JP2836138B2 - Method for manufacturing glass body - Google Patents
Method for manufacturing glass bodyInfo
- Publication number
- JP2836138B2 JP2836138B2 JP1297959A JP29795989A JP2836138B2 JP 2836138 B2 JP2836138 B2 JP 2836138B2 JP 1297959 A JP1297959 A JP 1297959A JP 29795989 A JP29795989 A JP 29795989A JP 2836138 B2 JP2836138 B2 JP 2836138B2
- Authority
- JP
- Japan
- Prior art keywords
- sio2
- steam treatment
- pressure steam
- glass
- gel
- 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 - Fee Related
Links
- 239000011521 glass Substances 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 238000000034 method Methods 0.000 title description 10
- 239000000758 substrate Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000010409 thin film Substances 0.000 claims description 14
- 150000002902 organometallic compounds Chemical class 0.000 claims description 7
- 239000007858 starting material Substances 0.000 claims description 7
- 238000003980 solgel method Methods 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 64
- 229910052681 coesite Inorganic materials 0.000 description 34
- 229910052906 cristobalite Inorganic materials 0.000 description 34
- 239000000377 silicon dioxide Substances 0.000 description 34
- 229910052682 stishovite Inorganic materials 0.000 description 34
- 229910052905 tridymite Inorganic materials 0.000 description 34
- 125000005372 silanol group Chemical group 0.000 description 27
- 235000012239 silicon dioxide Nutrition 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- -1 silicon alkoxide Chemical class 0.000 description 16
- 239000010408 film Substances 0.000 description 13
- 229920001223 polyethylene glycol Polymers 0.000 description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 229920000620 organic polymer Polymers 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 239000005361 soda-lime glass Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910003082 TiO2-SiO2 Inorganic materials 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000002419 bulk glass Substances 0.000 description 2
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 238000004433 infrared transmission spectrum Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000005373 porous glass Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910020175 SiOH Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 108010025899 gelatin film Proteins 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CRNJBCMSTRNIOX-UHFFFAOYSA-N methanolate silicon(4+) Chemical compound [Si+4].[O-]C.[O-]C.[O-]C.[O-]C CRNJBCMSTRNIOX-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/02—Pure silica glass, e.g. pure fused quartz
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/06—Doped silica-based glasses
- C03B2201/08—Doped silica-based glasses doped with boron or fluorine or other refractive index decreasing dopant
- C03B2201/10—Doped silica-based glasses doped with boron or fluorine or other refractive index decreasing dopant doped with boron
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)
- Manufacture, Treatment Of Glass Fibers (AREA)
Description
本発明は、シリコンアルコキシド等の金属有機化合物
を出発原料に用い、該金属有機化合物を加水分解縮重合
反応させることによりゲル化させ、これを熱処理するこ
とによりガラス体を製造する、いわゆるゾルゲル法によ
るガラス体の製造方法に関し、特に低温加熱により耐候
性，強度等の高いシラノール基含有量の低いガラス体を
製造する方法に関する。The present invention employs a so-called sol-gel method in which a metal organic compound such as a silicon alkoxide is used as a starting material, the metal organic compound is gelled by a hydrolysis-condensation reaction, and a glass body is produced by heat treatment of the metal organic compound. The present invention relates to a method for producing a glass body, and more particularly, to a method for producing a glass body having high silanol group content, such as high weather resistance and strength, by low-temperature heating.
従来、ゾルゲル法によるガラス体の作製方法における
シラノール基の低減方法として、（１）ゲルを高温まで
熱処理する方法。（例えば、R.Roy,J.Am.Cer.Soc.,54 3
44（1971））（２）塩素蒸気にさらす方法。（例えば、
R.E.Tressler et al.,J.Electrochem.Soc.,124,607（19
77））などが報告されている。 また、金属アルコキシドを含む溶液にポリエチレング
リコール等の増粘性有機高分子を添加しソーダ石灰ガラ
ス基板上に、有機高分子を含む柔軟なゲル膜を形成し、
これにサブミクロンオーダーの微細な凹凸を有する型を
押し当て、離型し、これを熱処理することにより有機高
分子を燃焼分解しガラス基板上に微細パターンを形成す
る方法も知られている。（例えば、N.Tohge et al.,J.N
on−Cryst.100,501（1988））Conventionally, as a method for reducing silanol groups in a method for producing a glass body by a sol-gel method, (1) a method in which a gel is heat-treated to a high temperature. (For example, R. Roy, J. Am. Cer. Soc., 543
44 (1971)) (2) Method of exposing to chlorine vapor. (For example,
RETressler et al., J. Electrochem. Soc., 124, 607 (19
77)) have been reported. Also, a thickening organic polymer such as polyethylene glycol is added to a solution containing a metal alkoxide to form a flexible gel film containing an organic polymer on a soda-lime glass substrate,
There is also known a method in which a mold having fine irregularities on the order of submicrons is pressed against the mold, the mold is released, and heat treatment is performed on the mold to burn off organic polymers to form a fine pattern on a glass substrate. (Eg, N. Tohge et al., JN
on-Cryst. 100, 501 (1988))
しかしながら、上記従来の方法においては、シラノー
ル基を十分低減するのに700℃以上の高温を必要とする
といった問題点があった。特に、プロセス上、熱処理温
度の上限が制限されるような場合、上記問題点は、きわ
めて大きな問題であった。 また、上記基板上に微細パターンを形成する方法によ
れば、基板等への微細加工が比較的容易に行えるが、ソ
ーダ石灰ガラス基板を基板として用いた場合、ソーダ石
灰ガラス基板が変形しない温度範囲での熱処理では、十
分な焼成が達成されず、得られる膜体が非常に多孔質で
あり、よって膜体中のシラノール基の濃度が高く吸着水
が付易くなうるという問題点があった。However, the above-mentioned conventional method has a problem that a high temperature of 700 ° C. or more is required to sufficiently reduce silanol groups. In particular, when the upper limit of the heat treatment temperature is limited due to the process, the above problem is an extremely large problem. According to the method of forming a fine pattern on the substrate, fine processing on the substrate or the like can be performed relatively easily. However, when a soda-lime glass substrate is used as a substrate, a temperature range in which the soda-lime glass substrate is not deformed is used. In the heat treatment in the above, there was a problem that sufficient sintering was not achieved, and the obtained film body was very porous, so that the concentration of silanol groups in the film body was high and it was easy for adsorbed water to adhere.
本発明は、上記従来の問題点を解決するためになされ
たものであって、金属有機化合物を含む溶液を出発原料
としてゲル体を形成し、該ゲル体を加熱してガラス体を
得る、ゾルゲル法によるガラス体の製造方法において、
該ゲル体を、10kPaないし1MPaの水蒸気、を含む雰囲気
と接触させている。 通常、ち密なガラスに対する水蒸気処理は、ガラス表
面に水を吸着させたり、シラノール基濃度を増大させる
が、本発明においては、上記従来の発想とは全く逆の高
圧水蒸気処理により、シラノール基の低減を行ってい
る。 本発明に使用できる、出発原料の金属有機化合物、特
にシリコンアルコキシドとしては、シリコンテトラメト
キシド、シリコンテトラエトキシド、シリコンテトラプ
ロポキシド、シリコンテトラブトキシド等任意のアルコ
キシドが適用できる。また、本発明によるシラノール基
の低減方法は、シリコンアルコキシドのみを出発原料と
したSiO2単一組成のものに限らず、シリコンアルコキシ
ドに、ホウ素アルコキシド、リンアルコキシド、チタニ
ウムアルコキシド、ジルコニウムアルコキシド、アルミ
ニウムアルコキシド、ゲルマニウムアクロキシド等を組
み合わせることによりB2O3−SiO2系、P2O5−SiO2系、Ti
O2−SiO2系、ZrO2−SiO2系、Al2O3−SiO2系、GeO2−SiO
2系などSiO2を含む多成分系についても適応することが
できる。 該水蒸気処理は、バルク（塊状物）、ファイバー、
（繊維）、フィルム（薄膜）等任意の形状のゲル体に施
すことができる。 該水蒸気処理をバルクに施すことにより低温でシラノ
ール基を低減した多孔質ガラスが得られる。またこうし
て得られた多孔質ガラスは、発泡、爆裂することなく焼
結が行え、緻密なバルクガラスが得られる。 該水蒸気処理をファイバーに施すことにより、吸収に
よる損失の少ないガラスファイバーが得られる。 また、該水蒸気処理をフィルムに施すことにより、低
温で緻密な吸着水分の少ないガラスフィルムが得られ
る。特にフィルムの場合は、バルクに比べその体積が少
ないため短時間で、有効な高圧水蒸気処理によるシラノ
ール基の低減が行える。 該高圧水蒸気処理を施すゲル体が、有機高分子等を含
む金属有機化合物溶液から調製され、かつ200〜500℃で
該有機高分子を燃焼分解した様な非常に気孔率の高いゲ
ル体であるような場合、もしくは、加水分解縮重合反応
を制御することにより非以上に高い気孔率が達成されて
いるゲル体であるとき、該ゲル体の高圧水蒸気処理によ
るシラノール基の低減が有効になされる。 本高圧水蒸気処理は、上記有機高分子を添加した後、
焼成して得られる多孔質な膜体のシラノール基の低減に
対して極めて有効である。 本高圧水蒸気処理の条件は、高温、湿度を変えること
により比較的自由に設定できるが、効果的に行うため、
水蒸気圧が、10kPaないし1MPaとなるように設定する。
処理条件の水蒸気圧が、10kPaより小さい場合、十分な
処理効果を得るのにきわめて長い時間が必要となる。ま
た1MPaより大きい水蒸気圧を設定しようとすると、効果
な装置が必要となる。処理条件は水蒸気圧が100kPaない
しい1MPaであることが特に好ましい。水蒸気圧が、100k
Paないし1MPaであるような処理条件は、例えば、110〜1
90℃の温度範囲において、相対温度を90％程度にするこ
とにより達成することができる。 該ゲル体と、10kPaないし1MPaの水蒸気、を含む雰囲
気との接触時間は、短いとシラノール基除去の本発明の
効果が現れにくく、また長すぎても、それ以上の効果が
上がらず、生産性が低下する。該接触時間では、10〜50
0時間が好ましい。 また、高圧水（液体）による処理においても、本高圧
水蒸気と類似の効果は得られるが、シラノール基低減の
効率の点において水蒸気（気体）により処理の方が、高
圧水処理よりも好ましい。The present invention has been made in order to solve the above-mentioned conventional problems, and a sol-gel in which a gel body is formed from a solution containing a metal organic compound as a starting material, and the gel body is heated to obtain a glass body. In the method for producing a glass body by the method,
The gel body is brought into contact with an atmosphere containing steam of 10 kPa to 1 MPa. Normally, steam treatment of dense glass causes water to be adsorbed on the glass surface and increases the concentration of silanol groups. However, in the present invention, silanol groups are reduced by high-pressure steam treatment, which is completely opposite to the conventional idea described above. It is carried out. As the metal organic compound as a starting material that can be used in the present invention, in particular, silicon alkoxide, any alkoxide such as silicon tetramethoxide, silicon tetraethoxide, silicon tetrapropoxide, and silicon tetrabutoxide can be applied. Further, the method for reducing silanol groups according to the present invention is not limited to a single SiO2 composition using only silicon alkoxide as a starting material, but also includes silicon alkoxide, boron alkoxide, phosphorus alkoxide, titanium alkoxide, zirconium alkoxide, aluminum alkoxide, germanium B2O3-SiO2, P2O5-SiO2, Ti
O2-SiO2, ZrO2-SiO2, Al2O3-SiO2, GeO2-SiO
It can also be applied to multi-component systems containing SiO2, such as two systems. The steam treatment can be performed in bulk (bulk), fiber,
It can be applied to a gel body of any shape such as (fiber) or film (thin film). By performing the steam treatment on the bulk, a porous glass having reduced silanol groups at a low temperature can be obtained. The porous glass thus obtained can be sintered without foaming or explosion, and a dense bulk glass can be obtained. By subjecting the fiber to the steam treatment, a glass fiber having a small loss due to absorption can be obtained. In addition, by performing the steam treatment on the film, a glass film which is dense and has low adsorbed moisture at a low temperature can be obtained. In particular, in the case of a film, the volume thereof is smaller than that of a bulk, so that silanol groups can be reduced by effective high-pressure steam treatment in a short time. The gel body subjected to the high-pressure steam treatment is a gel body having a very high porosity, such as prepared from a metal organic compound solution containing an organic polymer or the like and burning and decomposing the organic polymer at 200 to 500 ° C. In such a case, or when the gel body has achieved an extremely high porosity by controlling the hydrolysis-condensation polymerization reaction, the reduction of silanol groups by high-pressure steam treatment of the gel body is effectively performed. . This high-pressure steam treatment, after adding the organic polymer,
This is extremely effective for reducing silanol groups in a porous film obtained by firing. The conditions of this high-pressure steam treatment can be set relatively freely by changing the high temperature and humidity, but in order to perform it effectively,
The steam pressure is set so as to be 10 kPa to 1 MPa.
When the water vapor pressure of the processing conditions is smaller than 10 kPa, it takes an extremely long time to obtain a sufficient processing effect. To set a steam pressure higher than 1 MPa, an effective device is required. It is particularly preferred that the treatment conditions be such that the water vapor pressure is 100 kPa or 1 MPa. Water vapor pressure is 100k
Processing conditions such as Pa to 1 MPa are, for example, 110 to 1
This can be achieved by setting the relative temperature to about 90% in a temperature range of 90 ° C. If the contact time between the gel body and an atmosphere containing 10 kPa to 1 MPa of water vapor is short, the effect of the present invention for removing silanol groups is difficult to appear, and if it is too long, no further effect is obtained and productivity is not increased. Decrease. In the contact time, 10-50
0 hours is preferred. In the treatment with high-pressure water (liquid), an effect similar to that of the present high-pressure steam can be obtained, but the treatment with steam (gas) is more preferable than the treatment with high-pressure water in terms of silanol group reduction efficiency.
本発明は、上記従来の方法では、シラノール基を除去
するためには、700℃程度以上の高温あるいは、塩素処
理が、必要となることに鑑みなされたものである。 本発明によれは、高圧の水蒸気が、ゲル体中のシラノ
ール基間の脱水縮合反応を促進する作用をしており、こ
れによりい従来の方法よりも低温でシラノール基の低減
と、ゲル体のち密化が行える。The present invention has been made in view of the fact that in the above-mentioned conventional method, a high temperature of about 700 ° C. or more or a chlorination treatment is required to remove silanol groups. According to the present invention, high-pressure steam acts to accelerate the dehydration condensation reaction between silanol groups in the gel body, thereby reducing the silanol groups at a lower temperature than conventional methods and reducing the gel body. Densification can be performed.
実施例−１ 出発原料には、シリコンテトラエトキシド（Si（OC2H
5）４）を用いた。溶媒にはエタノール、加水分解触媒
には、塩化水素をそれぞれ用いた。加える水の量および
エタノールの量は、シリコンテトラエトキシドに対して
モル比でそれぞれ６および５とした。 シリコンテトラエトキシドのエタノール溶液に、希塩
酸（3wt％）を加え室温で60分間撹はんすることにより
加水分解を行った。こうして得られた溶液は、無色透明
であり、該溶液膜厚を制御するためにエタノールで更に
希釈した。こうして得られた溶液に、平均分子量200、6
00、1000のポリエチレングリコール（以後PEGと略称す
る）を、最終生成酸化物であるSiO2に対する重量比で
（PEG）／（SiO2）＝０、0.5、1.0あるいは、1.5、と添
加量をかえて加え、均一に溶解したものを塗布溶液１〜
10とした。 調製した塗布溶液１〜10の内容を第１表に示す。 該塗布溶液１〜10を用いて、シリコンウェハー基板及
び石英基板上に基板を溶液に浸漬し引き上げることによ
って薄膜を形成する、いわゆるディップコーティング法
によりPEG含有SiO2薄膜を形成した。こうして得られた
薄膜コート基板 をクリーンオーブン中で、300〜600℃のある温度で15分
間保持することにより焼成を行った。焼成後薄膜は、添
加したPEGが完全に燃焼分解し、多孔質なSiO2薄膜（膜
厚約250nm）になっていた。 こうして300〜600℃の焼成によって得られた多孔質Si
O2薄膜コート基板を135℃、相対湿度90％（水蒸気圧240
kPa）で約70時間保持することにより高圧水蒸気処理を
行った。 高圧水蒸気処理によるシラノール基の低減の一例とし
て、平均分子量600のPEGを重量比でSiO2に対して１添加
し、350℃で焼成を行ったSiO2薄膜についての結果を第
１図に示す。 第１図の赤外透過スペクトルは、135℃、相対湿度90
％条件下、０時間のものと70時間後のものを示してい
る。この図から明らかに高圧水蒸気処理によって、シラ
ノール基（SiOH）に帰属される950cm-1吸収ピークと300
0〜3800cm-1の吸収ピークが顕著に減少し、シラノール
基が低減されていることが判る。また同時に、Si−Ｏ結
合に帰属される1100cm-1の吸収ピークが、高周波数側に
シフトし、SiO2のネットワーク構造が強化され薄膜のち
密がなされていることが判った。 上記高圧水蒸気処理による、SiO2膜のシラノール基の
低減を示すIRスペクトル変化には、350℃で焼成を行っ
た平均分子量600のPEGをSiO2に対して１添加した膜体に
限らず、今回検討を行った300〜600℃の任意の焼成温度
に対して、また今回検討を行った任意のPEG添加量、分
子量のものについて同様の結果が得られた。 高圧水蒸気処理、０時間及び170時間後の石英基板上
に形成した多孔質SiO2薄膜の真の屈折率と水分が吸着し
た後の見かけの屈折率を分光反射率特性から求めた。第
２表にその結果を示す。 第２表中の試料番号は、第１表の試料番号と同一であ
る。 これより１〜10のいずれの塗布溶液から作製したSiO2
膜体とも、高圧水蒸気処理後、その真の屈折率が高くな
っていることと、水分吸着によ る屈折率増加（水分空着後の見かけの屈折率と真の屈折
率の差）が小さくなっていることが判る。 上記屈折率の高圧水蒸気処理による変化は、高圧水蒸
気処理によってSiO2膜中のシラノール基が、低減される
ことによって、膜体がち密化し、膜体の吸湿性が、低減
したことを示すものである。 実施例−２ 出発原料にシリコンテトラエトキシドおよびジルコニ
ウムテトラｎブトキシド（Zr（OnC4H9）４）を用い、溶
媒には、エタノール加水分解触媒には、塩化水素をそれ
ぞれ用いて20ZrO2・80SiO2（モル％）膜を作製した。 シリコンテトラエトキシドのアルコール溶液にモル比
で２倍の水の量になるように塩酸（10wt％）を加え、室
温で40分間加水分解を行った。その後ジルコニウムテト
ラｎブトキシドのエタノール溶液を加え更に10分間撹は
んした後、シリコンテトラエトキシドに対してモル比で
２倍の量の水を加えさらに30分撹はんを続けることによ
り反応させた。 こうして得られた溶液をエタノールで適当に希釈する
ことにより塗布溶液11とした。 塗布溶液11を用いてシリコンウェハー基板および石英
基板上にディップコーティング法により20ZrO2・80SiO2
薄膜を形成した。 20ZrO・80SiO2薄膜コート各種基板を先の実施例１同
様135℃、相対湿度90％の条件下で約50時間保持し高圧
水蒸気処理を行った。 先の実施例１の結果と同様の効果が得られ、高圧水蒸
気処理によりシラノール基に帰属される3000〜3800cm-1
ブロードな吸収および950cm-1のショルダーの強度が低
下した。また1100cm-1のSi−Ｏに帰属される吸収ピーク
が高波数側にシフトした。さらに真の薄膜の屈折率は、
高くなり同時に吸湿性も低減された。 上記高圧水蒸気処理によるシラノール基低減の効果
は、実施例１、２に於けるSiO2あるいは、ZrO2−SiO2系
に限らず、類似の作製方法で得られた、B2O3−SiO2系、
TiO2−SiO2系に、SnO2−SiO2系、GeO2−SiO2系薄膜にお
いても有効であった。 実施例−３ エトラエトキシシランのエタノール溶液にアンモニア
水を加えた。ここで加える水のシリコンテトラエトキシ
ドに対するモル比は、10とした。 アンモニア水を添加した後、溶液を激しく撹はんする
ことによりSiO2微粒子の白色沈澱を得た。 こうして得られた白色沈澱を200℃で24時間乾燥を行
った後、120℃相対湿度90％（水蒸気圧170kPa）で300時
間高圧水蒸気処理を行った。 高圧水蒸気処理後のSiO2微粒子を加圧成形後、最終的
に1400℃まで昇温し、塊状石英ガラスを得た。 上記高圧水蒸気処理を行った後1400℃で焼結を行うこ
とにより得られた塊状石英ガラスは、2.2、2.4及び2.78
μｍのOH基に起因する吸収帯の強度が、高圧水蒸気処理
を行わず1400℃で焼成を行うことにより得られた石英ガ
ラス基板よりも小さいことがわかった。 本実施例で、塊状石英ガラスを作製するために用いた
高圧水蒸気処理後のSiO2微粒子は、例えば石英ガラス光
ファイバーの原料としても用いることができる。 また本実施例における高圧水蒸気処理は、シリコンア
ルコキシドのみを出発原料とした石英ガラスの作製に限
らず、シリコンアルコキシドに、ホウ素アルコキシド、
リンアルコキシド、チタニウムアルコキシド、ジルコニ
ウムアルコキシド、アルミニウムアルコキシド、ゲルマ
ニウムアルコキシド等を組み合わせることによりB2O3−
SiO2系、P2O5−SiO2系、TiO2−SiO2系、ZrO2−SiO2系、
Al2O3−SiO2系、GeO2−SiO2系などSiO2を含む多成分系
塊状ガラスもしくは、ファイバーの作製においても適応
することができる。Example 1 Silicon tetraethoxide (Si (OC2H
5) 4) was used. Ethanol was used as a solvent, and hydrogen chloride was used as a hydrolysis catalyst. The amount of water added and the amount of ethanol were 6 and 5, respectively, in molar ratio to silicon tetraethoxide. Dilute hydrochloric acid (3 wt%) was added to an ethanol solution of silicon tetraethoxide, and the mixture was stirred at room temperature for 60 minutes to perform hydrolysis. The solution thus obtained was colorless and transparent, and was further diluted with ethanol to control the thickness of the solution. The solution thus obtained has an average molecular weight of 200, 6
A polyethylene glycol (hereinafter abbreviated as PEG) of 00, 1000 is added by weight ratio of (PEG) / (SiO2) = 0, 0.5, 1.0 or 1.5 with respect to SiO2 which is a final oxide produced. , Uniformly dissolve the coating solution 1
It was set to 10. Table 1 shows the contents of the prepared coating solutions 1 to 10. Using the coating solutions 1 to 10, a PEG-containing SiO2 thin film was formed on a silicon wafer substrate and a quartz substrate by a so-called dip coating method in which the substrate was immersed in the solution and pulled up to form a thin film. The thin film coated substrate thus obtained Was fired in a clean oven at a certain temperature of 300 to 600 ° C. for 15 minutes. After firing, the added PEG was completely burned and decomposed, resulting in a porous SiO2 thin film (about 250 nm thick). Porous Si thus obtained by firing at 300 to 600 ° C
O2 thin film coated substrate at 135 ° C, 90% relative humidity (water vapor pressure 240
(kPa) for about 70 hours to perform high-pressure steam treatment. As an example of the reduction of silanol groups by high-pressure steam treatment, FIG. 1 shows the results of a SiO2 thin film obtained by adding PEG having an average molecular weight of 600 to SiO2 in a weight ratio of 1 and firing at 350 ° C. The infrared transmission spectrum of FIG.
The results at 0 hour and after 70 hours under% conditions are shown. This figure clearly shows that the high-pressure steam treatment caused the absorption peak at 950 cm -1 attributed to the silanol group (SiOH)
It can be seen that the absorption peak at 0 to 3800 cm -1 is significantly reduced, and the silanol group is reduced. At the same time, it was found that the absorption peak at 1100 cm -1 attributed to the Si-O bond shifted to the higher frequency side, the network structure of SiO2 was strengthened, and the density of the thin film was increased. The IR spectrum change that indicates the reduction of silanol groups in the SiO2 film due to the high-pressure steam treatment is not limited to the film body obtained by baking at 350 ° C and adding PEG with an average molecular weight of 600 to SiO2. Similar results were obtained for the arbitrary firing temperature of 300 to 600 ° C. and for the arbitrary PEG addition amount and molecular weight examined in this study. The true refractive index of the porous SiO2 thin film formed on the quartz substrate after high-pressure steam treatment, 0 hours and 170 hours, and the apparent refractive index after moisture was adsorbed were determined from the spectral reflectance characteristics. Table 2 shows the results. The sample numbers in Table 2 are the same as the sample numbers in Table 1. SiO2 prepared from any of the coating solutions 1 to 10
Both membranes have a high true refractive index after high-pressure steam treatment. It can be seen that the increase in the refractive index (the difference between the apparent refractive index and the true refractive index after water deposition) is small. The change in the refractive index by the high-pressure steam treatment indicates that the silanol groups in the SiO2 film are reduced by the high-pressure steam treatment, so that the film is denser and the hygroscopicity of the film is reduced. . Example 2 Using silicon tetraethoxide and zirconium tetra-n-butoxide (Zr (OnC4H9) 4) as starting materials, and using hydrogen chloride as a solvent for an ethanol hydrolysis catalyst, 20ZrO2 · 80SiO2 (mol%). A film was prepared. Hydrochloric acid (10 wt%) was added to an alcohol solution of silicon tetraethoxide so that the amount of water became twice the molar ratio, and hydrolysis was performed at room temperature for 40 minutes. Thereafter, an ethanol solution of zirconium tetra-n-butoxide was added, and the mixture was further stirred for 10 minutes. Then, water was added at twice the molar ratio to silicon tetraethoxide, and the mixture was further stirred for 30 minutes to react. . The solution thus obtained was appropriately diluted with ethanol to obtain a coating solution 11. 20ZrO2 80SiO2 on silicon wafer substrate and quartz substrate by dip coating method using coating solution 11.
A thin film was formed. Various substrates coated with a 20ZrO / 80SiO2 thin film were held at 135 ° C. and a relative humidity of 90% for about 50 hours and subjected to high-pressure steam treatment as in Example 1 above. The same effect as the result of the previous Example 1 is obtained, and 3000 to 3800 cm −1 attributed to a silanol group by high-pressure steam treatment.
Broad absorption and reduced strength of the shoulder at 950 cm -1 . In addition, the absorption peak attributed to Si—O at 1100 cm −1 shifted to the higher wavenumber side. Furthermore, the refractive index of a true thin film is
It became higher and the hygroscopicity was reduced at the same time. The effect of reducing the silanol group by the high-pressure steam treatment is not limited to the SiO2 or ZrO2-SiO2 system in Examples 1 and 2, but the B2O3-SiO2 system obtained by a similar manufacturing method.
It was also effective for SnO2-SiO2 and GeO2-SiO2 thin films in addition to TiO2-SiO2. Example 3 Aqueous ammonia was added to an ethanol solution of etraethoxysilane. The molar ratio of the added water to silicon tetraethoxide was set to 10. After adding aqueous ammonia, the solution was vigorously stirred to obtain a white precipitate of SiO2 fine particles. The white precipitate thus obtained was dried at 200 ° C. for 24 hours, and then subjected to high-pressure steam treatment at 120 ° C. and 90% relative humidity (steam pressure 170 kPa) for 300 hours. After pressure-molding the SiO2 fine particles after the high-pressure steam treatment, the temperature was finally raised to 1400 ° C. to obtain a massive quartz glass. Lumped quartz glass obtained by performing sintering at 1400 ° C. after performing the high-pressure steam treatment is 2.2, 2.4 and 2.78.
It was found that the intensity of the absorption band caused by the OH group of μm was smaller than that of the quartz glass substrate obtained by firing at 1400 ° C. without performing high-pressure steam treatment. In this embodiment, the SiO2 fine particles after the high-pressure steam treatment used for producing the bulk quartz glass can be used as, for example, a raw material of a quartz glass optical fiber. Further, the high-pressure steam treatment in this embodiment is not limited to the production of quartz glass using only silicon alkoxide as a starting material.
By combining phosphorus alkoxide, titanium alkoxide, zirconium alkoxide, aluminum alkoxide, germanium alkoxide, etc.
SiO2, P2O5-SiO2, TiO2-SiO2, ZrO2-SiO2,
It can also be applied to the production of multi-component bulk glass containing SiO2, such as Al2O3-SiO2, GeO2-SiO2, or fibers.
本発明の、高圧水蒸気処理によるシラノール基の低減
方法は、実施例からも明かなとおり、従来法によるシラ
ノール基の低減方法よりも、低温で有効にゲル−ガラス
体の水分の吸着サイトあるいは、構造中の欠陥として作
用するシラノール基の低減が行え、同時にゲル−ガラス
体のち密化が行える。よってSiO2を含む種々の均一なガ
ラス体が作製できる。As is clear from the examples, the method for reducing silanol groups by high-pressure steam treatment of the present invention is more effective at a lower temperature than the conventional method for reducing silanol groups at a low temperature. Silanol groups acting as defects therein can be reduced, and at the same time, the gel-glass body can be densified. Therefore, various uniform glass bodies containing SiO2 can be produced.
第１図は、実施例１における本発明の高圧水蒸気処理に
よるシラノール基の低減の効果を示す赤外透過スペクト
ル。FIG. 1 is an infrared transmission spectrum showing the effect of reducing silanol groups by high-pressure steam treatment of the present invention in Example 1.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) C03B 8/00 C03B 8/02 C03B 8/04 C03B 19/12 - 20/00 C03C 17/00 - 17/44 C03C 23/00 C03C 25/00 - 25/06 C03B 37/016──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. 6 , DB name) C03B 8/00 C03B 8/02 C03B 8/04 C03B 19/12-20/00 C03C 17/00-17 / 44 C03C 23/00 C03C 25/00-25/06 C03B 37/016
Claims (2)
てゲル体を形成し、該ゲル体を加熱してガラス体を得
る、ゾルゲル法によるガラス体の製造方法において、該
ゲル体を、10kPaないし1MPaの水蒸気、を含む雰囲気と
接触させることを特徴とするガラス体の製造方法。A method for producing a glass body by a sol-gel method, wherein a gel body is formed from a solution containing a metal organic compound as a starting material, and the gel body is heated to obtain a glass body. A method for producing a glass body, which is brought into contact with an atmosphere containing 1 MPa of water vapor.
請求項１記載のガラス体の製造方法。2. The method for producing a glass body according to claim 1, wherein said gel body is a thin film gel body on a substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1297959A JP2836138B2 (en) | 1989-11-16 | 1989-11-16 | Method for manufacturing glass body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1297959A JP2836138B2 (en) | 1989-11-16 | 1989-11-16 | Method for manufacturing glass body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03159925A JPH03159925A (en) | 1991-07-09 |
| JP2836138B2 true JP2836138B2 (en) | 1998-12-14 |
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ID=17853304
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1297959A Expired - Fee Related JP2836138B2 (en) | 1989-11-16 | 1989-11-16 | Method for manufacturing glass body |
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| Country | Link |
|---|---|
| JP (1) | JP2836138B2 (en) |
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| Publication number | Publication date |
|---|---|
| JPH03159925A (en) | 1991-07-09 |
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