JPH0427177B2 - - Google Patents
Info
- Publication number
- JPH0427177B2 JPH0427177B2 JP60210329A JP21032985A JPH0427177B2 JP H0427177 B2 JPH0427177 B2 JP H0427177B2 JP 60210329 A JP60210329 A JP 60210329A JP 21032985 A JP21032985 A JP 21032985A JP H0427177 B2 JPH0427177 B2 JP H0427177B2
- Authority
- JP
- Japan
- Prior art keywords
- quartz glass
- rod
- base material
- temperature
- transparent
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/14—Other methods of shaping glass by gas- or vapour- phase reaction processes
- C03B19/1453—Thermal after-treatment of the shaped article, e.g. dehydrating, consolidating, sintering
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
- C03B37/01—Manufacture of glass fibres or filaments
- C03B37/012—Manufacture of preforms for drawing fibres or filaments
- C03B37/014—Manufacture of preforms for drawing fibres or filaments made entirely or partially by chemical means, e.g. vapour phase deposition of bulk porous glass either by outside vapour deposition [OVD], or by outside vapour phase oxidation [OVPO] or by vapour axial deposition [VAD]
- C03B37/01446—Thermal after-treatment of preforms, e.g. dehydrating, consolidating, sintering
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Glass Melting And Manufacturing (AREA)
- Manufacture, Treatment Of Glass Fibers (AREA)
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、高純度石英ガラスの製造方法に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing high-purity quartz glass.
［従来の技術］
従来より、石英ガラスを製造する方法の一つと
して、気相反応法により、多孔質石英ガラス母材
を形成し、この母材を加熱して透明ガラス化する
方法が採用されている。すなわち、四塩化珪素等
の珪素化合物を酸水素炎中で加水分解させ、石英
製の種棒の下端部にシリカ微粒子を付着、堆積さ
せて、多孔質石英ガラス母材を形成する。そし
て、この多孔質石英ガラス母材を加熱炉に入れ、
He雰囲気内でヒーター加熱して焼結することに
より透明ガラス化する方法である。Heガスは、
石英ガラス中の透過速度が、他種のガスに比べて
大きいので、多孔質石英母材を透明ガラス化する
際には、He雰囲気内で行なうことが必須条件で
ある（特開昭57−95840号）。[Prior Art] Conventionally, one of the methods for producing quartz glass has been to form a porous quartz glass base material using a gas phase reaction method, and then heat this base material to turn it into transparent glass. ing. That is, a silicon compound such as silicon tetrachloride is hydrolyzed in an oxyhydrogen flame, and silica fine particles are attached and deposited on the lower end of a quartz seed rod to form a porous quartz glass base material. Then, this porous quartz glass base material is placed in a heating furnace,
This method produces transparent glass by heating and sintering it with a heater in a He atmosphere. He gas is
Since the permeation rate through quartz glass is higher than that of other types of gases, it is essential to convert a porous quartz base material into transparent glass in a He atmosphere (Japanese Patent Laid-Open No. 57-95840). issue).
光フアイバーなどの外径の小さな石英ガラスロ
ツドの製造に際しては、VAD法といわれる透明
ガラス化方法が採用されている。この方法は、気
相反応合成法により、種棒の下端部にシリカ微粒
子を付着、堆積させて多孔質石英ガラス母材を形
成させながら、種棒を徐々に引上げてヒーターに
通し、透明ガラス化する方法である。この方法で
は、多孔質石英ガラス母材の形成と、この母材の
透明ガラス化とを連続的に行なうことができる。 A transparent vitrification method called the VAD method is used to manufacture quartz glass rods with small outer diameters such as optical fibers. This method uses a gas phase reaction synthesis method to attach and deposit silica particles to the lower end of the seed rod to form a porous quartz glass matrix, while gradually pulling the seed rod up and passing it through a heater to create transparent glass. This is the way to do it. In this method, the formation of a porous quartz glass base material and the transparent vitrification of this base material can be performed continuously.
一方、フオトマスク用の基板などのように大型
の石英ガラスを製造しようとする場合には、多孔
質石英ガラス母材が大口径、長尺であるために、
種棒の保護を目的に、上方よりヒーターを通し
て、透明ガラス化を行なわなければならない。 On the other hand, when manufacturing large quartz glass such as photomask substrates, the porous quartz glass base material has a large diameter and a long length.
To protect the seed rod, it must be passed through a heater from above to make it transparent and vitrified.
［発明が解決しようとする課題］
一般的に上記の方法によつて製造された石英ガ
ラスロツドは、ほぼ円柱状であり、また寸法上、
外径上の制限を受ける。したがつて、例えばフオ
トマスク用の基板に供されるような断面が正方形
の形状を有するガラスインゴツトにするために
は、1800℃付近の高温度で加圧成形が行なわれて
いる（特開昭57−67031号）。[Problems to be Solved by the Invention] Generally, the quartz glass rod manufactured by the above method has a substantially cylindrical shape, and also has a size of
Subject to limitations on outer diameter. Therefore, in order to make a glass ingot with a square cross section, which can be used as a substrate for a photomask, pressure molding is carried out at a high temperature of around 1800°C (Japanese Patent Application Laid-Open No. 57-67031).
上記の方法によつて製造された石英ガラスロツ
ドには、一般にクリストバライト等の結晶質の欠
点が存在する傾向があり、また、該欠点は微細な
クラツクを伴うことがある。かかる石英ガラスロ
ツドに前記透明ガラス化温度より高温度で加圧成
形を施すことによつて得られた石英ガラスインゴ
ツトにおいては、上記石英ガラスロツド中の欠点
が例えば、100μmから５mm程度にまで大型化した
気泡と化し、その結果石英ガラスインゴツト製品
の歩留りが著しく低下するという問題があつた。 Quartz glass rods produced by the above method generally tend to have crystalline defects such as cristobalite, and these defects may be accompanied by fine cracks. In the quartz glass ingot obtained by subjecting such a quartz glass rod to pressure molding at a temperature higher than the transparent vitrification temperature, the defects in the quartz glass rod have increased in size from, for example, 100 μm to about 5 mm. There was a problem in that the quartz glass ingots were turned into bubbles, and as a result, the yield of quartz glass ingot products was significantly reduced.
多孔質石英ガラス母材をHe雰囲気中で透明ガ
ラス化して、石英ガラスロツドを得る際に、該石
英ガラスインゴツト中にHeガスが溶解する。上
記の如き石英ガラスインゴツト中の大型化した気
泡の出現は、石英ガラスインゴツトを得るために
上記石英ガラスロツドを上記透明ガラス化の温度
よりも高温度に導いたとき、前記クリストバライ
ト結晶等の欠点が溶解し、一方、石英ガラスに対
するHeガスの溶解度が相対的に低下し、過飽和
な状態になるが故にHeガスが石英ガラスブロツ
ク中の前記欠点の箇所あるいは前記微細なクラツ
クを起点として析出し大型化した気泡を形成する
ことが主な原因であることが判明した。 When a porous quartz glass base material is transparently vitrified in a He atmosphere to obtain a quartz glass rod, He gas is dissolved in the quartz glass ingot. The appearance of large bubbles in the quartz glass ingot as described above is caused by the defects of the cristobalite crystals, etc., when the quartz glass rod is brought to a temperature higher than the temperature for transparent vitrification in order to obtain the quartz glass ingot. On the other hand, the solubility of He gas in quartz glass decreases relatively, resulting in a supersaturated state, and He gas precipitates starting from the defect points or the fine cracks in the quartz glass block, forming large cracks. The main cause was found to be the formation of bubbles.
本発明は、かかる問題点を解決するために鋭意
研究の結果、完成されたものであり、多孔質石英
ガラス母材を透明ガラス化した後に、所定の条件
で脱He処理を行なうことによつて、そのあとの
成形時に欠点が大型化するのを防止する方法を新
規に提供することを目的とするものである。 The present invention was completed as a result of intensive research in order to solve these problems, and after converting a porous quartz glass base material into transparent vitrification, a He removal treatment is performed under predetermined conditions. The object of the present invention is to provide a new method for preventing defects from becoming larger during subsequent molding.
［課題を解決するための手段］
本発明は、前述の問題点を解決すべくなされた
ものであり、気相反応合成法により種棒の下端部
にシリカ微粒子を付着、堆積させて形成した高純
度多孔質石英ガラス母材をHe雰囲気中で加熱し
て透明ガラス化した高純度石英ガラスロツドを
得、さらに該ガラスロツドを、脱He処理として
雰囲気の圧力が５×10-2Torr以下かつ温度範囲
1000〜1250℃の条件下で60〜120分間保持するこ
とを特徴とする高純度石英ガラスの製造法を提供
するものである。[Means for Solving the Problems] The present invention has been made to solve the above-mentioned problems, and includes a high-temperature silica particle formed by adhering and depositing fine silica particles on the lower end of a seed rod using a gas phase reaction synthesis method. A high-purity quartz glass rod is obtained by heating a pure porous quartz glass base material in a He atmosphere to make it transparent, and the glass rod is then subjected to a He removal treatment at an atmospheric pressure of 5×10 -2 Torr or less and within a temperature range.
The present invention provides a method for producing high-purity quartz glass, which is characterized by holding the glass at a temperature of 1000 to 1250°C for 60 to 120 minutes.
本発明の好ましい態様によれば、透明ガラス化
の完了した石英ガラスロツドを、1000〜1250℃の
温度範囲で５×10-2Torr以下の雰囲気中に60〜
120分間保持すればよい。このとき、保持温度が
1250℃を超えるとSiO2がSiOとして蒸発して、発
熱体や加熱炉を著しく劣化させる恐れがある。ま
た1000℃未満では、Heの拡散速度がおさえられ、
脱Heの効果が薄れる。従つて保持温度は、1000
〜1250℃の範囲が適当である。 According to a preferred embodiment of the present invention, the quartz glass rod that has been completely vitrified is placed in an atmosphere of 5 x 10 -2 Torr or less at a temperature range of 1000 to 1250°C for 60 to
Just hold it for 120 minutes. At this time, the holding temperature is
If the temperature exceeds 1250°C, SiO 2 will evaporate as SiO, which may significantly deteriorate the heating element and heating furnace. Furthermore, below 1000℃, the diffusion rate of He is suppressed,
The effect of He removal is weakened. Therefore, the holding temperature is 1000
A range of ~1250°C is suitable.
［作用］
成形により欠点が大型化する機構は、必ずしも
明確ではないが、大型気泡内のガス成分分析の結
果、H2Ｏ，O2，H2，Ar，N2等の成分は検出さ
れず、Heガス成分のみが検出されたこと、およ
び温度が高くなるにつれて石英ガラス中へのHe
ガス固溶量が低下するという事実から、欠点の大
型化は、透明ガラス化の間に石英ガラス中に固溶
したHeガスが、透明ガラス化温度よりも高温度
でしかも、石英ガラスの溶融点以上であるような
温度、例えば1750℃で成形を行なうことによつ
て、石英ガラスロツド中の欠点界面上に析出し
て、大型化することによつて、生起すると考えら
れる。[Effect] The mechanism by which defects become larger due to molding is not necessarily clear, but as a result of gas component analysis within large bubbles, components such as H 2 O, O 2 , H 2 , Ar, and N 2 were not detected. , only the He gas component was detected, and as the temperature increases, the amount of He into the quartz glass increases.
The larger drawback is due to the fact that the amount of gas dissolved in solid solution decreases. It is thought that this is caused by precipitating on the defective interface in the quartz glass rod and enlarging it when molding is carried out at the above temperature, for example, 1750°C.
本発明において、透明ガラス化終了後に、雰囲
気の圧力が５×10-2Torr以下かつ温度範囲1000
〜1250℃の条件下で60〜120分間保持することは、
石英ガラス中に固溶した過剰のHeガスを石英ガ
ラスから析出除去させる効果を有するものであ
る。 In the present invention, after the completion of transparent vitrification, the pressure of the atmosphere is 5 × 10 -2 Torr or less and the temperature range is 1000
Holding for 60-120 minutes under ~1250℃ condition is
This has the effect of precipitating and removing excess He gas dissolved in the quartz glass from the quartz glass.
［実施例］
直径300mm、長さ600mm程度のほぼ円柱状の多孔
質石英ガラス母材をSiCl4の酸水素炎中における
加水分解によつて生成するシリカ微粒子の種棒へ
の堆積によつて製造した後、これをHe濃度が92
％の加熱炉内で回転させながら加熱炉内を徐々に
下降させて、脱泡、透明ガラス化を行なわせ直径
120mm、長さ320mmの透明石英ガラスロツドを製造
した。1430℃の加熱炉内から室温の雰囲気に取り
出された前記石英ガラスロツド中には、直径
100μm程度のクリストバライト結晶欠点が13個存
在していた。[Example] A nearly cylindrical porous quartz glass base material with a diameter of 300 mm and a length of about 600 mm was produced by depositing silica fine particles produced by hydrolysis of SiCl 4 in an oxyhydrogen flame onto a seed rod. After that, the He concentration is 92
% in the heating furnace while rotating it and gradually lowering the inside of the heating furnace to defoam and make it transparent vitrification.
A transparent quartz glass rod with a length of 120 mm and a length of 320 mm was manufactured. The diameter of the quartz glass rod was taken out from the 1430°C heating furnace to the room temperature atmosphere.
There were 13 cristobalite crystal defects of about 100 μm.
この石英ガラスロツドを0.01Torrの雰囲気内
で1080℃の温度に60分保持して石英ガラスロツド
の脱He処理を行なつた。この石英ガラスロツド
に前記の成形操作を行つて得られた石英ガラスイ
ンゴツト中には、直径が200μm程度の気泡が13個
存在していた。欠点の大型化は認められず、欠点
の大型化を防止することができた。 This quartz glass rod was held at a temperature of 1080°C for 60 minutes in an atmosphere of 0.01 Torr to perform a He removal process. In the quartz glass ingot obtained by performing the above-described molding operation on this quartz glass rod, there were 13 bubbles with a diameter of about 200 μm. No increase in the size of the defects was observed, and it was possible to prevent the defects from increasing in size.
［発明の効果］
以上説明したように、高純度多孔質石英母材を
He雰囲気中で加熱して透明ガラス化し得られた
高純度石英ガラスロツドを高温で加圧成形する場
合、該成形操作に先立つて本発明を実施すること
により、成形前の微細な欠点が成形に伴つて大型
化することを防止できる。本発明の実施により、
成形による製品例えばフオトマスク用の基板に供
される石英ガラスインゴツトの歩留が著しく向上
する。[Effect of the invention] As explained above, high-purity porous quartz base material
When a high-purity quartz glass rod obtained by heating in a He atmosphere to form transparent glass is pressure-formed at high temperature, by carrying out the present invention prior to the molding operation, minute defects before molding can be avoided during molding. This can prevent the structure from becoming larger. By implementing the present invention,
The yield of quartz glass ingots used as substrates for molded products such as photomasks is significantly improved.
Claims (1)
微粒子を付着、堆積させて形成した高純度多孔質
石英ガラス母材をHe雰囲気中で加熱して透明ガ
ラス化した高純度石英ガラスロツドを得、さらに
該ガラスロツドを、脱He処理として雰囲気の圧
力が５×10-2Torr以下かつ温度範囲1000〜1250
℃の条件下で60〜120分間保持することを特徴と
する高純度石英ガラスの製造法。1 A high-purity porous quartz glass base material formed by adhering and depositing silica particles on the lower end of a seed rod by a gas phase reaction synthesis method is heated in a He atmosphere to obtain a high-purity quartz glass rod that is made into transparent glass. Furthermore, the glass rod is subjected to He removal treatment at an atmospheric pressure of 5×10 -2 Torr or less and a temperature range of 1000 to 1250.
A method for producing high-purity quartz glass characterized by holding it for 60 to 120 minutes under conditions of ℃.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21032985A JPS6272537A (en) | 1985-09-25 | 1985-09-25 | Production of high-purity quartz glass |
| JP35938291A JPH0558653A (en) | 1985-09-25 | 1991-12-27 | Production of high-purity quartz glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21032985A JPS6272537A (en) | 1985-09-25 | 1985-09-25 | Production of high-purity quartz glass |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35938291A Division JPH0558653A (en) | 1985-09-25 | 1991-12-27 | Production of high-purity quartz glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6272537A JPS6272537A (en) | 1987-04-03 |
| JPH0427177B2 true JPH0427177B2 (en) | 1992-05-11 |
Family
ID=16587616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21032985A Granted JPS6272537A (en) | 1985-09-25 | 1985-09-25 | Production of high-purity quartz glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6272537A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0558653A (en) * | 1985-09-25 | 1993-03-09 | Asahi Glass Co Ltd | Production of high-purity quartz glass |
| US5356449A (en) * | 1993-05-24 | 1994-10-18 | At&T Bell Laboratories | Vad process improvements |
| US20040118164A1 (en) * | 2002-12-19 | 2004-06-24 | Boek Heather D. | Method for heat treating a glass article |
| JP6191222B2 (en) * | 2013-04-26 | 2017-09-06 | 住友電気工業株式会社 | Manufacturing method of glass base material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5934660A (en) * | 1982-08-21 | 1984-02-25 | Mitsubishi Electric Corp | Semiconductor device |
-
1985
- 1985-09-25 JP JP21032985A patent/JPS6272537A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6272537A (en) | 1987-04-03 |
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