JPH02208230A - Production of high-purity, high-viscosity silica glass - Google Patents
Production of high-purity, high-viscosity silica glassInfo
- Publication number
- JPH02208230A JPH02208230A JP2857589A JP2857589A JPH02208230A JP H02208230 A JPH02208230 A JP H02208230A JP 2857589 A JP2857589 A JP 2857589A JP 2857589 A JP2857589 A JP 2857589A JP H02208230 A JPH02208230 A JP H02208230A
- Authority
- JP
- Japan
- Prior art keywords
- gel
- atmosphere
- silica glass
- heat treatment
- less
- 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.)
- Granted
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000012298 atmosphere Substances 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- 238000003980 solgel method Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims description 7
- 238000010304 firing Methods 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 12
- 229910052736 halogen Inorganic materials 0.000 abstract description 6
- 150000002367 halogens Chemical class 0.000 abstract description 6
- 239000004065 semiconductor Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 238000000280 densification Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 150000004820 halides Chemical class 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 150000004756 silanes Chemical class 0.000 abstract description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 229910003910 SiCl4 Inorganic materials 0.000 abstract 1
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract 1
- 230000003287 optical effect Effects 0.000 abstract 1
- 239000005416 organic matter Substances 0.000 abstract 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 abstract 1
- 238000000034 method Methods 0.000 description 20
- 239000012535 impurity Substances 0.000 description 17
- 239000011521 glass Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 4
- 239000013307 optical fiber Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- -1 CfL Chemical class 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000007569 slipcasting Methods 0.000 description 2
- 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 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004017 vitrification 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
- C03B19/12—Other methods of shaping glass by liquid-phase reaction processes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Melting And Manufacturing (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は特に半導体用プロセス材料や光フアイバ用支持
管として好適な高純度・高粘性シリカガラスの製造方法
に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing high-purity, high-viscosity silica glass, which is particularly suitable as a process material for semiconductors and a support tube for optical fibers.
半導体用プロセス材料や光フアイバ用支持管として用い
られるシリカガラスは、金属不純物、ハロゲン、ＯＨ基
などの含有量が極めて少ないことが要求される。従来、
こうした用途のシリカガラスの製造方法としては、以下
のような種々の方法が提案されている。Silica glass used as a process material for semiconductors or a support tube for optical fibers is required to have extremely low contents of metal impurities, halogens, OH groups, and the like. Conventionally,
The following various methods have been proposed as methods for producing silica glass for such uses.
■スリップキャスティング法などにより成形された５ｉ
０２成形体を約７５０℃で仮焼した後、Ｈｅ ”ｅｖ
Ｎ ｅの雰囲気下にて１６００℃以上の温度で焼成する
方法（特開昭４９−１３１２１０号公報）。■5i molded by slip casting method etc.
After calcining the 02 molded body at about 750°C,
A method of firing at a temperature of 1600°C or higher in an Ne atmosphere (Japanese Patent Laid-Open No. 131210/1983).
■気相反応により形成された５ｉ０２成形体を約１０ｍ
ｍＨｇの雰囲気中にて１１００〜１４００℃で予備焼結
して脱水した後、急熱溶融する方法（特公昭４７−５２
７２号公報）。■ Approximately 10 m of 5i02 molded body formed by gas phase reaction
A method of preliminary sintering at 1100 to 1400°C in an mHg atmosphere, dehydration, and rapid heat melting (Japanese Patent Publication No. 47-52
Publication No. 72).
■スリップキャスティング法により成形されたＳｉＯ□
成形体を１２００℃以下で焼成して可燃物を除去した後
、Ｈｅ雰囲気中又は真空中にて１６００℃以上まで急熱
する方法（特公昭５３−３３！３Ｅ１５号公報）。■SiO□ molded by slip casting method
A method in which the molded body is fired at 1200° C. or lower to remove combustible materials, and then rapidly heated to 1600° C. or higher in a He atmosphere or in a vacuum (Japanese Patent Publication No. 53-33!3E15).
■多孔質シリカガラス成形体を塩素含有雰囲気中にて６
００〜１０００℃で加熱してＯＨ基を除去した後、窒素
雰囲気中にて加熱してガラスを緻密化させる方法（特公
昭４２−２３０３８号公報）。■ Porous silica glass molded body in chlorine-containing atmosphere
A method of heating at 00 to 1000°C to remove OH groups and then heating in a nitrogen atmosphere to make the glass dense (Japanese Patent Publication No. 42-23038).
■５ｉ０２原料（珪酸ゲルを含む）を四塩化珪素などの
雰囲気中にて加熱処理した後、この原料を溶融させてシ
リカガラスを製造する方法（特公昭４Ｂ−９１４３号公
報）
■シリカ原料からゾル−ゲル法により管状ゲルを作製し
た後、Ｈｅ雰囲気又は減圧下にて１２００℃程度で加熱
して閉孔化し、更に１５００〜２２００℃で再加熱する
方法（特開昭８２−４６９３３号公報）。■A method of manufacturing silica glass by heat-treating the 5i02 raw material (including silicic acid gel) in an atmosphere of silicon tetrachloride or the like and then melting this raw material (Japanese Patent Publication No. 4B-9143) ■Sol from the silica raw material - A method in which a tubular gel is produced by a gel method, then heated at about 1200° C. in a He atmosphere or under reduced pressure to close the pores, and then reheated at 1500 to 2200° C. (Japanese Unexamined Patent Publication No. 82-46933).
■シリカ原料からゾル−ゲル法により所定形状のゲルを
調製し、４００℃以下で加熱して吸着水を除去し、４０
０〜１２００℃で加熱して脱炭素を行い、塩化物、フッ
化物を含むＨｅ、Ｎｅなどの雰囲気中にて７００〜１２
００℃で加熱して脱ＯＨ基を行い、Ｈｅ、Ｎｅなどの雰
囲気中にて７００〜１２００℃で加熱した後、Ｈｅ雰囲
気中にて１０００〜１５００℃で加熱して脱ハロゲンを
行い、更に１０００〜１８００℃で加熱して透明化する
方法（Ｕ Ｓ Ｐ ４．［１Ｂ０．０４８）。■Prepare a gel of a predetermined shape from silica raw material by the sol-gel method, heat it at 400°C or less to remove adsorbed water,
Decarbonization is performed by heating at 0 to 1200°C, and 700 to 12
After heating at 00°C to remove OH groups, heating at 700 to 1200°C in an atmosphere of He, Ne, etc., removing halogen by heating at 1000 to 1500°C in a He atmosphere, and then removing OH groups at 1000°C. Method of transparency by heating at ~1800°C (US P 4. [1B0.048).
しかしながら、上述した従来の方法にはいずれも以下の
ような問題がある。However, all of the conventional methods described above have the following problems.
すなわち、■、■、■、■の方法では、一般にシリカガ
ラス中のアルカリ金属その他の金属不純物の含有量が多
く、こうしたシリカガラスは特に半導体用プロセス材料
などの用途には使用困難である。That is, in the methods (1), (2), (2), and (2), the content of alkali metals and other metal impurities in the silica glass is generally large, and such silica glass is difficult to use, especially as a process material for semiconductors.
また、■、■、■の方法ではシリカガラス中のＯＨ基含
有量は低減されるが、ＣｆＬなどのハロゲンが残留する
ため低粘性となり、こうしたシリカガラスは高温使用が
制限される。Furthermore, although the OH group content in the silica glass is reduced in the methods (1), (2), and (4), the viscosity becomes low due to residual halogens such as CfL, which limits the use of such silica glass at high temperatures.
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、金属不純物、ＯＨ基、／＼ロゲンの含有量が少ない
、高純度かつ高粘性のシリカガラスを製造し得る方法を
提供することを目的とする。The present invention has been made to solve the above problems, and aims to provide a method for producing high purity and high viscosity silica glass with a low content of metal impurities, OH groups, and /\logene. purpose.
本発明の高純度・高粘性シリカガラスの製造方法は、ゾ
ル−ゲル法によりシリカ源となる原料のゲルを調製し、
このゲルを水蒸気を含む雰囲気中にて３００〜１０００
℃で熱処理した後、水蒸気分圧０．５ ｍｍ）１ｇ以下
の乾燥気体雰囲気中又は真空中にて３００〜１０００℃
で熱処理し、更に水蒸気分圧０．５ ｍｍＨｇ以下の乾
燥気体雰囲気中又は真空中にて１０００〜２０００℃で
焼成することを特徴とするものである。The method for producing high-purity, high-viscosity silica glass of the present invention involves preparing a raw material gel serving as a silica source by a sol-gel method,
This gel was heated to 300 to 1000 in an atmosphere containing water vapor.
After heat treatment at 300 to 1000 °C in a dry gas atmosphere with a water vapor partial pressure of 0.5 mm) or less than 1 g or in vacuum.
It is characterized by being heat treated at 1,000 to 2,000° C. in a dry gas atmosphere with a water vapor partial pressure of 0.5 mmHg or less or in vacuum.
本発明において、シリカ源となる原料としては、５ｉｃ
ｋ。、ハロゲン化シラン、アルコキシシラン、アルキル
シラン、金属ケイ酸塩、シリカ微粉末などが挙げられる
。In the present invention, 5ic
k. , halogenated silane, alkoxysilane, alkylsilane, metal silicate, fine silica powder, etc.
こうしたシリカ源となる原料はゾル−ゲル法によりゲル
化される。必要に応じて生成したゲルを水、酸、アンモ
ニアなどの溶液で洗浄した後、乾燥する。Such a raw material serving as a silica source is gelled by a sol-gel method. If necessary, the generated gel is washed with a solution such as water, acid, or ammonia, and then dried.
なお、必要に応じて後述する水蒸気を含む雰囲気での熱
処理の前に、Ｃ１，，５ＯＣ１ｘ、Ｓｉ０文。、Ｈｅ見
、ＣＨＣ文３、フッ化物などの各種ハロゲン化物を含む
雰囲気中にて３００〜１０００℃で熱処理を行うことに
より金属不純物を除去する。Note that, if necessary, before heat treatment in an atmosphere containing water vapor, which will be described later, C1,,5OC1x, Si0. , He, CHC 3, metal impurities are removed by heat treatment at 300 to 1000° C. in an atmosphere containing various halides such as fluoride.
次に、上記のようなゲルを水蒸気を含む雰囲気中にて３
００〜１０００℃で熱処理する。この工程の目的は、ゲ
ル中の有機物、ハロゲン、ハロゲン化物を除去すること
にある。この工程の処理温度を３００〜１０００℃とし
たのは以下のような理由による。すなわち、３００℃未
満では、前記不純物を実質的に除去することが困難であ
り、高粘性のシリカガラスを得ることができない。一方
、１０００℃を超えると、ゲルの緻密化が急速に進行し
、前記不純物がゲル中に取り残されるため、得られるシ
リカガラスは粘性が低く、また気泡の多いものとなる。Next, the above gel was placed in an atmosphere containing water vapor for 3
Heat treatment at 00-1000°C. The purpose of this step is to remove organic substances, halogens, and halides in the gel. The reason why the treatment temperature in this step was set to 300 to 1000°C is as follows. That is, if the temperature is lower than 300°C, it is difficult to substantially remove the impurities, and high viscosity silica glass cannot be obtained. On the other hand, if the temperature exceeds 1000°C, the gel becomes denser rapidly and the impurities are left behind in the gel, resulting in the resulting silica glass having low viscosity and many bubbles.
その後、水蒸気分圧０．５ ｍｍＨｇ以下の乾燥気体雰
囲気中又は真空中にて３００〜１０００℃で熱処理する
。この工程の目的は、実質的に無水の雰囲気で加熱処理
することにより、ゲル中に含有されているＯＨ基を拡散
させて除去することにある。この際、雰囲気ガスとして
はＨｅやＨ２のような透過性の高いガスを用いることが
望ましい。この工程は真空中で行なってもよい。また、
この工程は減圧下でも、加圧下でも可能であるが、いず
れにしても水蒸気分圧が０．５ ｍｍＨｇ以下であるこ
とが必要である。この工程の水蒸気分圧を０．５ ｍｍ
Ｈｇ以下と限定したのは以下のような理由による。すな
わち、水蒸気分圧が０．５ ｍｍＨｇを超える場合、例
えば水蒸気分圧１ ｍｍＨｇでは、粘性が４Ｘ１０”ポ
イズ（この粘性では事実上粘性流動が起らない）になる
温度（歪点）が１０８０℃となり、更に水素分圧を高め
たときには歪点が１０８０〜１０００℃の低粘性シリカ
ガラスしか得られない。これに対して、水蒸気分圧０．
５ ｍｍＨｇ以下、例えば０．４ ｍｍＨｇでは、歪点
が１１００℃以上の高粘性シリカガラスが得られ、更に
水蒸気分圧が低い場合には歪点が１１００〜１１５０℃
の高粘性シリカガラスを得ることができる。この工程の
処理温度を３００〜１０００℃と限定したのは以下のよ
うな理由による。すなわち、３００℃未満では、吸着水
の除去は可能であるが、ゲルと反応してゲル中にＯＨ基
として残留している水分を除去するには極めて長時間を
要するため、現実的ではない。一方、１０００℃を超え
ると、ゲルの緻密化が急速に進行し、ゲル中からのＯＨ
基の拡散が充分でない状態で緻密ガラス化が完了する。Thereafter, heat treatment is performed at 300 to 1000° C. in a dry gas atmosphere with a water vapor partial pressure of 0.5 mmHg or less or in vacuum. The purpose of this step is to diffuse and remove the OH groups contained in the gel by heat treatment in a substantially anhydrous atmosphere. At this time, it is desirable to use a highly permeable gas such as He or H2 as the atmospheric gas. This step may be performed in vacuum. Also,
This step can be carried out under reduced pressure or increased pressure, but in either case it is necessary that the water vapor partial pressure is 0.5 mmHg or less. The water vapor partial pressure in this process was set to 0.5 mm.
The reason why it was limited to Hg or less is as follows. That is, when the water vapor partial pressure exceeds 0.5 mmHg, for example, when the water vapor partial pressure is 1 mmHg, the temperature (strain point) at which the viscosity becomes 4 x 10" poise (at this viscosity, viscous flow does not occur in fact) is 1080 ° C. Therefore, when the hydrogen partial pressure is further increased, only a low-viscosity silica glass with a strain point of 1080 to 1000°C can be obtained.On the other hand, when the water vapor partial pressure is 0.
At 5 mmHg or less, for example 0.4 mmHg, a highly viscous silica glass with a strain point of 1100°C or more is obtained, and when the water vapor partial pressure is further low, the strain point is 1100 to 1150°C.
Highly viscous silica glass can be obtained. The reason why the processing temperature in this step was limited to 300 to 1000°C is as follows. That is, at temperatures below 300° C., it is possible to remove the adsorbed water, but it is not practical because it takes a very long time to react with the gel and remove the water remaining as OH groups in the gel. On the other hand, when the temperature exceeds 1000°C, the gel densification progresses rapidly and OH from the gel is released.
Dense vitrification is completed in a state where the groups are not sufficiently diffused.
この結果、その後にＯＨ基を除去しようとしても長時間
を要し、通常の時間内の処理では高粘性のシリカガラス
を得ることができない。また、次工程の１０００〜２０
００℃における加熱処理でガラス中に気泡が発生する原
因となる。As a result, even if an attempt is made to remove the OH groups thereafter, it takes a long time, and highly viscous silica glass cannot be obtained by processing within a normal time. In addition, 1000 to 20
Heat treatment at 00°C causes bubbles to be generated in the glass.
更に、水蒸気分圧０．５ ｍｍＨｇ以下の乾燥気体雰囲
気中又は真空中にて１０００〜２０００℃で焼成する。Furthermore, it is fired at 1000 to 2000°C in a dry gas atmosphere with a water vapor partial pressure of 0.5 mmHg or less or in vacuum.
この工程の目的は、ゲルを焼成して緻密化することによ
り、高純度、高粘性の透明シリカガラスを得ることにあ
る。この際にも、乾燥気体としてはＨｅやＨ２のような
透過性の高いガスを用いることが望ましい。この工程は
真空中で行なってもよい。また、この工程は減圧下でも
、加圧下でも可能であるが、いずれにしても水蒸気分圧
が０．５ ｍｍＨｇ以下であることが必要である。この
工程の水蒸気分圧を０．５ ｍｍ）１ｇ以下と限定した
のは以下のような理由による。すなわち、前工程で水蒸
気分圧０．５ ｍｍＨｇ以下でＯＨ基を充分に除去した
としても、緻密化完了までに水蒸気分圧が０．５ ｍｍ
Ｈｇを超えると、雰囲気中の水分との再結合により、低
粘性シリカガラスしか得られないおそれがある。この工
程の処理温度を１０００〜２０００℃と限定したのは以
下のような理由による。すなわち、１０００℃未満では
、緻密化に長時間を要するため、現実的ではない。一方
、２０００℃を超えると、粘性流動が大きくなり、焼成
体の形状を維持することが困難となる。The purpose of this step is to obtain transparent silica glass with high purity and high viscosity by baking the gel and making it dense. Also in this case, it is desirable to use a highly permeable gas such as He or H2 as the drying gas. This step may be performed in vacuum. Further, this step can be carried out under reduced pressure or increased pressure, but in either case, it is necessary that the water vapor partial pressure is 0.5 mmHg or less. The reason why the water vapor partial pressure in this step was limited to 0.5 mm) 1 g or less is as follows. In other words, even if the OH groups are sufficiently removed at a water vapor partial pressure of 0.5 mmHg or less in the previous step, the water vapor partial pressure will still reach 0.5 mmHg by the time densification is completed.
If it exceeds Hg, there is a risk that only low-viscosity silica glass will be obtained due to recombination with moisture in the atmosphere. The reason why the treatment temperature in this step was limited to 1000 to 2000°C is as follows. That is, if the temperature is less than 1000°C, it will take a long time for densification, which is not practical. On the other hand, when the temperature exceeds 2000°C, viscous flow becomes large and it becomes difficult to maintain the shape of the fired body.
これらの工程により、高純度で高粘性を示す透明なシリ
カガラスを得ることができる。Through these steps, transparent silica glass having high purity and high viscosity can be obtained.
以下、本発明の詳細な説明する。 The present invention will be explained in detail below.
実施例１
テトラエトキシシラｙ３００ ｍｌ、０．０２Ｎ塩酸２
００ｍ１、微粉末シリカ８０ｇを混合・撹拌し、超音波
照射、遠心分離、ろ過を行い、均質度の高いゾルを得た
。このゾルをｐＨ５に調整した後、直ちに内径１００
ｍｍの回転円筒に注入し、その遠心力で円筒内壁にゾル
を伺着させながらゲル化させた。得られたゲルを乾燥し
た後、雰囲気処理炉に装入し、０文２を２％含有するＨ
ｅを０．２文／ｗｉｎの流量で流しながら７００℃まで
昇温し、７００℃で１時間保持した。その後、雰囲気ガ
スを４０℃の純水を通過させて水分を含有させたＨｅに
切換え、７００℃で２時間保持した。その後、雰囲気ガ
スを水分を含まない（露点−４０℃以下、水蒸気分圧０
．１ ｍｍＨｇ以下の）Ｈｅに切換え、７００℃で４時
間保持した。Example 1 Tetraethoxysilane 300 ml, 0.02N hydrochloric acid 2
00ml and 80g of finely powdered silica were mixed and stirred, followed by ultrasonic irradiation, centrifugation, and filtration to obtain a highly homogeneous sol. After adjusting this sol to pH 5, immediately
The sol was injected into a rotating cylinder of mm diameter, and the centrifugal force caused the sol to adhere to the inner wall of the cylinder and form a gel. After drying the obtained gel, it was placed in an atmosphere treatment furnace and treated with H containing 2% of Omon2.
The temperature was raised to 700° C. while flowing e at a flow rate of 0.2 sentences/win, and held at 700° C. for 1 hour. Thereafter, the atmospheric gas was changed to He containing water by passing pure water at 40°C, and the temperature was maintained at 700°C for 2 hours. After that, the atmospheric gas is made free of moisture (dew point -40°C or lower, water vapor partial pressure 0).
．． The temperature was changed to He (below 1 mmHg) and maintained at 700°C for 4 hours.
次いで、このゲルを１７００℃まで加熱可能な炉に移し
、水分を含まないＨｅガスを０．２Ｊｌｊ／ｗｉｎの流
量で流しながら、１０℃／ｗｉｎの昇温速度で昇温し、
１６５０℃で１０分間保持した。これにより、外径５Ｏ
ｎ＋ｍ、内径４０ｍ＋ｎ、長さ７５ｍｍの透明なガラス
体が得られた。Next, this gel was transferred to a furnace capable of heating up to 1700 ° C., and the temperature was raised at a temperature increase rate of 10 ° C./win while flowing He gas containing no moisture at a flow rate of 0.2 Jlj/win.
It was held at 1650°C for 10 minutes. As a result, the outer diameter is 50
A transparent glass body with an inner diameter of 40 m+n and a length of 75 mm was obtained.
得られたガラス体の不純物含有量は、金属不純物：合計
１ ｐｐｍ以下、ＯＨ：２ｐｐｍ以下、０文：５ ｐｐ
ｍ以下、Ｃ： ５ ｐｐｍ以下であった。このガラス体
の粘性をファイバーエロンゲーション法で測定したとこ
ろ、歪点は１１４０℃と極めて高い値であった。また、
１３００℃にて片持ち（一端側固定）で水平保持しても
変形は少なかった。The impurity content of the obtained glass body is: metal impurities: 1 ppm or less in total, OH: 2 ppm or less, 0 parts: 5 ppm
C: 5 ppm or less. When the viscosity of this glass body was measured by the fiber elongation method, the strain point was an extremely high value of 1140°C. Also,
Even when held horizontally with a cantilever (one end fixed) at 1300°C, there was little deformation.
比較例１
水蒸気処理を省略した以外は上記実施例１と全く同様に
してガラス体を得た。得られたガラス体の不純物含有量
は、金属不純物：合計１ ｐｐｍ以下、ＯＨ：２ｐＰｍ
以下であったが、０文：２１０ｐｐｍと高い値を示した
。前記と同様にこのガラス体の粘性を測定したところ、
歪点は１０８０℃で、実施例１よりも５０℃の低い値と
なった。また、１３００℃にて片持ちで水平保持したと
ころ、容易に変形して円弧状となった。Comparative Example 1 A glass body was obtained in exactly the same manner as in Example 1 above, except that the steam treatment was omitted. The impurity content of the obtained glass body was as follows: metal impurities: 1 ppm or less in total, OH: 2 pPm
However, 0 sentences showed a high value of 210 ppm. When the viscosity of this glass body was measured in the same manner as above,
The strain point was 1080°C, which was 50°C lower than that of Example 1. Furthermore, when held horizontally with a cantilever at 1300°C, it was easily deformed into an arc shape.
比較例２
塩素処理、水蒸気処理及び乾燥雰囲気処理を省略した以
外は上記実施例１と全く同様にしてガラス体を得た。得
られたガラス体の不純物含有量は、金属不純物：合計１
５ｐｐｍ 、 ＯＨ： １５０ ｐｐｍであった。この
ガラス体の歪点は１０８０℃と低かった。また、このガ
ラス体は若干気泡の多いものであった。Comparative Example 2 A glass body was obtained in exactly the same manner as in Example 1 above, except that the chlorine treatment, steam treatment, and dry atmosphere treatment were omitted. The impurity content of the obtained glass body was: metal impurities: total 1
5 ppm, OH: 150 ppm. The strain point of this glass body was as low as 1080°C. Moreover, this glass body had a slightly large number of bubbles.
実施例２
半導体用ポリシリコン製造の副産物である高純度５ｉＣ
ｕ。５００ｇを純水３文に注入し、得られたゲルを乾燥
し、粒径１０ｐｍ〜２ｍｍに粉砕した。Example 2 High purity 5iC, a by-product of semiconductor polysilicon production
u. 500 g was injected into 3 cups of pure water, and the resulting gel was dried and ground to a particle size of 10 pm to 2 mm.
このゲルを石英ガラス製ポートに入れ、８００℃に加熱
した管状炉に装入し、４０℃の純水を通過させて水分を
含有させた空気を０．２文／ｍｉｎの流量で流しながら
、２時間保持した。その後、雰囲気を露点−４０℃以下
、水蒸気分圧０．１ ｍｍＨｇ＋７） Ｈｅに切換え、
０．２文／ｍｉｎの流量で流しながら、５時間保持した
。次いで、そのまま３０℃／ｈの昇温速度で１２５０℃
まで昇温し、１時間保持して焼結を終了した。このよう
にして粒径１．５ ｍｍ以下の透明なシリカガラス粉を
得た。This gel was placed in a quartz glass port and placed in a tubular furnace heated to 800°C, and while air containing moisture through 40°C pure water was flowed at a flow rate of 0.2 g/min. It was held for 2 hours. After that, the atmosphere was changed to He with a dew point of -40°C or less and a water vapor partial pressure of 0.1 mmHg + 7).
It was maintained for 5 hours while flowing at a flow rate of 0.2 sentences/min. Then, the temperature was increased to 1250°C at a heating rate of 30°C/h.
The sintering was completed by raising the temperature to a temperature of 100.degree. C. and maintaining the temperature for 1 hour. In this way, transparent silica glass powder with a particle size of 1.5 mm or less was obtained.
得られたガラス粉の不純物含有量は、金属不純物二合計
１ ｐｐｍ以下、ＯＨ： １０ｐｐｍ以下、Ｃ文＝５
ｐｐｒａ以下であった。また、このガラス粉を用いて作
製した単結晶引上用るつぼの不純物含有量は、金属不純
物二合計１ ｐｐｍ以下、ＯＨ：５ｐｐ＋ｗ以下、Ｃ１
：５ｐｐｍ以下、Ｂ ： ０．０１ｐｐｍ以下と極めて
高純度であり、気泡もなく、歪点は１１４０℃と高い値
を示した。The impurity content of the obtained glass powder was 1 ppm or less in total for two metal impurities, OH: 10 ppm or less, C content = 5
It was less than ppra. In addition, the impurity content of the single crystal pulling crucible made using this glass powder is 1 ppm or less in total of two metal impurities, OH: 5 pp+w or less, C1
B: 5 ppm or less, B: 0.01 ppm or less, with extremely high purity, no bubbles, and a high strain point of 1140°C.
以上詳述したように本発明方法によれば、金属不純物、
ＯＨ基、ハロゲンの含有量が少ない、高純度力つ高粘性
のシリカガラスを製造することができ、こうしたシリカ
ガラスを半導体用プロセスチューブ、単結晶引上用るつ
ぼ、光フアイバ用支持管などとして好適に使用すること
ができる。As detailed above, according to the method of the present invention, metal impurities,
It is possible to produce high-purity, strong, and highly viscous silica glass with low content of OH groups and halogens, and this silica glass is suitable for semiconductor process tubes, crucibles for pulling single crystals, support tubes for optical fibers, etc. It can be used for.
出願人代理人 弁理士 鈴江武彦Applicant's agent: Patent attorney Takehiko Suzue
Claims (1)
、このゲルを水蒸気を含む雰囲気中にて３００〜１００
０℃で熱処理した後、水蒸気分圧０．５ｍｍＨｇ以下の
乾燥気体雰囲気中又は真空中にて３００〜１０００℃で
熱処理し、更に水蒸気分圧０．５ｍｍＨｇ以下の乾燥気
体雰囲気中又は真空中にて１０００〜２０００℃で焼成
することを特徴とする高純度・高粘性シリカガラスの製
造方法。A raw material gel that is a silica source is prepared by the sol-gel method, and this gel is heated to 300 to 100% in an atmosphere containing water vapor.
After heat treatment at 0°C, heat treatment at 300 to 1000°C in a dry gas atmosphere with a water vapor partial pressure of 0.5 mmHg or less or in a vacuum, and further in a dry gas atmosphere with a water vapor partial pressure of 0.5 mmHg or less or in a vacuum. A method for producing high purity and high viscosity silica glass, which comprises firing at 1000 to 2000°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1028575A JP2732643B2 (en) | 1989-02-09 | 1989-02-09 | Manufacturing method of high purity and high viscosity silica glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1028575A JP2732643B2 (en) | 1989-02-09 | 1989-02-09 | Manufacturing method of high purity and high viscosity silica glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02208230A true JPH02208230A (en) | 1990-08-17 |
| JP2732643B2 JP2732643B2 (en) | 1998-03-30 |
Family
ID=12252409
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1028575A Expired - Fee Related JP2732643B2 (en) | 1989-02-09 | 1989-02-09 | Manufacturing method of high purity and high viscosity silica glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2732643B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0677872A1 (en) * | 1994-04-11 | 1995-10-18 | Dow Corning Corporation | Method of forming Si-O containing coatings |
| KR20000060200A (en) * | 1999-03-12 | 2000-10-16 | 윤종용 | Manufacturing method of silica glass for sol-gel process |
| KR100326173B1 (en) * | 1999-12-30 | 2002-02-27 | 윤종용 | Control method of heat treatment in fabrication process for high purity silica glass |
| JP2006176377A (en) * | 2004-12-24 | 2006-07-06 | Shinetsu Quartz Prod Co Ltd | Method for manufacturing synthetic silica glass having controlled oh group concentration and silica glass body |
-
1989
- 1989-02-09 JP JP1028575A patent/JP2732643B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0677872A1 (en) * | 1994-04-11 | 1995-10-18 | Dow Corning Corporation | Method of forming Si-O containing coatings |
| KR20000060200A (en) * | 1999-03-12 | 2000-10-16 | 윤종용 | Manufacturing method of silica glass for sol-gel process |
| KR100326173B1 (en) * | 1999-12-30 | 2002-02-27 | 윤종용 | Control method of heat treatment in fabrication process for high purity silica glass |
| JP2006176377A (en) * | 2004-12-24 | 2006-07-06 | Shinetsu Quartz Prod Co Ltd | Method for manufacturing synthetic silica glass having controlled oh group concentration and silica glass body |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2732643B2 (en) | 1998-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5048445B2 (en) | Black synthetic quartz glass with transparent layer | |
| KR100219250B1 (en) | Synthetic silica glass powder | |
| JP3092675B2 (en) | Oxynitride glass and method for producing the same | |
| JPH02208230A (en) | Production of high-purity, high-viscosity silica glass | |
| JP3818603B2 (en) | Method for producing quartz glass | |
| JP4204398B2 (en) | Method for producing quartz glass | |
| JP3187510B2 (en) | Method of manufacturing member for heat treatment of semiconductor wafer | |
| JP2671062B2 (en) | Method for manufacturing quartz glass crucible | |
| JPH0776093B2 (en) | Quartz glass manufacturing method | |
| JP2675819B2 (en) | Manufacturing method of quartz glass | |
| JP3724084B2 (en) | Method for producing synthetic quartz powder and quartz glass molded body | |
| JP3036993B2 (en) | Manufacturing method of synthetic quartz glass member | |
| JPH02172832A (en) | Synthesized quartz glass and production thereof | |
| JPH01320232A (en) | Production of quartz glass | |
| JPH0717389B2 (en) | Method for producing synthetic quartz glass | |
| JP3859303B2 (en) | Method for producing synthetic quartz glass powder and quartz glass molded body | |
| JP3371399B2 (en) | Cristobalite crystalline phase-containing silica glass and method for producing the same | |
| JPH0264027A (en) | Production of silica glass | |
| JPH07115881B2 (en) | Quartz glass material for heat treatment | |
| JPH0226848A (en) | Production of high-purity quartz glass | |
| JPH04238824A (en) | Production of synthetic optical quartz glass having high viscosity | |
| JPH04325431A (en) | Production of optical fiber | |
| JPH0745326B2 (en) | Method for producing synthetic quartz glass ingot and synthetic quartz crucible | |
| JP2001192225A (en) | Method for manufacturing quartz glass | |
| JPH0729790B2 (en) | Method for producing anhydrous synthetic quartz glass |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| LAPS | Cancellation because of no payment of annual fees |