description 33
- 239000011521 glass Substances 0.000 abstract description 14
- 239000000377 silicon dioxide Substances 0.000 abstract description 13
- 239000012535 impurity Substances 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 150000004703 alkoxides Chemical class 0.000 abstract description 3
- 239000007858 starting material Substances 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 description 23
- 239000010703 silicon Substances 0.000 description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 22
- 238000000034 method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 235000012431 wafers Nutrition 0.000 description 5
- 238000010828 elution Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- -1 copper (0.05pp+*) Chemical class 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000005049 silicon tetrachloride Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- VCGRFBXVSFAGGA-UHFFFAOYSA-N (1,1-dioxo-1,4-thiazinan-4-yl)-[6-[[3-(4-fluorophenyl)-5-methyl-1,2-oxazol-4-yl]methoxy]pyridin-3-yl]methanone Chemical compound CC=1ON=C(C=2C=CC(F)=CC=2)C=1COC(N=C1)=CC=C1C(=O)N1CCS(=O)(=O)CC1 VCGRFBXVSFAGGA-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 238000005406 washing Methods 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
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、シリコン単結晶引上げ用の石英ガラスるつぼ
に関し、特に、シリコンウェハーの製造に好適な単結晶
引上げ用石英ガラスるつぼに関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a quartz glass crucible for pulling silicon single crystals, and particularly to a quartz glass crucible for pulling single crystals suitable for manufacturing silicon wafers.
従来、石英ガラスるつぼの製造は、通常、内側にるつぼ
状凹型を備えた回転する水冷シリンダーを用い、その中
にいれたガラス粉末をｍｒ ％溶融法、特に、アーク溶
融により遠心成形する方法が広く採用されている。Traditionally, quartz glass crucibles have been manufactured by using a rotating water-cooled cylinder with a crucible-shaped concave mold inside, and centrifugally molding the glass powder in the cylinder by mr % melting method, especially by arc melting. It has been adopted.
シリコン単結晶の引上げは２通常、約１ｓｏｏ℃付近の
高温で行われるので、そのような高い温度条件下では１
石英ガラスるつぼの大きな変形が生じ、単結晶の歩留ま
りが低下するという不都合があった。そのため、高温に
おける粘性の高い天然石英ガラス（水晶）が上記不都合
を軽減する材料として使用されてきた。しかし、天然の
水晶には、通常。Since the pulling of silicon single crystals is usually carried out at high temperatures around 1 soo Celsius, under such high temperature conditions
This has the disadvantage of causing large deformation of the quartz glass crucible and lowering the yield of single crystals. Therefore, natural quartz glass (crystal), which has high viscosity at high temperatures, has been used as a material to alleviate the above disadvantages. However, natural crystals usually have
例えば、アルミニウム（２０ｐｐｍ） ＊鉄（１ｐｐｍ
） ＋ナトリウム（２ｐｐＨ） ｙカリウム（２ｐｐｓ
＋） ｒ銅（０，０５ｐｐ＋＊）等の金属化合物や、は
う素（０，０３ｐｐＩ１１） 、 りん（０，０３ｐｐ
ｉｎ）等の各種の不純物類が含ま九、これらの不純物類
はシリコン融液に溶出するので、シリコン単結晶に微小
欠陥を発生させるばかりでなく、それらの溶出によって
、はう素やりんのドープを定量的に行うことができない
。このため、シリコン単結晶引上げ用るつぼとして必ず
しも満足し得るものではなかった。For example, aluminum (20ppm) *iron (1ppm
) + Sodium (2ppH) y Potassium (2pps
+) rMetal compounds such as copper (0.05pp+*), boron (0.03ppI11), phosphorus (0.03pp
Contains various impurities such as cannot be carried out quantitatively. For this reason, the crucible was not necessarily satisfactory for pulling silicon single crystals.
一方、合成石英ガラスはＯＨ基を３００〜１２００ｐｐ
ｍ含有しているため、純度は高いが高温での粘性が低い
ので、シリコン単結晶の引上げ時に、るつぼとしての形
を保ち難く、またシリコン融液との反応性に富み、溶出
してシリコンインゴット中の酸素濃度を増加させ、また
、るつぼに穴があくという致命的な欠陥があった。On the other hand, synthetic quartz glass contains 300 to 1200 pp of OH groups.
Since it contains m, its purity is high but its viscosity at high temperatures is low, so it is difficult to maintain the shape of a crucible when pulling a silicon single crystal, and it is highly reactive with silicon melt, so it dissolves and forms a silicon ingot. It had the fatal flaw of increasing the oxygen concentration inside the crucible and creating a hole in the crucible.
かかる実状に立脚して、天然石英ガラスのるつぼの内面
に合成石英ガラスの層をライニングさせたるつぼが提案
された（特公昭５ｇ−５０９５５号公報）。Based on this situation, a crucible was proposed in which the inner surface of a crucible made of natural quartz glass was lined with a layer of synthetic quartz glass (Japanese Patent Publication No. 5G-50955).
しかし、その合成石英ガラス層は、四塩化けい素を加水
分解した粉を溶融したもので、ＯＨ含量が多く、高温で
の粘性が低いこと、また外側石英ガラスからの不純物拡
散があり、依然としてシリコン単結晶の引上げ用るつぼ
として満足し得るものではない。However, the synthetic silica glass layer is made by melting powder obtained by hydrolyzing silicon tetrachloride, has a high OH content, has low viscosity at high temperatures, and has impurity diffusion from the outer quartz glass. This is not satisfactory as a crucible for pulling single crystals.
更に、合成石英ガラスのＯＨａ度を低下させたものを試
みた。ゾル−ゲル法によってできた乾燥ゲルをハロゲン
で処理することでＯＨ値をｐｐｍ以下にし、溶融したる
つぼを試作して使用したところ、変形、０２溶出は天然
石英より悪かった。これより本発明者らは、高粘性の石
英ガラスを得るためには、結晶に近い構造をガラス中に
残存させること（いわゆるクリストバライトを経由する
）が、ＯｔＩ値を低減させることと同時に満たすべき条
件であることを発見した。この高粘性化は、るつぼが大
口径化の傾向にある実情から非常に重要な特性である。Furthermore, we tried a synthetic quartz glass with a lower OHa degree. When a dried gel produced by the sol-gel method was treated with halogen to reduce the OH value to ppm or less and a melted crucible was made and used as a prototype, deformation and 02 elution were worse than natural quartz. From this, the present inventors have determined that in order to obtain a highly viscous quartz glass, it is necessary to allow a structure close to crystal to remain in the glass (via so-called cristobalite), and at the same time to reduce the OtI value. I discovered that. This high viscosity is a very important characteristic due to the fact that crucibles tend to have larger diameters.
このようなシリコン単結晶の引上げ用るつぼの実状に鑑
み、本発明者らは、上記譜欠点を解消する方法として、
ゲル状シリカを加熱脱水した時に結晶の変態が起こり、
α−グリス］−パライトに変化すること、その変態時に
ＯＨ基の除去を伴うことを発見し、これを石英ガラスる
つぼの原料として用いることを考案した。In view of the actual situation of crucibles for pulling silicon single crystals, the present inventors have developed a method to eliminate the above-mentioned score defects.
When gelled silica is heated and dehydrated, crystal transformation occurs,
It was discovered that the transformation into [alpha]-gris]-palite was accompanied by the removal of OH groups during the transformation, and the inventor devised the use of this as a raw material for silica glass crucibles.
すなわち、本発明の技術的課題ないし目的は、特に、シ
リコン単結晶の引上げにおける高温領域で適切な高粘性
を有し、しかもＯＨ基が少ないために実質的にシリコン
と反応しない高純度の石英ガラスるつぼを提供すること
にある。That is, the technical problem or object of the present invention is to develop a high-purity quartz glass that has a high viscosity suitable for the high-temperature region used for pulling silicon single crystals, and that does not substantially react with silicon because it contains few OH groups. It is about providing a melting pot.
本発明者らは、上記目的を達成するために、研究を重ね
た結果、金属アルコキシドを通常知られたゾル−ゲル法
によってゲル状シリカにし、これを更に加熱溶融して形
成された α−クリストバライトを含むガラス粉を少な
くとも内面層に有するるつぼが、上記技術的課題を効果
的に解消し得る実用的に極めて望ましいるつぼを提供す
ることを見出した。In order to achieve the above object, the present inventors have conducted repeated research and found that α-cristobalite is formed by converting metal alkoxide into gel-like silica using the commonly known sol-gel method, and then heating and melting the gel-like silica. It has been found that a crucible having at least the inner surface layer a glass powder containing glass powder provides a practically extremely desirable crucible that can effectively solve the above technical problems.
すなわち１本発明は、ゾル−ゲル法による合成シリカよ
り作成した α−クリストバライトを含むガラス粉を溶
融形成させて成るシリコン単結晶引上げ用石英ガラスる
つぼを提供する。That is, one aspect of the present invention provides a quartz glass crucible for pulling a silicon single crystal, which is formed by melting glass powder containing α-cristobalite made from synthetic silica using a sol-gel method.
また１本発明は、金属アルコキシドよりゾル−ゲル法に
よりゲル状シリカを得、これを加熱してあらかじめα−
クリストバライトを少なくとも一部形成させ、その粉末
をアーク溶融法により回転式成形型の内表面部で溶融さ
せるか、ゾル状シリカを回転式成形型表面にキャスティ
ングし、これを加熱して溶融形成させるシリコン単結晶
弓１上げ用石英ガラスるつぼの効果的製造方法を提供す
る。In addition, in the present invention, gelled silica is obtained from a metal alkoxide by a sol-gel method, and this is heated to preliminarily produce α-
Silicone formed by forming at least a portion of cristobalite and melting the powder on the inner surface of the rotary mold by arc melting, or by casting sol-like silica on the surface of the rotary mold and heating it to melt and form the powder. To provide an effective method for manufacturing a quartz glass crucible for raising a single crystal bow.
本発明のるつぼは、上記のように、α−クリストバライ
トを含むガラス粉の溶融成形層で構成させて成るもので
ある。As described above, the crucible of the present invention is constituted by a melt-molded layer of glass powder containing α-cristobalite.
本発明のるつぼに用いられるα−クリストバライトを含
むガラス粉は１例えば、ｙｏｇｙｏ ｋｙｏｋａｉ ｓ
ｈｉ、、８７−８．１９７９ （ｙａｍａｎｅら）に開
示された方法によって製造される合成シリカゾルが好都
合に利用でき、これを加熱、溶融して容易に作ることが
できる。The glass powder containing α-cristobalite used in the crucible of the present invention is 1, for example, yogyo kyokais.
Synthetic silica sol produced by the method disclosed in Yamane et al., 87-8.
本発明のるつぼは、例えば１次のようにして製造される
。The crucible of the present invention is manufactured, for example, in the following manner.
まず、金かアルコキシドを出発原料として従来公知のゾ
ル−ゲル法によりゲル状シリカを合成し。First, gelled silica was synthesized using a conventionally known sol-gel method using gold alkoxide as a starting material.
これを８００〜１６００℃程度の温度に加熱、結晶化さ
せてクリストバライトを形成する。この温度は、結晶化
の速度及びコストから１１００−１４００℃でおこなう
ことが好ましい。これを粉砕して適度の粉粒度に調整す
る６次いで、その粉末をるつぼ形成用回転式水冷シリン
ダーの型内に導入し、該シリンダーを回転させながらア
ーク溶融させる方法により容易に製造することができる
。この回転溶融成形においては１通常、最外層部まで溶
融させないで、型から取り出されたるつぼの外側の粉を
取り除き、上部をカットして所望形状のるつぼとして提
供される、また、シリカゾル液を、るつぼ形成用回転式
水冷シリンダーの型の内表面にキャスティングし、その
シリンダーを回転させながらゾル液をゲル化させ、乾燥
した後ゆっくり昇温させて、例えば、８００〜１６００
℃の温度でα−クリストバライトを形成させ、のちにガ
ラス化以上の温度、例えば、 ２０００℃で溶融するこ
とによっても効果的に製造することができる。This is heated to a temperature of about 800 to 1600°C to crystallize it to form cristobalite. This temperature is preferably 1100 to 1400°C from the viewpoint of crystallization speed and cost. The powder is pulverized and adjusted to an appropriate particle size.6 Next, the powder is introduced into the mold of a rotary water-cooled cylinder for forming a crucible, and the cylinder is rotated while arc melting, which makes it easy to manufacture. . In this rotary melt molding, 1. Usually, the outermost layer of the crucible is not melted, the powder on the outside of the crucible is removed from the mold, and the upper part is cut to provide a crucible of the desired shape. Casting is carried out on the inner surface of a rotary water-cooled cylinder mold for forming a crucible, the sol solution is gelled while the cylinder is rotated, and after drying, the temperature is slowly raised to a temperature of, for example, 800 to 1600.
It can also be effectively produced by forming α-cristobalite at a temperature of 10°C and then melting it at a temperature higher than vitrification, for example 2000°C.
α−クリストバライトを含むガラス粉を溶融してなる合
成石英ガラスるつぼが、高温時に高粘性を有する理由は
明らかではないが、該ゾルからのアモルファス状のゲル
状シリカを加熱、脱水させるとき、クリストバライトに
変化して結晶の変態が生じ、その際のＯＨ基含有濃度の
減少が高温時の粘性と密接に関連すること、及びその濃
度減少に応じて粘性が高くなる傾向を、有することが判
った。また、そのＯＨ基濃度は、約１１００ｐｐを超え
ると高温時の粘性が低く、シリコンｊｌｉ結晶の引上げ
用るつぼとして適当ではないことも判った。従って１本
発明におけるα−クリストバライトを含むガラス粉は、
実質的に約１１００ｐｐ以下のＯＨ基濃度の結晶化物で
あることが好ましい。この場合、α−クリストバライト
量は、８０重斌％となる。It is not clear why a synthetic silica glass crucible made by melting glass powder containing α-cristobalite has high viscosity at high temperatures, but when amorphous gel-like silica from the sol is heated and dehydrated, cristobalite It was found that the decrease in the concentration of OH groups at this time is closely related to the viscosity at high temperatures, and that the viscosity tends to increase as the concentration decreases. It was also found that when the OH group concentration exceeds about 1100 pp, the viscosity at high temperatures is low, making it unsuitable as a crucible for pulling silicon JLI crystals. Therefore, the glass powder containing α-cristobalite in the present invention is
Preferably, the crystallized product has an OH group concentration of substantially less than about 1100 pp. In this case, the amount of α-cristobalite is 80% by weight.
本発明の石英ガラスるつぼは、高純度α−クリストバラ
イトを含むガラス粉を溶融形成したもので、シリコン融
液への溶出が実質的になく、また。The quartz glass crucible of the present invention is formed by melting glass powder containing high-purity α-cristobalite, and is substantially free from elution into silicon melt.
るつぼ自体の高温時の粘性が高いので大口径のシリコン
インゴットを引き上げる時のるつぼの変形が少なく自動
制御が容易で、単結晶の小止りが向上する。更に、るつ
ぼ内面層の特異性に関連し５て、引きしげられるシリコ
ン単結晶に対する悪影響は実質的になく、微小欠陥の発
生も極めて少ない。Since the crucible itself has high viscosity at high temperatures, there is little deformation of the crucible when pulling up a large diameter silicon ingot, making automatic control easy and improving the small size of the single crystal. Furthermore, due to the specificity of the inner layer of the crucible, there is virtually no adverse effect on the pulled silicon single crystal, and the occurrence of minute defects is extremely low.
次に、具体例により１本発明を更に詳細に説明する。 Next, the present invention will be explained in more detail using a specific example.
実施例 １
前記ｙｏｇｙｏ ｋｙｏｋａｉ ｓｈｉ、、８７−８．
１９７９に記載の方法でゲル状シリカを調製し、１２０
℃の温度で２４時間乾燥後、温度１３００℃で３時間加
熱処理して結晶化α−クリストバライト含有ガラス粉を
得た。Example 1 Said yogyo kyokai shi, 87-8.
Gel silica was prepared by the method described in 1979, and 120
After drying at a temperature of 1300° C. for 24 hours, the mixture was heat-treated at a temperature of 1300° C. for 3 hours to obtain a glass powder containing crystallized α-cristobalite.
得られた結晶のＯ）Ｉ基濃度はｌ０ＰＰ！＋（結晶の割
合は９５重量％）であった。これを粉砕して５０＃〜８
０＃に粒度を調整した。このクリストバライトの含有不
純物を分析した結果は、 Ａ Ｑ ： ０．１ｐｐ−以
下、Ｆｅ：０、ｌｐｐｍ以下、 Ｎａ ： ０．１ｐｐ
ｉ＋以下、 Ｋ ： ０．ｌｐｐｍ以下。The O)I group concentration of the obtained crystal is 10PP! + (the proportion of crystals was 95% by weight). Grind this to 50#~8
The particle size was adjusted to 0#. The results of analyzing the impurities contained in this cristobalite are as follows: AQ: 0.1pp- or less, Fe: 0, lppm or less, Na: 0.1pp-
i+ or less, K: 0. lppm or less.
Ｂ ： ０．０ＩＰＰＲ１以下、 Ｐ ： ０．０１ｐ
ｐｍ以下であった。B: 0.0IPPR1 or less, P: 0.01p
It was below pm.
この粉体を回転式水冷シリンダーに詰め、回転条件下に
三相アークで溶融させた。溶融成形して得られたるつぼ
は、外径４５８０１１１ 、肉厚８ｍ＋ｏ及び高さ４６
０ｍｍであった。これを高さ３８０ｍｍで切断してシリ
コン単結晶引き上げ用るつぼとして使用し、ノンドープ
で６インチの単結晶を引き上げた。単結晶から得られた
シリコンウェハーの特性値（０２１度、Ｃ温度及び電気
抵抗）を測定し、後記第１表に示した。This powder was packed into a rotating water-cooled cylinder and melted with a three-phase arc under rotating conditions. The crucible obtained by melt molding has an outer diameter of 4580111, a wall thickness of 8m+o, and a height of 46.
It was 0 mm. This was cut to a height of 380 mm and used as a crucible for pulling a silicon single crystal, and a 6-inch single crystal was pulled without doping. Characteristic values (021 degrees, C temperature, and electrical resistance) of the silicon wafer obtained from the single crystal were measured and shown in Table 1 below.
なお、るつぼ自体のＯＨ基濃度及び高温粘性値は、上記
の切断された部分を使い、赤外線吸収スペクトル及びＦ
ｉｂｅｒ ｅｌｏｎｇａｔｉｏｎ法で測定したもので、
それらの結果を第１表に併記した。The OH group concentration and high-temperature viscosity value of the crucible itself can be determined using the above-mentioned cut section, and the infrared absorption spectrum and F
It was measured by the iber elongation method,
The results are also listed in Table 1.
実施例２．比較例 １〜２
実施例１で調製し、乾燥したゲル状シリカを用いて、高
温での結晶化の加熱処理における温度と時間を変えた三
種の結晶化α−クリストバライト含有ガラス粉を作り、
それぞれの粒度調製粉末を用いて、同様にるつぼを作成
した。Example 2. Comparative Examples 1-2 Using the dried gel-like silica prepared in Example 1, three types of crystallized α-cristobalite-containing glass powders were prepared by changing the temperature and time of the heat treatment for crystallization at high temperatures,
A crucible was similarly created using each particle size-adjusted powder.
それぞれの加熱処理時間は、 １３００℃×５０分（実
施例２）、 １３００℃×１０分（比較例 １）及び１
０００℃ＸｔＯ分（比較例２）である。The respective heat treatment times were: 1300°C x 50 minutes (Example 2), 1300°C x 10 minutes (Comparative Example 1), and 1
000°C XtO min (Comparative Example 2).
各るつぼ自体の特性、及びそれを使用して引き上げられ
たシリコン単結晶から得られたシリコンウェハーの特性
は第１表の通りである。The characteristics of each crucible itself and the characteristics of the silicon wafer obtained from the silicon single crystal pulled using the crucible are shown in Table 1.
なお、シリコンウェハーの特性の測定は、それぞれ次の
装置による。Note that the characteristics of the silicon wafer were measured using the following devices.
Ｏｘ ６度（原子／ａｊ）：ＦＴ−ＩＲＯ濃度（原子／
ａ＋？） ： Ｆ Ｔ−Ｉ Ｒ抵抗値（Ω・ａｎ）：４
端針抵抗計
比較例３
天然水晶を粉砕、浮遊選鉱、酸洗浄を行った粉末を水冷
回転シリンダーに詰め、三相アークで溶融して同様にる
つぼを製造した。このるつぼに含まれる不純物の分析値
は、次の通りであった。Ox 6 degrees (atoms/aj): FT-IRO concentration (atoms/aj)
a+? ): F T-IR resistance value (Ω・an): 4
End Needle Resistance Meter Comparative Example 3 Powder obtained by crushing natural quartz, flotation, and acid washing was packed into a water-cooled rotating cylinder and melted with a three-phase arc to produce a crucible in the same manner. The analytical values of impurities contained in this crucible were as follows.
Ａ１．！ ： １８ｐｐｍ、 Ｆｅ： ２ｐｐｍ、 Ｎ
ａ： １．８ｐｐＨｌ、 Ｋ ： １．２ｐｐ＋＋＋、
［３： ０．Ｏ５ｐｐｍ、 Ｐ ： ０．０４ｐｐｌ
＋＋比較例４
四塩化けい素を火炎分解し、径２００ ｗ＋φ及び長さ
４００ｍのインゴットを成形した８その中心に、径３０
晴φの穴をあけ、高周波溶融して径４６０＋ｎｍφ。A1. ! : 18ppm, Fe: 2ppm, N
a: 1.8ppHl, K: 1.2pp+++,
[3: 0. O5ppm, P: 0.04ppl
++ Comparative Example 4 Silicon tetrachloride was flame decomposed and an ingot with a diameter of 200 w + φ and a length of 400 m was formed.
Drill a clear φ hole and high-frequency melt it to a diameter of 460+nmφ.
肉厚５１１１１１のパイプを成形した。そのパイプの一
端を酸水素バーナーで封じ、球状に成形してるつぼを作
った。このるつぼは、含有不純物の少ない実施例１と実
質的に同程度のものであった。A pipe with a wall thickness of 511111 mm was molded. One end of the pipe was sealed with an oxyhydrogen burner and molded into a spherical shape to create a crucible. This crucible contained substantially the same level of impurities as Example 1.
上記比較例１及び２のるつぼについても同様の測定を行
い、それらの結果を第１表にまとめて示すと共に、上記
各側のるつぼにおける単結晶引上げ評価を付記した。Similar measurements were performed on the crucibles of Comparative Examples 1 and 2, and the results are summarized in Table 1, with evaluations of single crystal pulling in the crucibles on each side listed above.
第 １ 表
−るコＶ狩独−シリコンウェハ士二
例Ｎｏ、 Ｏ！（５度粘性値 Ｏａ度 Ｃ濃度 抵抗値
結晶引上（ｐｐｌＩｌ） Ｃ拳１）（ａｔｏｌ］ｌ
／ａ＋？） （同左）（Ω・個）げ評価実施例１１２
比較例１３１０
１２．５ ８ＸＩ０１′
３．５ ２Ｘ１０１７
０．６ ６Ｘ １０１７
０．２ ７Ｘ１０１７
ｉ、ｇ ５Ｘ１０”
０．２ ７ｘ １０”
良好−
食事１
良ψ１
打電′
３ＸＩＯ” １０３２
２ＸＩＯ” ９５３
３Ｘ１０” ５６７不
４ＸｌＯ” ５９２不
６Ｘ１０” ２９５ 良
３ｘｌＯ” ３２０不
ただし、＄１は、１４００℃の温度におけるＸ １０”
ｐｏｉ、５ｅｅ−２は、歩出り８０％以上で引き上げら
れた。Table 1 - Ruko V Karidoku - Silicon wafer engineer 2 examples No, O! (5 degree viscosity value Oa degree C concentration resistance value crystal pulling (pplIl) C fist 1) (atol]l
/a+? ) (Same as left) (Ω・pcs) Evaluation Example 112 Comparative Example 1310 12.5 8XI01' 3.5 2X1017 0.6 6X 1017 0.2 7X1017 i, g 5X10" 0.2 7x 10" Good - Meal 1 Good ψ1 3XIO” 1032 2XIO” 953 3X10” 567 Not 4X10” 592 Not 6X10” 295 Good 3x1O” 320 Bad However, $1 is X 10” at a temperature of 1400℃
poi, 5ee-2 was raised with a yield of 80% or more.
傘１は、引上げ開始３時間後に単結晶が得られなくなっ
た。In Umbrella 1, no single crystal could be obtained 3 hours after the start of pulling.
Ｃは、引上げ開始２．５時間後に単結晶が９ｊ）られな
くなった。In C, a single crystal no longer formed 9j) 2.5 hours after the start of pulling.
本発明のるつぼは、従来技術と比較し、ゲル状シリカよ
り製造したα−クリストバライトを含む石英ガラス粉を
溶融しであるため、極端に○Ｈ濃度が低く、且つ合成石
英ガラスと同様の高純度の特性をもつものである。Compared to the conventional technology, the crucible of the present invention melts quartz glass powder containing α-cristobalite produced from gel-like silica, so it has an extremely low concentration of ○H and has a high purity similar to that of synthetic silica glass. It has the following characteristics.
この石英ガラスるつぼをシリコン単結晶引上げに使用し
た場合、Ｂ、Ｐの溶出が完全に抑えることができるため
、加えたＢ−＋Ｐのドープ剤の理論量で抵抗が制御でき
る。また、Ａ Ｑ 、 Ｆｅ、 Ｎａ。When this quartz glass crucible is used to pull a silicon single crystal, the elution of B and P can be completely suppressed, so the resistance can be controlled by the theoretical amount of the added B-+P dopant. Also, AQ, Fe, Na.
Ｋ等の金属の溶出も殆どないため、シリコン単結晶中の
結合に害を及ぼすことがなく、微小欠陥が極めて少ない
ものが得られる。更に、本発明の利点は、安価なゾル−
ゲル法により、比較的低温でα−クリストバライトを生
成させ、これを従来の溶融法で容易にるつぼに成形する
ことができるので、産業上優れた有意性をもつものであ
る。Since there is almost no elution of metals such as K, there is no harm to the bonds in the silicon single crystal, and a product with extremely few micro defects can be obtained. Furthermore, an advantage of the present invention is that inexpensive sol-
The gel method produces α-cristobalite at a relatively low temperature and can be easily formed into a crucible using the conventional melting method, so it has great industrial significance.
Claims (1)
を含む石英ガラス粉を溶融して成ることを特徴とする石
英ガラスるつぼ。 ２、上記α−クリストバライトを含む石英ガラス粉を溶
融したるつぼの水酸基濃度が１００ｐｐｍ以下であり、
粘性値が１４００℃において１０＾１＾０ポイズ以上で
あることを特徴とする請求項１記載の石英ガラスるつぼ
。[Scope of Claims] 1. A quartz glass crucible made by melting quartz glass powder containing α-cristobalite produced by a sol-gel method. 2. The hydroxyl group concentration of the crucible in which the quartz glass powder containing α-cristobalite is melted is 100 ppm or less,
The quartz glass crucible according to claim 1, having a viscosity value of 10^1^0 poise or more at 1400°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15960788A JPH029783A (en) | 1988-06-28 | 1988-06-28 | Quartz crucible |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15960788A JPH029783A (en) | 1988-06-28 | 1988-06-28 | Quartz crucible |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH029783A true JPH029783A (en) | 1990-01-12 |
Family
ID=15697407
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15960788A Pending JPH029783A (en) | 1988-06-28 | 1988-06-28 | Quartz crucible |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH029783A (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03208880A (en) * | 1990-01-10 | 1991-09-12 | Mitsubishi Materials Corp | Quartz crucible and production thereof |
| JPH03252387A (en) * | 1990-03-01 | 1991-11-11 | Shin Etsu Chem Co Ltd | Synthetic quartz glass crucible and production thereof |
| WO2000006811A1 (en) * | 1998-07-31 | 2000-02-10 | Shin-Etsu Quartz Products Co., Ltd. | Quartz glass crucible for pulling up silicon single crystal and process for producing the same |
| JP2003517990A (en) * | 1999-12-22 | 2003-06-03 | 信越石英株式会社 | Quartz glass crucible and its manufacturing method |
| KR100710049B1 (en) * | 2002-12-27 | 2007-04-20 | 주식회사 실트론 | A Quartz crucible of grower of silicon single crystals |
| US10618833B2 (en) | 2015-12-18 | 2020-04-14 | Heraeus Quarzglas Gmbh & Co. Kg | Preparation of a synthetic quartz glass grain |
| US10676388B2 (en) | 2015-12-18 | 2020-06-09 | Heraeus Quarzglas Gmbh & Co. Kg | Glass fibers and pre-forms made of homogeneous quartz glass |
| US10730780B2 (en) | 2015-12-18 | 2020-08-04 | Heraeus Quarzglas Gmbh & Co. Kg | Preparation of a quartz glass body in a multi-chamber oven |
| US11053152B2 (en) | 2015-12-18 | 2021-07-06 | Heraeus Quarzglas Gmbh & Co. Kg | Spray granulation of silicon dioxide in the preparation of quartz glass |
| US11236002B2 (en) | 2015-12-18 | 2022-02-01 | Heraeus Quarzglas Gmbh & Co. Kg | Preparation of an opaque quartz glass body |
| US11299417B2 (en) | 2015-12-18 | 2022-04-12 | Heraeus Quarzglas Gmbh & Co. Kg | Preparation of a quartz glass body in a melting crucible of refractory metal |
| US11339076B2 (en) | 2015-12-18 | 2022-05-24 | Heraeus Quarzglas Gmbh & Co. Kg | Preparation of carbon-doped silicon dioxide granulate as an intermediate in the preparation of quartz glass |
| US11492282B2 (en) | 2015-12-18 | 2022-11-08 | Heraeus Quarzglas Gmbh & Co. Kg | Preparation of quartz glass bodies with dew point monitoring in the melting oven |
| US11492285B2 (en) | 2015-12-18 | 2022-11-08 | Heraeus Quarzglas Gmbh & Co. Kg | Preparation of quartz glass bodies from silicon dioxide granulate |
| US11952303B2 (en) | 2015-12-18 | 2024-04-09 | Heraeus Quarzglas Gmbh & Co. Kg | Increase in silicon content in the preparation of quartz glass |
-
1988
- 1988-06-28 JP JP15960788A patent/JPH029783A/en active Pending
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03208880A (en) * | 1990-01-10 | 1991-09-12 | Mitsubishi Materials Corp | Quartz crucible and production thereof |
| JPH03252387A (en) * | 1990-03-01 | 1991-11-11 | Shin Etsu Chem Co Ltd | Synthetic quartz glass crucible and production thereof |
| WO2000006811A1 (en) * | 1998-07-31 | 2000-02-10 | Shin-Etsu Quartz Products Co., Ltd. | Quartz glass crucible for pulling up silicon single crystal and process for producing the same |
| US6280522B1 (en) | 1998-07-31 | 2001-08-28 | Shin-Etsu Quartz Products Co. Ltd. | Quartz glass crucible for pulling silicon single crystal and production process for such crucible |
| JP2003517990A (en) * | 1999-12-22 | 2003-06-03 | 信越石英株式会社 | Quartz glass crucible and its manufacturing method |
| JP4746240B2 (en) * | 1999-12-22 | 2011-08-10 | 信越石英株式会社 | A method for producing a quartz glass crucible. |
| KR100710049B1 (en) * | 2002-12-27 | 2007-04-20 | 주식회사 실트론 | A Quartz crucible of grower of silicon single crystals |
| US10676388B2 (en) | 2015-12-18 | 2020-06-09 | Heraeus Quarzglas Gmbh & Co. Kg | Glass fibers and pre-forms made of homogeneous quartz glass |
| US10618833B2 (en) | 2015-12-18 | 2020-04-14 | Heraeus Quarzglas Gmbh & Co. Kg | Preparation of a synthetic quartz glass grain |
| US10730780B2 (en) | 2015-12-18 | 2020-08-04 | Heraeus Quarzglas Gmbh & Co. Kg | Preparation of a quartz glass body in a multi-chamber oven |
| US11053152B2 (en) | 2015-12-18 | 2021-07-06 | Heraeus Quarzglas Gmbh & Co. Kg | Spray granulation of silicon dioxide in the preparation of quartz glass |
| US11236002B2 (en) | 2015-12-18 | 2022-02-01 | Heraeus Quarzglas Gmbh & Co. Kg | Preparation of an opaque quartz glass body |
| US11299417B2 (en) | 2015-12-18 | 2022-04-12 | Heraeus Quarzglas Gmbh & Co. Kg | Preparation of a quartz glass body in a melting crucible of refractory metal |
| US11339076B2 (en) | 2015-12-18 | 2022-05-24 | Heraeus Quarzglas Gmbh & Co. Kg | Preparation of carbon-doped silicon dioxide granulate as an intermediate in the preparation of quartz glass |
| US11492282B2 (en) | 2015-12-18 | 2022-11-08 | Heraeus Quarzglas Gmbh & Co. Kg | Preparation of quartz glass bodies with dew point monitoring in the melting oven |
| US11492285B2 (en) | 2015-12-18 | 2022-11-08 | Heraeus Quarzglas Gmbh & Co. Kg | Preparation of quartz glass bodies from silicon dioxide granulate |
| US11708290B2 (en) | 2015-12-18 | 2023-07-25 | Heraeus Quarzglas Gmbh & Co. Kg | Preparation of a quartz glass body in a multi-chamber oven |
| US11952303B2 (en) | 2015-12-18 | 2024-04-09 | Heraeus Quarzglas Gmbh & Co. Kg | Increase in silicon content in the preparation of quartz glass |
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