JPH085739B2 - Quartz glass crucible manufacturing method - Google Patents
Quartz glass crucible manufacturing methodInfo
- Publication number
- JPH085739B2 JPH085739B2 JP61315580A JP31558086A JPH085739B2 JP H085739 B2 JPH085739 B2 JP H085739B2 JP 61315580 A JP61315580 A JP 61315580A JP 31558086 A JP31558086 A JP 31558086A JP H085739 B2 JPH085739 B2 JP H085739B2
- Authority
- JP
- Japan
- Prior art keywords
- quartz glass
- glass crucible
- crucible
- concentration
- single crystal
- 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.)
- Expired - Lifetime
Links
Landscapes
- Surface Treatment Of Glass (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Glass Melting And Manufacturing (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は石英ガラスルツボの製造方法に関し、特にシ
リコン単結晶の引上げに用いられるものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a silica glass crucible, and is particularly used for pulling a silicon single crystal.
半導体バイスの基板として用いられるシリコン単結晶
は主にCZ法により製造されている。この方法は、原理的
にはルツボ内に多結晶シリコン原料を装填し、周囲から
加熱して多結晶シリコン原料を溶融した後、上方から種
結晶を吊下してシリコン融液に浸し、これを引上げるこ
とによりシリコン単結晶インゴットを引上げるものであ
る。実用的には、上記ルツボとしては石英ガラス製のも
のが用いられている。The silicon single crystal used as the substrate of the semiconductor vice is mainly manufactured by the CZ method. In this method, in principle, the polycrystalline silicon raw material is loaded in the crucible, the polycrystalline silicon raw material is melted by heating from the surroundings, and then the seed crystal is suspended from above and immersed in the silicon melt, By pulling up, the silicon single crystal ingot is pulled up. Practically, the crucible is made of quartz glass.
ところで、半導体デバイスでは、シリコン基板に含ま
れる金属不純物の影響により素子特性が悪影響を受ける
ことはよく知られている。上述したシリコン単結晶引上
げ操作中においても、石英ガラスルツボがシリコン融液
に浸食されることが原因となって、石英ガラスルツボ中
の金属不純物がシリコン単結晶中に取込まれるため、ル
ツボ中の金属不純物を減少させる努力もなされている。
実際に、現在使用されている石英ガラスルツボでは、全
肉厚の平均値すなわち後述の実施例に示されるような石
英ガラスルツボから全肉厚にわたるブロック状の試料を
切り出してこれを粉砕して測定される値で、アルカリ金
属等の含有量は0.1ppm以下、Alについても７〜8ppm程度
と極めて少なくなっている。By the way, it is well known that in semiconductor devices, the element characteristics are adversely affected by the influence of metal impurities contained in the silicon substrate. Even during the above-described silicon single crystal pulling operation, the silica glass crucible is eroded by the silicon melt, and the metal impurities in the silica glass crucible are taken into the silicon single crystal. Efforts are also being made to reduce metallic impurities.
Actually, in the currently used quartz glass crucible, an average value of the total wall thickness, that is, a block-shaped sample over the entire wall thickness is cut out from the quartz glass crucible as shown in the examples described below, and this is ground and measured. The content of alkali metals and the like is 0.1 ppm or less, and Al is 7 to 8 ppm, which is extremely small.
しかし、上述したようにAlの含有量が少ない石英ガラ
スルツボを用いた場合でも、引上げられたシリコン単結
晶には半導体デバイスの特性い対する影響という観点か
ら無視できない程度のAlが含まれてしまうという問題が
あった。However, even if a quartz glass crucible with a low Al content is used as described above, the pulled silicon single crystal contains Al that cannot be ignored in terms of the effect on the characteristics of the semiconductor device. There was a problem.
本発明は上記問題点を解決するためになされたもので
あり、実質的にシリコン単結晶に取り込まれるAlを少な
くすることができる石英ガラスルツボを容易に製造し得
る方法を提供することを目的とする。The present invention has been made to solve the above problems, and an object of the present invention is to provide a method capable of easily producing a quartz glass crucible capable of substantially reducing Al taken into a silicon single crystal. To do.
本発明者らは上述したように石英ガラスルツボ中のAl
含有量が十分少ないにもかかわらず、シリコン単結晶に
取込まれるAlの量が多くなる原因について検討した結
果、以下のようなことを究明した。すなわち、石英ガラ
スルツボ内のAl濃度は上述したように７〜8ppmである
が、これは全体的な平均値であり、実際にはAl濃度は石
英ガラスルツボの内表面側で150〜1000ppmと極端に高
く、内部へ向うにつれて急激に減少するという分布を有
していることを見出した。したがって、石英ガラスルツ
ボの内表面がシリコン融液によって浸食されると、シリ
コン単結晶には予想以上のAlが取込まれることになる。As described above, the present inventors have found that Al in the quartz glass crucible is
As a result of investigating the cause of increasing the amount of Al taken into the silicon single crystal despite the fact that the content is sufficiently low, the following was clarified. That is, the Al concentration in the quartz glass crucible is 7 to 8 ppm as described above, but this is an overall average value. It was found that it has a distribution that is extremely high and decreases sharply toward the inside. Therefore, when the inner surface of the quartz glass crucible is eroded by the silicon melt, more than expected Al is taken into the silicon single crystal.
なお、石英ガラスルツボ内でAl濃度が上述したような
分布をもつ原因は不明であるが、石英ガラスルツボの通
常の製造方法であるアーク溶融法に何らかの問題がある
と考えられる。The cause of the distribution of the Al concentration in the quartz glass crucible as described above is unknown, but it is considered that there is some problem in the arc melting method which is a usual method for manufacturing a quartz glass crucible.
本発明はこのような知見に基づいてなされたものであ
る。すなわち本発明の石英ガラスルツボの製造方法は、
SiO2原料を通常のアーク溶融法によりルツボ形状とした
後、その内表面をHF水溶液で30μｍ以上エッチングする
ことを特徴とするものである。このHF水溶液による処理
条件は、例えば50％HF水溶液で30分以上である。The present invention has been made based on such findings. That is, the manufacturing method of the quartz glass crucible of the present invention,
It is characterized in that the SiO 2 raw material is crucible-shaped by a usual arc melting method, and then the inner surface thereof is etched by 30 μm or more with an HF aqueous solution. The treatment condition with this HF aqueous solution is, for example, 30 minutes or more with a 50% HF aqueous solution.
このような本願発明によれば、内表面が溶融シリコン
により浸食されても、シリコン単結晶中に取込まれるAl
を減少させることができ、ひいては半導体デバイスの素
子特性への悪影響を低減することができる石英ガラスル
ツボを容易に製造することができる方法を提供できる。According to such an invention of the present application, even if the inner surface is eroded by molten silicon, Al taken into the silicon single crystal
Therefore, it is possible to provide a method capable of easily manufacturing a quartz glass crucible capable of reducing the adverse effect on the element characteristics of the semiconductor device.
以下、本発明の実施例を説明する。 Examples of the present invention will be described below.
原料として高純度SiO2粉末を用い、アーク溶融法によ
り14インチ径、肉厚約7mmの石英ガラスルツボを作製し
た。この石英ガラスルツボから全肉厚にわたるブロック
状の試料を切出し、これを粉砕して金属元素の濃度を測
定した。この結果を下記第１表のＴ（totalの略）に示
す。Using a high-purity SiO 2 powder as a raw material, a quartz glass crucible having a diameter of 14 inches and a wall thickness of about 7 mm was produced by an arc melting method. A block-shaped sample having a total thickness was cut out from the quartz glass crucible, and this was crushed to measure the concentration of the metal element. The results are shown in T (abbreviation of total) in Table 1 below.
次に、この石英ガラスルツボ内に50％HF水溶液を入れ
て30分間保持し、石英ガラスルツボの内表面をエッチン
グした後、回収したHF水溶液中に溶解しているSiO2量及
び金属元素の濃度を測定した。そして、SiO2量から溶解
した石英ガラスルツボの厚みを換算するとともに、その
厚みの石英ガラス中の金属元素の濃度を計算した。この
結果を下記第１表のＳ（surfaceの略）に示す。Next, after putting 50% HF aqueous solution into this quartz glass crucible and holding it for 30 minutes to etch the inner surface of the quartz glass crucible, the amount of SiO 2 and the concentration of metallic elements dissolved in the recovered HF aqueous solution. Was measured. Then, the thickness of the fused silica glass crucible was converted from the amount of SiO 2 , and the concentration of the metal element in the silica glass having that thickness was calculated. The results are shown in S (abbreviation of surface) in Table 1 below.
また、HF処理後の石英ガラスルツボから全肉厚にわた
るブロック状の試料を切出し、これを粉砕して金属元素
の濃度を測定した。この結果を下記第１表のＴ′に示
す。In addition, a block-shaped sample having the entire thickness was cut out from the quartz glass crucible after the HF treatment, and this was crushed to measure the concentration of the metal element. The results are shown in T'of Table 1 below.
次いで、この石英ガラスルツボ内に50％HF水溶液を再
び入れて30分間保持し、石英ガラスルツボの内表面をエ
ッチングした後、回収したHF水溶液中に溶解しているSi
O2量及び金属元素の濃度を測定した。そして、SiO2量か
ら溶解した石英ガラスルツボの厚みを換算するととも
に、その厚みの石英ガラス中の金属元素の濃度を計算し
た。この結果を下記第１表のＳ′に示す。Then, 50% HF aqueous solution was again put into the quartz glass crucible and kept for 30 minutes to etch the inner surface of the quartz glass crucible, and then Si dissolved in the recovered HF aqueous solution.
The amount of O 2 and the concentration of the metal element were measured. Then, the thickness of the fused silica glass crucible was converted from the amount of SiO 2 , and the concentration of the metal element in the silica glass having that thickness was calculated. The results are shown in S'in Table 1 below.
更に、上記と同様なHF処理を繰返し行ない、HF水溶液
に溶解した石英ガラスルツボの厚み及びその厚みの石英
ガラス中の金属元素の濃度を求めた。この結果をもとに
して、石英ガラスルツボの作製当初の内表面からの厚み
と、Al濃度との関係を第１図に示す。Further, the same HF treatment as described above was repeated to determine the thickness of the quartz glass crucible dissolved in the HF aqueous solution and the concentration of the metal element in the quartz glass of that thickness. Based on these results, FIG. 1 shows the relationship between the Al concentration and the thickness from the inner surface of the quartz glass crucible at the initial production.
第１表及び第１図から明らかなように、Al濃度は作製
当初の石英ガラスルツボの内表面で150ppmと極端に高
く、内部へ向かうにつれて７〜8ppmまで急激に減少する
という分布を有しており、作製当初の石英ガラスルツボ
の内表面からの厚みが30μｍ以上であれば、Al濃度が50
ppmよりかなり低くなる。 As is clear from Table 1 and FIG. 1, the Al concentration is extremely high at 150 ppm on the inner surface of the quartz glass crucible at the beginning of production, and has a distribution that it rapidly decreases to 7 to 8 ppm as it goes inward. If the thickness from the inner surface of the quartz glass crucible at the time of manufacture was 30 μm or more, the Al concentration was 50
Well below ppm.
また、アーク溶融法により作製したままの石英ガラス
ルツボ（比較例）と、上述したのと同様なHF処理を１回
行なった石英ガアスルツボ（実施例）とを用い、CZ法に
よるシリコン単結晶の引上げを行ない、それぞれ得られ
たシリコン単結晶中のAl濃度を測定した。その結果、実
施例のルツボを用いた場合には比較例のルツボを用いた
場合よりも、シリコン単結晶中のAl濃度が大幅に減少し
た。Further, using a quartz glass crucible (comparative example) as produced by the arc melting method and a quartz gas crucible (example) subjected to the same HF treatment as described above once, a silicon single crystal is pulled by the CZ method. Then, the Al concentration in each obtained silicon single crystal was measured. As a result, when the crucible of the example was used, the Al concentration in the silicon single crystal was significantly reduced as compared with the case of using the crucible of the comparative example.
以上詳述したように本発明によれば、シリコン単結晶
中に取込まれるAlを減少させることができ、ひいては半
導体デバイスの素子特性への悪影響を低減することがで
きる石英ガラスルツボを容易に製造することができる方
法を提供できるものである。As described above in detail, according to the present invention, it is possible to easily manufacture a silica glass crucible that can reduce Al taken in a silicon single crystal and can reduce adverse effects on element characteristics of a semiconductor device. It is possible to provide a method that can be done.
第１図はアーク溶融法により作製された石英ガラスルツ
ボの内表面からの厚みとAl濃度との関係を示す特性図で
ある。FIG. 1 is a characteristic diagram showing the relationship between the thickness from the inner surface of a quartz glass crucible manufactured by the arc melting method and the Al concentration.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 吉田 博幸 東京都新宿区西新宿１丁目26番２号 東芝 セラミックス株式会社内 (56)参考文献 特公 昭58−49516（ＪＰ，Ｂ２) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hiroyuki Yoshida Inventor Hiroyuki Yoshida 1-26-2 Nishishinjuku, Shinjuku-ku, Tokyo Inside Toshiba Ceramics Co., Ltd. (56) References Japanese Patent Publication Sho 58-49516 (JP, B2)
Claims (1)
とした後、その内表面をHF水溶液により30μｍ以上エッ
チングすることを特徴とする石英ガラスルツボの製造方
法。1. A method for producing a quartz glass crucible, which comprises forming a SiO 2 raw material into a crucible shape by an arc melting method, and then etching the inner surface of the SiO 2 raw material with an HF aqueous solution to a depth of 30 μm or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61315580A JPH085739B2 (en) | 1986-12-26 | 1986-12-26 | Quartz glass crucible manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61315580A JPH085739B2 (en) | 1986-12-26 | 1986-12-26 | Quartz glass crucible manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63166791A JPS63166791A (en) | 1988-07-09 |
| JPH085739B2 true JPH085739B2 (en) | 1996-01-24 |
Family
ID=18067060
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61315580A Expired - Lifetime JPH085739B2 (en) | 1986-12-26 | 1986-12-26 | Quartz glass crucible manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH085739B2 (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0226031A (en) * | 1988-07-14 | 1990-01-29 | Toshiba Ceramics Co Ltd | Silicon wafer |
| JPH0653634B2 (en) * | 1989-01-13 | 1994-07-20 | 三菱マテリアル株式会社 | Regeneration method of quartz crucible for pulling silicon single crystal |
| JPH0725561B2 (en) * | 1990-08-28 | 1995-03-22 | 信越半導体株式会社 | Quartz glass crucible |
| DE69508473T2 (en) | 1994-07-06 | 1999-10-28 | Shin-Etsu Handotai Co., Ltd. | Process for producing silicon single crystal and crucible made of molten silica therefor |
| JP2811290B2 (en) * | 1995-04-04 | 1998-10-15 | 信越石英株式会社 | Quartz glass crucible for pulling silicon single crystal |
| US6510707B2 (en) * | 2001-03-15 | 2003-01-28 | Heraeus Shin-Etsu America, Inc. | Methods for making silica crucibles |
| JP4678667B2 (en) * | 2004-06-07 | 2011-04-27 | 信越石英株式会社 | Silica glass crucible for pulling silicon single crystal and method for producing the same |
| US8272234B2 (en) | 2008-12-19 | 2012-09-25 | Heraeus Shin-Etsu America, Inc. | Silica crucible with pure and bubble free inner crucible layer and method of making the same |
| JP4975012B2 (en) | 2008-12-29 | 2012-07-11 | ジャパンスーパークォーツ株式会社 | Silica glass crucible for pulling silicon single crystal and manufacturing method thereof |
| US9003832B2 (en) | 2009-11-20 | 2015-04-14 | Heraeus Shin-Etsu America, Inc. | Method of making a silica crucible in a controlled atmosphere |
| JP5611904B2 (en) * | 2011-08-10 | 2014-10-22 | コバレントマテリアル株式会社 | Silica glass crucible for pulling silicon single crystal and method for producing the same |
| KR20180095880A (en) | 2015-12-18 | 2018-08-28 | 헤래우스 크바르츠글라스 게엠베하 ＆ 컴파니 케이지 | Manufacture of synthetic quartz glass grain |
| KR20180095616A (en) | 2015-12-18 | 2018-08-27 | 헤래우스 크바르츠글라스 게엠베하 ＆ 컴파니 케이지 | Preparation of silica glass body using dew point control in melting furnace |
| WO2017103153A1 (en) | 2015-12-18 | 2017-06-22 | Heraeus Quarzglas Gmbh & Co. Kg | Glass fibers and preforms made of quartz glass having low oh, cl, and al content |
| CN108698892A (en) | 2015-12-18 | 2018-10-23 | 贺利氏石英玻璃有限两合公司 | Quartz glass body is prepared from silica dioxide granule |
| 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 |
| US11053152B2 (en) | 2015-12-18 | 2021-07-06 | Heraeus Quarzglas Gmbh & Co. Kg | Spray granulation of silicon dioxide in the preparation of quartz glass |
| TW201731782A (en) | 2015-12-18 | 2017-09-16 | 何瑞斯廓格拉斯公司 | Preparation of a quartz glass body in a multi-chamber oven |
| JP7044454B2 (en) | 2015-12-18 | 2022-03-30 | ヘレウス クワルツグラス ゲーエムベーハー ウント コンパニー カーゲー | Preparation of carbon-doped silicon dioxide granules as an intermediate 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 |
| US11952303B2 (en) | 2015-12-18 | 2024-04-09 | Heraeus Quarzglas Gmbh & Co. Kg | Increase in silicon content in the preparation of quartz glass |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5849516B2 (en) * | 1977-03-17 | 1983-11-04 | 東芝セラミツクス株式会社 | Method for manufacturing silicon single crystal with few impurities |
| JPH0229528B2 (en) * | 1981-09-16 | 1990-06-29 | Toyota Motor Co Ltd | ENJINSHIJISOCHI |
| JPS59169956A (en) * | 1983-03-17 | 1984-09-26 | Seiko Epson Corp | Purification of glass material |
-
1986
- 1986-12-26 JP JP61315580A patent/JPH085739B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63166791A (en) | 1988-07-09 |
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