JP2835540B2 - Method of manufacturing quartz glass member for excimer laser - Google Patents

Method of manufacturing quartz glass member for excimer laser

Info

Publication number
JP2835540B2
JP2835540B2 JP3182858A JP18285891A JP2835540B2 JP 2835540 B2 JP2835540 B2 JP 2835540B2 JP 3182858 A JP3182858 A JP 3182858A JP 18285891 A JP18285891 A JP 18285891A JP 2835540 B2 JP2835540 B2 JP 2835540B2
Authority
JP
Japan
Prior art keywords
quartz glass
glass
temperature
transparent
excimer laser
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
Application number
JP3182858A
Other languages
Japanese (ja)
Other versions
JPH05186234A (en
Inventor
裕幸 西村
朗 藤ノ木
利勝 松谷
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shin Etsu Quartz Products Co Ltd
Original Assignee
Shin Etsu Quartz Products Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to JP3182858A priority Critical patent/JP2835540B2/en
Application filed by Shin Etsu Quartz Products Co Ltd filed Critical Shin Etsu Quartz Products Co Ltd
Priority to DE69219445T priority patent/DE69219445T2/en
Priority to KR1019930700573A priority patent/KR0165695B1/en
Priority to EP92913798A priority patent/EP0546196B1/en
Priority to DE199292913798T priority patent/DE546196T1/en
Priority to PCT/JP1992/000821 priority patent/WO1993000307A1/en
Priority to US07/977,397 priority patent/US5364433A/en
Publication of JPH05186234A publication Critical patent/JPH05186234A/en
Priority to US08/286,538 priority patent/US5523266A/en
Application granted granted Critical
Publication of JP2835540B2 publication Critical patent/JP2835540B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00Other methods of shaping glass
    • C03B19/14Other methods of shaping glass by gas- or vapour- phase reaction processes
    • C03B19/1453Thermal after-treatment of the shaped article, e.g. dehydrating, consolidating, sintering

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【産業上の利用分野】本発明は、紫外線、特にエキシマ
レーザーの照射に対して優れた安定性を有する光学用石
英ガラス部材の製造方法に関する。また、本発明は、半
導体チップ製造用のエキシマレーザーを用いたリソグラ
フィー用のステッパーレンズ、その他エキシマレーザー
光に使用される光学部材に好適に使用される石英ガラス
部材の製造方法に関するものである。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an optical quartz glass member having excellent stability against irradiation of ultraviolet rays, particularly excimer laser. The present invention also relates to a method for manufacturing a quartz glass member suitably used for a lithography stepper lens using an excimer laser for manufacturing a semiconductor chip and other optical members used for excimer laser light.

【0002】[0002]

【従来の技術】近年、LSIの高集積化に伴い、ウエハ
ー上に集積回路パターンを描画する光リソグラフィー技
術においても、サブミクロン単位の描画技術が要求され
ており、より微細な線幅描画を行うために、露光系の光
源の短波長化が進められてきている。このため、例え
ば、リソグラフィー用のステッパーレンズには、優れた
均質性と優れた紫外線の透過性、及び紫外線照射に対し
て強い耐性が要求されている。ところが、従来の一般的
な光学ガラスを用いたレンズでは紫外線の透過性が極め
て悪く、例えば、使用波長が365nm(i線)より短
い波長領域では光透過率が急激に減少し、実質上使用す
ることが困難であった。また、光吸収によるレンズの発
熱によって、レンズの焦点距離やその他の特性を狂わせ
る要因となっている。このようなことから、紫外線透過
材料として、石英ガラスが用いられてきた。
2. Description of the Related Art In recent years, with the increase in integration of LSIs, a drawing technique of a submicron unit is required also in an optical lithography technique for drawing an integrated circuit pattern on a wafer, and a finer line width drawing is performed. Therefore, the wavelength of the light source of the exposure system has been shortened. For this reason, for example, a stepper lens for lithography is required to have excellent homogeneity, excellent transmittance of ultraviolet rays, and strong resistance to ultraviolet irradiation. However, a conventional lens using general optical glass has extremely poor ultraviolet transmittance. For example, in a wavelength region where the wavelength used is shorter than 365 nm (i-line), the light transmittance sharply decreases, and the lens is practically used. It was difficult. In addition, heat generation of the lens due to light absorption causes a change in the focal length and other characteristics of the lens. For this reason, quartz glass has been used as an ultraviolet transmitting material.

【0003】しかしながら、天然の水晶を原料とした石
英ガラスは、250nm以下の波長領域の光透過性が悪
く、また、紫外線の照射によって、紫外線領域に新たな
光の吸収を生じて、紫外線領域における光の透過性は更
に低下する。この石英ガラスにおける光の吸収は、石英
ガラス中の不純物に起因するために、紫外線領域で使用
される光学部材には、不純物含有量の少ない合成石英ガ
ラス(合成シリカガラス)が用いられている。この合成
石英ガラスは、通常、紫外線吸収の原因となる金属不純
物の混入を避けるために、高純度のシリコン化合物、例
えば四塩化けい素(SiCl4)などの蒸気を、直接酸
水素炎中に導入して、火炎加水分解させてガラス微粒子
を直接回転する耐熱性基体上に堆積・溶融ガラス化させ
て、透明なガラスとして製造されている。
[0003] However, quartz glass made from natural quartz has poor light transmittance in the wavelength region of 250 nm or less. In addition, irradiation of ultraviolet light causes new absorption of light in the ultraviolet light region, thereby causing the absorption of light in the ultraviolet light region. Light transmission is further reduced. Since the absorption of light in the quartz glass is caused by impurities in the quartz glass, a synthetic quartz glass (synthetic silica glass) having a small impurity content is used for an optical member used in an ultraviolet region. This synthetic quartz glass usually introduces a vapor of a high-purity silicon compound, for example, silicon tetrachloride (SiCl 4 ), directly into the oxyhydrogen flame in order to avoid mixing of metal impurities that cause ultraviolet absorption. Then, the glass fine particles are deposited on a heat-resistant substrate that is directly rotated and then melted and vitrified by flame hydrolysis to produce a transparent glass.

【0004】このようにして製造された透明な合成石英
ガラス部材は、190nm程度の短波長領域まで良好な
光透過性を示し、紫外線レーザー光、例えば具体的には
前記i線の他に、KrF(248nm),XeCl(3
08nm),XeBr(282nm),XeF(35
1、353nm),ArF(193nm)等のエキシマ
レーザー光及びYAGの4倍高調波(250nm)等に
ついての透過材料として用いられてきた。
[0004] The transparent synthetic quartz glass member manufactured in this manner shows good light transmittance up to a short wavelength region of about 190 nm, and in addition to ultraviolet laser light, for example, KrF (248 nm), XeCl (3
08 nm), XeBr (282 nm), XeF (35
It has been used as a transmission material for excimer laser light such as 1,353 nm) and ArF (193 nm) and the fourth harmonic (250 nm) of YAG.

【0005】また、原料としての四塩化けい素の一層の
高純度化と共に、酸水素燃焼炎による火炎加水分解の工
程を改善することによって、金属不純物元素が0.1p
pm以下の高純度石英ガラスを合成し、かつ前記火炎加
水分解の条件を調節することによって製造される合成石
英ガラス中に所定濃度のOH基が含まれるようにし、こ
れによって耐レーザー性に優れた光学用の石英ガラス部
材を得る試みがなされている(特開平1−167258
号公報)。
In addition, by further improving the purity of silicon tetrachloride as a raw material and improving the flame hydrolysis process using an oxyhydrogen combustion flame, metal impurity elements can be reduced to 0.1 p.
pm or less, and a predetermined concentration of OH groups is contained in the synthetic quartz glass produced by adjusting the conditions of the flame hydrolysis, thereby providing excellent laser resistance. Attempts have been made to obtain a quartz glass member for optics (JP-A-1-167258).
No.).

【0006】しかしながら、これらの方法は一応効果は
あるものの、未だ十分とはいえない。また、製造工程の
制御に困難を伴う技術的、経済的不利がある。ところ
で、合成石英ガラスに紫外線を照射することによって新
たに生じる紫外線領域における光の吸収は、専ら、石英
ガラス中の固有欠陥から光反応により、生じた常磁性欠
陥によるものと考えられている。このような常磁性欠陥
による光吸収は、これまでESRスペクトルなどで数多
く同定されており、例えば、E’センター(Si・)や
NBOHC(Si−O・)などがある。
[0006] Although these methods are effective, they are not yet satisfactory. In addition, there are technical and economic disadvantages that make it difficult to control the manufacturing process. By the way, it is considered that the absorption of light in the ultraviolet region newly generated by irradiating the synthetic quartz glass with ultraviolet light is mainly caused by a paramagnetic defect generated by a photoreaction from an intrinsic defect in the quartz glass. Many light absorptions due to such paramagnetic defects have been identified in ESR spectra and the like, and include, for example, E ′ center (Si.) And NBOHC (Si—O.).

【0007】以上のように、常磁性欠陥は、一般的に
は、光学的吸収帯を有している。したがって、石英ガラ
スに紫外線を照射した場合、石英ガラスの常磁性欠陥に
よる紫外線領域で問題となる吸収帯は、例えば、E’セ
ンターの215nmと、まだ正確に同定されていない
が、260nmがある。これらの吸収帯は比較的ブロー
ドでかつ、強い吸収を生じるときがあり、例えば、Ar
Fレーザー(193nm)やKrFレーザー(248n
m)の透過材料として用いる場合には大きな問題となっ
ている。常磁性欠陥の原因となる石英ガラス中の固有欠
陥は、例えばSiOHやSiClなどのSiO2以外の
構造をしたものや、Si−Si,Si−O−O−Siな
どの酸素欠損、酸素過剰の構造をしたものである。この
ような理由から、エキシマレーザーに使用される合成石
英ガラスには、より強い耐紫外線性が要求されている。
本発明は、エキシマレーザーに使用される合成石英ガラ
スにおいて、強い紫外線照射にともなって生じる紫外線
領域における光透過率の低下に係る問題点を解決するこ
とを目的としている。
[0007] As described above, paramagnetic defects generally have an optical absorption band. Therefore, when the quartz glass is irradiated with ultraviolet rays, the absorption band which causes a problem in the ultraviolet region due to the paramagnetic defect of the quartz glass is, for example, 215 nm at the E ′ center, which has not been accurately identified yet, but is 260 nm. These bands are relatively broad and may give rise to strong absorptions, for example, Ar
F laser (193nm) and KrF laser (248n
This is a major problem when used as a transparent material of m). Specific defects in quartz glass that cause paramagnetic defects include, for example, those having a structure other than SiO 2 such as SiOH and SiCl, oxygen deficiencies such as Si—Si, Si—O—O—Si, and excess oxygen. It is a structure. For these reasons, synthetic quartz glass used for excimer lasers is required to have higher UV resistance.
SUMMARY OF THE INVENTION An object of the present invention is to solve a problem associated with a decrease in light transmittance in an ultraviolet region caused by strong ultraviolet irradiation in a synthetic quartz glass used for an excimer laser.

【0008】[0008]

【課題を解決するための手段】本発明者らは、上記の課
題を解決するために、ガラス中のOH濃度及び不純物濃
度に着目し、極力これらがガラス中に含有されない製造
法を確立することによって、耐紫外線性の優れた石英ガ
ラスが得られることを見いだし、本発明に到達したもの
である。本発明は、エキシマレーザーに光学部材として
使用される合成石英ガラスにおいて、強い紫外線照射に
伴って生じる紫外線領域における光透過率の低下を極力
低減した合成石英ガラスの製造方法を提供するものであ
り、特に、エキシマレーザー用のステッパーレンズに好
適に使用しうる光学用石英ガラス部材の製造方法を提供
するものである。
Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have focused on OH concentration and impurity concentration in glass and established a production method in which these are not contained in glass as much as possible. As a result, it has been found that quartz glass having excellent ultraviolet resistance can be obtained, and the present invention has been achieved. The present invention provides a method for producing a synthetic quartz glass in which a decrease in light transmittance in an ultraviolet region caused by strong ultraviolet irradiation is reduced as much as possible in a synthetic quartz glass used as an optical member for an excimer laser, In particular, an object of the present invention is to provide a method for manufacturing an optical quartz glass member that can be suitably used for a stepper lens for an excimer laser.

【0009】即ち、本発明は、揮発性けい素化合物を、
酸水素炎により火炎加水分解し、生成する微粒子シリカ
を耐熱性基体上に堆積させてシリカガラスの多孔質母材
を製造し、該シリカガラスの多孔質母材を1×10-2
ール以上の高真空度で加熱して、透明な石英ガラスを形
成し、該透明石英ガラスを均質化処理することにより、
少なくとも一方向に脈理を有しない高均質石英ガラスを
形成し、該高均質石英ガラスを成形後アニール処理する
ことを特徴とするエキシマレーザ用石英ガラス部材の製
造方法にある。
That is, the present invention provides a method for producing a volatile silicon compound,
The fine particle silica produced by flame hydrolysis with an oxyhydrogen flame is deposited on a heat-resistant substrate to produce a porous preform of silica glass, and the porous preform of silica glass is 1 × 10 -2 torr or more. By heating at a high vacuum to form a transparent quartz glass and homogenizing the transparent quartz glass,
A method for producing a quartz glass member for an excimer laser, characterized in that a highly homogeneous quartz glass having no striae in at least one direction is formed, and the highly homogeneous quartz glass is annealed after being formed.

【0010】本発明において、石英ガラスの原料として
は、金属不純物の混入を少なくするために、例えば、メ
チルトリメトキシシラン〔Si(CH3)(OC
33〕、テトラメトキシシラン〔Si(CH3)(O
CH33〕等のアルキルポリアルコキシシラン若しくは
アルコキシシラン又はその他のシラン化合物或は四塩化
けい素等の揮発性無機けい素化合物などの揮発性けい素
化合物が使用される。
In the present invention, as a raw material of quartz glass, for example, methyltrimethoxysilane [Si (CH 3 ) (OC)
H 3 ) 3 ], tetramethoxysilane [Si (CH 3 ) (O
CH 3 ) 3 ] or other volatile polysilicon compounds such as alkylpolyalkoxysilanes or alkoxysilanes or other silane compounds or volatile inorganic silicon compounds such as silicon tetrachloride.

【0011】本発明において、揮発性けい素化合物は、
揮発させて、直接火炎加水分解法により、加水分解され
て、微粒子状のシリカガラスを生成し、このシリカガラ
スを耐熱性基体上に堆積させて、合成シリカガラスの棒
状の多孔質母材、所謂スートを製造する。本発明におい
て、合成シリカガラスの多孔質母材は、例えば、気相軸
付け法(VAD法)及び外付けCVD法で製造でき、も
とより、本発明における合成シリカガラスの多孔質母材
は、合成シリカガラスの多孔質集合体であれば足りるの
で、これらの製造方法に限定されるものではない。
In the present invention, the volatile silicon compound is
It is volatilized and hydrolyzed by a direct flame hydrolysis method to produce finely divided silica glass, and this silica glass is deposited on a heat-resistant substrate to form a rod-shaped porous preform of synthetic silica glass, so-called. Manufacture soot. In the present invention, the porous preform of the synthetic silica glass can be produced by, for example, a vapor phase axial method (VAD method) and an external CVD method. Since a porous aggregate of silica glass is sufficient, the present invention is not limited to these production methods.

【0012】本発明において、この合成シリカガラスの
多孔質母材中には、酸水素炎により形成されるOH基が
混入しているので、OH基による固有欠陥の生成を避け
るために、合成シリカガラス中のOH基の除去が行われ
る。従来、例えば光ファイバー用のガラスでは、ガラス
中のOH基を極力減少させるために、多孔質のシリカガ
ラスの合成段階又は透明ガラス化の段階で、塩素ガス
(Cl2)を脱水剤とし、塩素ガス中で熱処理する方法
が行われている。しかし、この方法では、OHを低減さ
せても、ガラス中に塩素が残留してしまう。また不活性
ガス中で熱処理するとしても、常圧で処理する限り、ガ
ラス中にガスが溶け込んで、何れも固有欠陥を生成す
る。
In the present invention, the porous matrix of the synthetic silica glass contains OH groups formed by oxyhydrogen flame. Removal of OH groups in the glass is performed. Conventionally, for example, in glass for optical fibers, in order to reduce OH groups in the glass as much as possible, chlorine gas (Cl 2 ) is used as a dehydrating agent and chlorine gas (Cl 2 ) is used at the stage of synthesis or transparent vitrification of porous silica glass. There is a method of performing heat treatment inside. However, in this method, even if OH is reduced, chlorine remains in the glass. Further, even if heat treatment is performed in an inert gas, as long as the treatment is performed at normal pressure, the gas dissolves in the glass, and any of them generates intrinsic defects.

【0013】そこで、本発明においては、前記合成シリ
カガラスを、1×10-2トール以上の高真空度即ち1×
10-2トール以下の圧力の雰囲気中で、例えば1350
乃至1700℃の温度範囲内の温度に加熱して、透明ガ
ラス化が行なわれる。この合成シリカガラスの透明ガラ
ス化の処理の真空度及び加熱温度は、合成シリカガラス
に含有されるOH基及び金属不純物を、揮散し除去でき
るように選ばれ、多孔質母材の大きさ及び透明化処理時
間に関連して、上記温度範囲内でできる限り低い温度域
とするのが好ましい。
Therefore, in the present invention, the synthetic silica glass is used in a high vacuum of 1 × 10 −2 Torr or more, that is, 1 × 10 −2 Torr or more.
In an atmosphere at a pressure of 10 -2 torr or less, for example, 1350
Heating to a temperature within the temperature range of 1700 ° C. to 1700 ° C. results in vitrification. The degree of vacuum and the heating temperature in the process of vitrifying the synthetic silica glass are selected so that OH groups and metal impurities contained in the synthetic silica glass can be volatilized and removed. It is preferable to set the temperature range as low as possible within the above temperature range in relation to the chemical treatment time.

【0014】上記合成シリカガラスの多孔質母材の透明
ガラス化は、該母材のシリカガラス微粒子の表面のシラ
ノール基(SiOH)の脱水縮合反応が、次の反応式の
ように起こり、透明ガラス化が起こる。 2SiOH→SiOSi+H2O この反応で生成する水分子は、石英ガラス微粒子間から
外部に拡散することによって除去されるので、OH基の
除去には、石英ガラス微粒子間から外部に拡散する時間
が必要である。
In the above-mentioned synthetic vitreous silica glass, the vitrification of the porous glass is carried out by a dehydration-condensation reaction of silanol groups (SiOH) on the surfaces of the silica glass fine particles of the glass as shown in the following reaction formula. Transformation occurs. 2SiOH → SiOSi + H 2 O Water molecules generated by this reaction are removed by diffusing from between the quartz glass fine particles to the outside. Therefore, removal of the OH group requires time to diffuse from between the quartz glass fine particles to the outside. is there.

【0015】したがって、この反応の際に、ガラス化温
度が1700℃以上であると、石英ガラス表面におい
て、石英ガラス微粒子間の焼結反応が早く進行して、上
記の脱水縮合反応が十分に完結しない中に、前記多孔質
母材が透明ガラス化されて、石英ガラス中にOH基が除
去されずに残留することとなる。一方、上記の脱水縮合
反応は、焼結温度よりも低い温度、例えば、800℃程
度の温度でも進行するので、石英ガラスからOH基を除
去するには、石英ガラスの微粒子間の焼結が進行しない
間に、上記の脱水縮合反応を完結させ、OH基の拡散除
去を行うようにすることが必要である。
Therefore, if the vitrification temperature is 1700 ° C. or higher during this reaction, the sintering reaction between the quartz glass particles proceeds rapidly on the quartz glass surface, and the above-mentioned dehydration condensation reaction is sufficiently completed. In the meantime, the porous base material is vitrified transparently, and OH groups remain in the quartz glass without being removed. On the other hand, since the above-mentioned dehydration condensation reaction proceeds even at a temperature lower than the sintering temperature, for example, a temperature of about 800 ° C., sintering between fine particles of quartz glass proceeds to remove OH groups from quartz glass. It is necessary to complete the above-mentioned dehydration-condensation reaction and to carry out the diffusion removal of the OH group while not being performed.

【0016】そこで、石英ガラスからOH基を除去する
のに、例えば、800乃至1200℃の温度範囲内の温
度に一定時間保持して、上記の脱水縮合反応を促進させ
た後、より高い温度に加熱して、石英ガラス微粒子間の
焼結を行って、透明ガラス化を行うという、二段階の透
明ガラス化を行うことができる。また、ゾーンメルト法
の場合には、上記の脱水縮合反応をできるだけ緩やかに
行うような条件でガラス化することが必要である。即
ち、加熱領域の移動をできるだけゆっくりと行うか、加
熱温度をできるだけ低温で行うべきである。一般的に
は、大きな多孔質石英ガラス母材になるほど、加熱領域
の移動は遅くする方が好ましい。
Therefore, in order to remove OH groups from the quartz glass, for example, the temperature is kept at a temperature in the range of 800 to 1200 ° C. for a certain period of time to accelerate the above-mentioned dehydration condensation reaction, and then to a higher temperature. Heating and sintering between the silica glass fine particles to perform transparent vitrification can be performed in two stages of transparent vitrification. In the case of the zone melt method, it is necessary to vitrify under the condition that the above-mentioned dehydration condensation reaction is performed as slowly as possible. That is, the heating area should be moved as slowly as possible or the heating temperature should be set as low as possible. Generally, it is preferable that the larger the porous quartz glass base material, the slower the movement of the heating area.

【0017】透明ガラス化時の脱水縮合反応により生成
する水(H2O)を、できるだけ早く拡散させて、外部
に放出させるには、少なくとも10-2トール以上の高真
空雰囲気をガラス化処理中に保持することが必要なこと
が分かった。ここで重要なことは、脱水縮合反応時及び
透明ガラス化反応時には、10-2トール以上の高真空度
に保つことが必要である。なお、処理されるシリカガラ
スの多孔質母材が大きい場合には、生成するH2Oの量
もかなり多くなるため、使用する真空排気装置は、到達
真空度の高いものより、排気速度の高いものが有効であ
る。
In order to diffuse water (H 2 O) generated by the dehydration condensation reaction at the time of transparent vitrification as quickly as possible and discharge it to the outside, a high vacuum atmosphere of at least 10 −2 Torr or more is required during the vitrification treatment. It was found necessary to hold it. What is important here is that it is necessary to maintain a high vacuum of 10 -2 Torr or more during the dehydration condensation reaction and the transparent vitrification reaction. When the porous base material of the silica glass to be treated is large, the amount of H 2 O generated is considerably large. Therefore, the evacuation apparatus used has a higher evacuation speed than that of the ultimate vacuum degree. Things are valid.

【0018】このようにして製造された合成石英ガラス
は、OH濃度が低濃度であり、つまり合成石英ガラス中
のOHの含有量が50ppm以下、好ましくは、30p
pm以下であり、金属不純物の含有量も極めて少なく、
高純度の透明石英ガラスである。
The synthetic quartz glass thus produced has a low OH concentration, that is, the synthetic quartz glass has an OH content of 50 ppm or less, preferably 30 ppm.
pm or less, the content of metal impurities is extremely small,
High purity transparent quartz glass.

【0019】CVD法により製造された石英ガラスは、
その製造時の温度変化によって、耐熱性基体上のシリカ
ガラス微粒子堆積体に密度の揺らぎを生じるが、この揺
らぎが、透明ガラス化後に脈理として残留するので、通
常CVD法により製造された透明石英ガラスは、脈理を
有していることが一般的である。しかし、ステッパーレ
ンズ等の光学用部材とするには、この脈理を除去しなけ
ればならない。そこで、本発明においては、前記高純度
の透明石英ガラスを、例えば、米国特許第2,904,
713号、米国特許第3,128,166号、米国特許
第3,128,169号、米国特許第3,485,61
3号等に開示された方法により処理して、脈理を除去す
る必要がある。
The quartz glass manufactured by the CVD method is:
Due to the temperature change during the production, fluctuations in the density occur in the silica glass fine particle deposit on the heat-resistant substrate. However, since the fluctuations remain as striae after the vitrification, the transparent quartz usually produced by the CVD method is used. Glass generally has striae. However, in order to form an optical member such as a stepper lens, the stria must be removed. Therefore, in the present invention, the high-purity transparent quartz glass is used, for example, in US Pat.
No. 713, U.S. Pat. No. 3,128,166, U.S. Pat. No. 3,128,169, U.S. Pat. No. 3,485,61.
It is necessary to remove the striae by performing the treatment by the method disclosed in No. 3 or the like.

【0020】例えば、脈理のある棒状の透明石英ガラス
を旋盤で保持し、棒状の透明石英ガラスを局部にバーナ
ーもしくは電気加熱の方法で、少なくとも軟化点以上に
加熱し、旋盤を回転させ、脈理が消えるまで棒状の石英
ガラスを捻る方法がある。この方法においては、脈理を
除去する際に、棒状の石英ガラスの加熱位置を順次移動
することによって、最終的には棒状のガラス体全体が均
質化される。この際の加熱温度は、石英ガラスの軟化点
以上にすることが必要であり、例えば1600℃以上で
ある。もちろん、石英ガラス上の加熱位置の移動速度な
どは、処理する石英ガラス部材の形状や重さによって適
当に選択されるものである。
For example, a bar-shaped transparent quartz glass having a striae is held on a lathe, and the bar-shaped transparent quartz glass is locally heated by a burner or an electric heating method to at least a softening point or higher, and the lathe is rotated to rotate the lathe. There is a method of twisting the rod-shaped quartz glass until the reason disappears. In this method, when the stria is removed, the heating position of the rod-shaped quartz glass is sequentially moved, so that the entire rod-shaped glass body is finally homogenized. The heating temperature at this time needs to be higher than the softening point of the quartz glass, and is, for example, 1600 ° C. or higher. Of course, the moving speed of the heating position on the quartz glass and the like are appropriately selected depending on the shape and weight of the quartz glass member to be processed.

【0021】脈理が除去された透明石英ガラスは、次
に、最終的な製品、例えばステッパーレンズ等に使用す
るために適した形状、サイズに成形される。この成形
は、一般に、所望の形状のルツボ内に脈理を除去した透
明石英ガラスを入れ、これを加熱炉で少なくとも150
0℃以上に加熱し、石英ガラスの自重で成形する。この
場合、従来法と同様に、カーボン製のルツボが一般に使
用される。また、加熱炉も、従来法と同様に、カーボン
ヒータ仕様のものが使用される。このため、成形雰囲気
は、真空、もしくはHe,N2などの不活性ガス中で行
う。加熱温度、加熱時間などの条件は、所望する成形体
のサイズや形状に応じて適宜選択される。
The transparent quartz glass from which the stria has been removed is then formed into a shape and size suitable for use in a final product such as a stepper lens. This molding is generally carried out by placing a transparent quartz glass from which a stria has been removed in a crucible having a desired shape, and placing it in a heating furnace for at least 150 minutes.
It is heated to 0 ° C. or higher and formed by its own weight of quartz glass. In this case, as in the conventional method, a carbon crucible is generally used. As the heating furnace, a heating furnace having a carbon heater specification is used similarly to the conventional method. Therefore, the molding is performed in a vacuum or in an inert gas such as He or N 2 . Conditions such as the heating temperature and the heating time are appropriately selected according to the desired size and shape of the molded body.

【0022】一般的に光学材料は歪が5nm/cm以下
であることが要求されるので、本発明においては、成形
された透明石英ガラスは、その成形歪をアニール処理に
より除去することが必要である。この成形歪みの除去
は、成形された透明石英ガラスを、石英ガラスの歪点よ
りも高い温度まで加熱し、その後、該透明石英ガラスを
徐冷することにより行われる。
Generally, optical materials are required to have a strain of 5 nm / cm or less, so in the present invention, it is necessary to remove the forming strain of the formed transparent quartz glass by annealing. is there. The removal of the forming distortion is performed by heating the formed transparent quartz glass to a temperature higher than the strain point of the quartz glass, and then gradually cooling the transparent quartz glass.

【0023】一般に、合成石英ガラスの歪点は約102
5℃であるので、本発明においては、成形された透明石
英ガラスは、成形歪みをほぼ完全に除去させるために、
1100℃乃至1250℃の範囲内の温度まで加熱し、
徐冷される。徐冷はできるだけゆっくり行われるのが好
ましい。本発明においては、アニール処理は石英ガラス
中の屈折率分布の均一化にも貢献している。
Generally, the strain point of synthetic quartz glass is about 102
Since the temperature is 5 ° C., in the present invention, the molded transparent quartz glass is used to almost completely eliminate molding distortion.
Heating to a temperature in the range of 1100 ° C. to 1250 ° C.,
It is cooled slowly. Slow cooling is preferably performed as slowly as possible. In the present invention, the annealing treatment also contributes to making the refractive index distribution in the quartz glass uniform.

【0024】石英ガラスの屈折率は、主に、OH基や塩
素などの不純物含有量と仮想温度(fictive temperatu
re)により決定される。これらのうち、OH基は数10
ppm以下なので無視でき、その他の不純物も合成石英の
場合、実質的に無視することができるので、アニール処
理の際の仮想温度の設定が重要である。つまり、均一な
屈折率分布を得るためには、処理するガラス成形体全体
の仮想温度を均一にしなければならない。この為、一旦
徐冷点以上の温度に石英ガラスを加熱したのち、一定時
間その温度で保持してガラス内部の温度分布を均一に
し、その後できるだけゆっくりと降温する。これは、石
英ガラス全体で、できるだけ温度差を生じないようにす
るためである。この場合、もし、この降温スピードを速
くすると、石英ガラス中の任意の位置で温度差が生じ、
その結果、異なる仮想温度が設定され、均一な屈折率分
布が得られない。
The refractive index of quartz glass mainly depends on the content of impurities such as OH groups and chlorine and the fictive temperatu
re). Of these, OH groups are several tens
Since it is less than ppm, it can be neglected, and other impurities can be substantially neglected in the case of synthetic quartz. Therefore, it is important to set a virtual temperature at the time of annealing. That is, in order to obtain a uniform refractive index distribution, the virtual temperature of the entire glass molded article to be processed must be uniform. For this reason, once the quartz glass is heated to a temperature equal to or higher than the annealing point, the temperature is maintained at that temperature for a certain period of time to make the temperature distribution inside the glass uniform, and then the temperature is lowered as slowly as possible. This is for minimizing a temperature difference as much as possible in the entire quartz glass. In this case, if this cooling rate is increased, a temperature difference occurs at an arbitrary position in the quartz glass,
As a result, different virtual temperatures are set, and a uniform refractive index distribution cannot be obtained.

【0025】本発明においては、上記のアニール処理に
おける加熱温度は1200℃程度であり、加熱時間及び
降温スピードは処理する素材の大きさや形状を考慮し
て、適当に選ばれる。一般的に、大きな素材ほど加熱時
間を長くし、かつ、降温スピードを遅くするのが好まし
い。
In the present invention, the heating temperature in the above annealing treatment is about 1200 ° C., and the heating time and the temperature decreasing speed are appropriately selected in consideration of the size and shape of the material to be treated. Generally, it is preferable that the larger the material, the longer the heating time and the lower the temperature decreasing speed.

【0026】本発明においては、揮発性ケイ素化合物
を、酸水素炎により火炎加水分解し、生成する微粒子シ
リカを耐熱性基体上に堆積させてシリカガラスの多孔質
母材を製造し、該シリカガラスの多孔質母材を1×10
-2トール以上の高真空度で加熱して、透明な石英ガラス
を形成し、該透明石英ガラスを均質化処理することによ
り、少なくとも一方向、好ましくは三方向に脈理を有し
ない高均質石英ガラスを形成し、該高均質石英ガラスを
成形後アニール処理するので、得られる石英ガラス部材
は、紫外線照射によって生成する常磁性欠陥のもとにな
る固有欠陥、例えばSiOHや塩素などのその他の不純
物濃度が低減され、結果的に常磁性欠陥の生成は抑制さ
れる。
In the present invention, the volatile silicon compound is flame-hydrolyzed by an oxyhydrogen flame, and the resulting fine silica particles are deposited on a heat-resistant substrate to produce a porous silica glass preform. 1 × 10 porous base material
By heating at a high vacuum of -2 Torr or more to form a transparent quartz glass and homogenizing the transparent quartz glass, a highly homogeneous quartz having no striae in at least one direction, preferably three directions. Since the glass is formed and the highly homogeneous quartz glass is annealed after being formed, the resulting quartz glass member has inherent defects such as SiOH and chlorine, which are the source of paramagnetic defects generated by ultraviolet irradiation. The concentration is reduced, and as a result, generation of paramagnetic defects is suppressed.

【0027】以上のように本発明により製造されたエキ
シマレーザー用石英ガラス部材は、均質性がよく、か
つ、耐エキシマレーザー性に優れており、殊に、エキシ
マレーザーを光源とするステッパーレンズ用の石英ガラ
スとして好適であり、また、紫外線照射に伴う紫外線領
域の吸収の増加を抑制することができる。
As described above, the quartz glass member for excimer laser manufactured according to the present invention has good homogeneity and excellent excimer laser resistance, and is particularly useful for a stepper lens using an excimer laser as a light source. It is suitable as quartz glass and can suppress an increase in absorption in the ultraviolet region due to ultraviolet irradiation.

【0028】[0028]

【実施例】本発明の実施態様について、以下、例を挙げ
て説明するが、本発明は、以下の説明及び例示によっ
て、何等制限されるものではない。 例1.四塩化けい素を蒸留処理して不純物を除去した
後、これを原料として、CVD法で外形150mm,長
さ600mmの円柱状の多孔質石英ガラス母材を作製し
た。該多孔質石英ガラス母材を、カーボンヒーター仕様
の真空炉にいれ、10-5トールまで真空排気した。この
後、ヒーターを昇温し、母材を加熱した。加熱条件は8
00℃まで10℃/min.で、800〜1400℃で
は1℃/min.の昇温速度で加熱し、1400℃に達
した時点で加熱をストップし、自然冷却した。外径10
5mm,長さ550mmの円柱状の透明ガラス体が得ら
れた。得られた透明ガラス体のOH濃度は約25ppm
であった。
The embodiments of the present invention will be described below by way of examples, but the present invention is not limited by the following description and examples. Example 1 After removing impurities by distilling silicon tetrachloride, a cylindrical porous silica glass preform having an outer diameter of 150 mm and a length of 600 mm was prepared by using the raw material as a raw material by a CVD method. The porous quartz glass base material was placed in a vacuum furnace of a carbon heater specification and evacuated to 10 −5 Torr. Thereafter, the heater was heated to heat the base material. Heating condition is 8
10 ° C / min. At 800 to 1400 ° C., 1 ° C./min. , And when the temperature reached 1400 ° C., the heating was stopped and the product was naturally cooled. Outer diameter 10
A cylindrical transparent glass body having a length of 5 mm and a length of 550 mm was obtained. The OH concentration of the obtained transparent glass body is about 25 ppm
Met.

【0029】該円柱状透明ガラス体の両端に石英ガラス
製の支持棒を取り付け、旋盤のチャックに固定した。プ
ロパンガスバーナーにより、上記の多孔質石英母材より
作製した透明ガラス部分を加熱し、旋盤を回転させ、該
透明ガラス部分を捻った。この時の作業温度は、約20
00℃であった。捻られた透明ガラス部分には3方向に
は脈理は観測されなかった。しかるのち、該透明石英ガ
ラス部分を切り出し、カーボンヒーター仕様の加熱炉で
成形し、外径250mm,長さ75mmの円柱状の成形
体を得た。この時の成形温度は約1700℃で、窒素ガ
ス雰囲気中で行った。
A support rod made of quartz glass was attached to both ends of the columnar transparent glass body and fixed to a chuck of a lathe. The transparent glass portion produced from the porous quartz base material was heated by a propane gas burner, and the lathe was rotated to twist the transparent glass portion. The working temperature at this time is about 20
00 ° C. No striae were observed on the twisted transparent glass part in three directions. Thereafter, the transparent quartz glass portion was cut out and molded in a heating furnace of a carbon heater specification to obtain a cylindrical molded body having an outer diameter of 250 mm and a length of 75 mm. The molding temperature at this time was about 1700 ° C., and the molding was performed in a nitrogen gas atmosphere.

【0030】該成形体を歪み取りのためのアニール熱処
理を行った。熱処理条件は、1100℃まで昇温したの
ち、0.1℃/min.で600℃まで降温した。熱処
理は大気中の雰囲気で行った。得られたガラス体の複屈
折は2nm/cm以下であり、屈折率分布も実質上均一
であり、屈折率の最大値と最小値の差は1×10-6以下
であった。
The molded body was subjected to an annealing heat treatment for removing strain. The heat treatment conditions are as follows: after heating up to 1100 ° C., 0.1 ° C./min. To 600 ° C. The heat treatment was performed in an air atmosphere. The birefringence of the obtained glass body was 2 nm / cm or less, the refractive index distribution was substantially uniform, and the difference between the maximum value and the minimum value of the refractive index was 1 × 10 −6 or less.

【0031】紫外線照射に対する常磁性欠陥の生成を調
べるために、上記の透明石英ガラス成型体の一部を切り
出し、境面に研磨した10 × 10 × 40(mm)の
ガラス体に加工した。該石英ガラス体にArFレーザー
を照射し、193nmの光の透過率の変化を調べた。A
rFレーザーの照射条件は、エネルギー密度200mJ
/cm2・パルス、周波数100ヘルツで行った。図1
にArF照射パルス数に対する193nm吸収強度を示
した。なお、縦軸の吸収強度はサンプルの厚さ1cm当
りの吸光度(−Log(内部透過率))で示している。
In order to examine the generation of paramagnetic defects due to ultraviolet irradiation, a part of the above-mentioned transparent quartz glass molded body was cut out and processed into a 10 × 10 × 40 (mm) glass body having a polished boundary surface. The quartz glass body was irradiated with an ArF laser, and the change in the transmittance of light of 193 nm was examined. A
Irradiation condition of rF laser is energy density 200mJ
/ Cm 2 pulse at a frequency of 100 Hz. FIG.
Shows the 193 nm absorption intensity with respect to the number of ArF irradiation pulses. Note that the absorption intensity on the vertical axis is represented by the absorbance (-Log (internal transmittance)) per 1 cm thickness of the sample.

【0032】例2.四塩化けい素を蒸留処理して不純物
を除去した後、これを原料として、CVD法で外形70
mm、長さ600mmの円柱状の多孔質石英ガラス母材
を作製した。該多孔質石英ガラス母材を、カーボンヒー
ター仕様の真空炉にいれ、10-5トールまで真空排気し
た。この後、ヒーターを昇温し、母材を加熱した。加熱
条件は800℃まで10℃/min.で、800〜14
00℃では1℃/min.の昇温速度で加熱し、140
0℃に達した時点で加熱ストップし、自然冷却した。外
径50mm,長さ550mmの円柱状の透明ガラス体が
得られた。得られた透明ガラス体のOH濃度は約15p
pmであった。
Example 2 After removing impurities by distilling silicon tetrachloride, using the raw material as a raw material, the outer shape is reduced by a CVD method.
A columnar porous quartz glass base material having a length of 600 mm and a length of 600 mm was prepared. The porous quartz glass base material was placed in a vacuum furnace of a carbon heater specification and evacuated to 10 −5 Torr. Thereafter, the heater was heated to heat the base material. The heating condition is 10 ° C / min. And 800-14
At 00 ° C, 1 ° C / min. Heating at a heating rate of 140
When the temperature reached 0 ° C., the heating was stopped, and the mixture was naturally cooled. A cylindrical transparent glass body having an outer diameter of 50 mm and a length of 550 mm was obtained. The OH concentration of the obtained transparent glass body is about 15p
pm.

【0033】該円柱状透明ガラス体を同様の方法で均質
化し、しかるのち、該透明石英ガラス部分を切り出し、
カーボンヒーター仕様の加熱炉で成形し、外径120m
m、長さ80mmの円柱状の成形体を得た。この時の成
形温度は約1700℃で、窒素ガス雰囲気中で行った。
The columnar transparent glass body is homogenized by the same method, and thereafter, the transparent quartz glass portion is cut out.
Molded in a heating furnace of carbon heater specification, outer diameter 120m
m, a columnar molded body having a length of 80 mm was obtained. The molding temperature at this time was about 1700 ° C., and the molding was performed in a nitrogen gas atmosphere.

【0034】該成形体を歪み取りのためのアニール熱処
理を行った。熱処理条件は、1100℃まで昇温したの
ち、0.2℃/min.で600℃まで降温した。熱処
理は大気中の雰囲気で行った。得られたガラス体の複屈
折は、2nm/cm以下であり、屈折率分布も実質上均
一であり、屈折率の最大値と最小値の差は、0.8×1
-6であった。実施例1と同様の条件でArFレーザー
を照射し、結果をまとめて図1に示した。
The compact was subjected to an annealing heat treatment for removing strain. The heat treatment conditions were as follows: after the temperature was raised to 1100 ° C, 0.2 ° C / min. To 600 ° C. The heat treatment was performed in an air atmosphere. The birefringence of the obtained glass body is 2 nm / cm or less, the refractive index distribution is substantially uniform, and the difference between the maximum value and the minimum value of the refractive index is 0.8 × 1.
It was 0 -6 . An ArF laser was irradiated under the same conditions as in Example 1, and the results are summarized in FIG.

【0035】比較例1.上記実施例1の場合と同様にし
て作製した多孔質石英ガラス母材を、カーボン仕様の炉
にいれ、Heガス雰囲気中で透明ガラス化した。加熱条
件は、1600℃まで10℃/min.で昇温し、16
00℃に達した時点で加熱をストップし、自然冷却し
た。得られた透明ガラス体のOH濃度は約300ppm
であった。しかるのち、実施例1と同じ条件で、均質化
工程、成形工程、アニール工程の処理を施した。複屈折
及び屈折率分布は、実施例1の場合とほぼ同じであっ
た。実施例1と同様の条件でArFレーザーを照射し、
結果をまとめて図1に示した。
Comparative Example 1 The porous quartz glass preform prepared in the same manner as in Example 1 was placed in a furnace having a carbon specification, and vitrified in a He gas atmosphere. The heating condition is 10 ° C./min. The temperature is increased by 16
When the temperature reached 00 ° C., the heating was stopped and the product was naturally cooled. The OH concentration of the obtained transparent glass body is about 300 ppm
Met. Thereafter, under the same conditions as in Example 1, the processes of the homogenization step, the molding step, and the annealing step were performed. The birefringence and the refractive index distribution were almost the same as in Example 1. Irradiate ArF laser under the same conditions as in Example 1,
The results are summarized in FIG.

【0036】比較例2.一般的に用いられている光学用
の合成石英ガラスについて、上記実施例1と同様の条件
でArFレーザーを照射し、評価した。これは、四塩化
けい素を直接火炎加水分解法(酸素・水素火炎によるダ
イレクト法)により合成した石英ガラスである。このガ
ラスのOH濃度は約900ppmであった。この石英ガ
ラスに実施例1と同じ条件で、均質化工程、成形工程、
アニール工程の処理を施した。複屈折及び屈折率分布
は、実施例1の場合とほぼ同じであった。実施例1と同
様の条件でArFレーザーを照射し、結果をまとめて図
1に示した。
Comparative Example 2 The synthetic silica glass for optics generally used was evaluated by irradiating an ArF laser under the same conditions as in Example 1 above. This is quartz glass obtained by synthesizing silicon tetrachloride by a direct flame hydrolysis method (a direct method using an oxygen / hydrogen flame). The OH concentration of this glass was about 900 ppm. Homogenization step, molding step,
An annealing process was performed. The birefringence and the refractive index distribution were almost the same as in Example 1. An ArF laser was irradiated under the same conditions as in Example 1, and the results are summarized in FIG.

【0037】実施例1、2と比較例1、2では、複屈
折、及び屈折率分布は、ほぼ同じ値を示した。しかしな
がら、ArFレーザー照射に対する耐性は図1の結果に
示されるように、実施例1、2の場合、吸光度の増加
が、他の比較例1、2と較べて著しく抑制されているこ
とが判る。特に比較例2と較べた場合、実施例1、2の
吸光度の増加は約4分の1に抑制されている。これは、
ArFレーザー照射にともなって生成する常磁性欠陥の
生成量が低いこと、及び真空雰囲気での透明ガラス化処
理に依ってより紫外線の照射に対して安定なガラスが作
製できることを示している。
In Examples 1 and 2 and Comparative Examples 1 and 2, the birefringence and the refractive index distribution showed almost the same values. However, as shown in the results of FIG. 1, the resistance to ArF laser irradiation was found to be significantly reduced in Examples 1 and 2 as compared with Comparative Examples 1 and 2 in Examples 1 and 2. In particular, when compared with Comparative Example 2, the increase in absorbance of Examples 1 and 2 was suppressed to about one-fourth. this is,
This indicates that the amount of paramagnetic defects generated by ArF laser irradiation is low, and that a glass more stable to ultraviolet irradiation can be produced by vitrification in a vacuum atmosphere.

【0038】[0038]

【発明の効果】本発明においては、高純度四塩化けい素
等の高純度揮発性けい素化合物を、酸水素炎により火炎
加水分解し、この分解により生成する微粒子シリカを耐
熱性基体上に堆積させてシリカガラスの多孔質母材を製
造し、該シリカガラスの多孔質母材を1×10-2トール
以上の高真空度で加熱して、透明な石英ガラスを形成
し、該透明石英ガラスを均質化処理することにより、少
なくとも一方向に脈理を有しない高均質石英ガラスを形
成し、該高均質石英ガラスを成形後アニール処理するの
で、従来の製法によるエキシマレーザー用石英ガラス部
材と比較して、不純物の混入を極力抑えることができ、
かつ、ガラスの固有欠陥濃度の低いガラスを作成するこ
とができる。その結果、本発明によると、従来の方法に
比して、紫外線照射に対して、常磁性欠陥の生成を抑制
することができ、耐紫外線性の優れた石英ガラスが得ら
れる。
According to the present invention, a high-purity volatile silicon compound such as high-purity silicon tetrachloride is flame-hydrolyzed by an oxyhydrogen flame, and fine silica produced by the decomposition is deposited on a heat-resistant substrate. Then, a porous preform of silica glass is manufactured, and the porous preform of silica glass is heated at a high vacuum of 1 × 10 −2 torr or more to form transparent quartz glass. By forming a highly homogeneous quartz glass having no striae in at least one direction by performing homogenization treatment and annealing after forming the highly homogeneous quartz glass, it is compared with a quartz glass member for excimer laser by a conventional manufacturing method. As a result, contamination of impurities can be minimized,
In addition, glass having a low intrinsic defect concentration of glass can be produced. As a result, according to the present invention, it is possible to suppress the generation of paramagnetic defects with respect to ultraviolet irradiation as compared with the conventional method, and to obtain quartz glass having excellent ultraviolet resistance.

【図面の簡単な説明】[Brief description of the drawings]

【図1】本発明の実施例及び比較例におけるArFレー
ザ照射パルス数に対する193nmの光の吸収曲線を示
す図である。
FIG. 1 is a graph showing an absorption curve of 193 nm light with respect to the number of ArF laser irradiation pulses in Examples and Comparative Examples of the present invention.

───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6,DB名) C03B 20/00 C03B 8/04──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. 6 , DB name) C03B 20/00 C03B 8/04

Claims (4)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】 揮発性けい素化合物を、酸水素炎により
火炎加水分解し、生成する微粒子シリカを耐熱性基体上
に堆積させてシリカガラスの多孔質母材を製造し、該シ
リカガラスの多孔質母材を1×10-2トール以上の高真
空度で加熱して、透明な石英ガラスを形成し、該透明石
英ガラスを均質化処理することにより、少なくとも一方
向に脈理を有しない高均質石英ガラスを形成し、該高均
質石英ガラスを成形後アニール処理することを特徴とす
るエキシマレーザー用石英ガラス部材の製造方法。
1. A volatile silicon compound is flame-hydrolyzed by an oxyhydrogen flame, and the resulting fine silica particles are deposited on a heat-resistant substrate to produce a porous silica glass matrix. The transparent base material is heated at a high vacuum of 1 × 10 -2 torr or more to form a transparent quartz glass, and the transparent quartz glass is homogenized to obtain a high-strength material having no striae in at least one direction. A method for producing a quartz glass member for an excimer laser, comprising forming a homogeneous quartz glass, forming the highly homogeneous quartz glass, and performing an annealing treatment.
【請求項2】 石英ガラスの均質化処理が1600℃以
上の温度で行われることを特徴とする請求項1に記載の
エキシマレーザー用石英ガラス部材の製造方法。
2. The method for producing a quartz glass member for an excimer laser according to claim 1, wherein the homogenizing treatment of the quartz glass is performed at a temperature of 1600 ° C. or higher.
【請求項3】 高均質の石英ガラスの成形が1500℃
以上の温度で行われることを特徴とする請求項1に記載
のエキシマレーザー用石英ガラス部材の製造方法。
3. The molding of highly homogeneous quartz glass at 1500 ° C.
The method for producing a quartz glass member for an excimer laser according to claim 1, wherein the method is performed at the above temperature.
【請求項4】 アニール処理が800℃乃至1250℃
の温度範囲の温度下で行われることを特徴とする請求項
1に記載のエキシマレーザー用成形ガラス部材の製造方
法。
4. The annealing treatment is performed at 800 ° C. to 1250 ° C.
The method for producing a molded glass member for an excimer laser according to claim 1, wherein the method is performed at a temperature within a temperature range of:
JP3182858A 1991-06-29 1991-06-29 Method of manufacturing quartz glass member for excimer laser Expired - Lifetime JP2835540B2 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
JP3182858A JP2835540B2 (en) 1991-06-29 1991-06-29 Method of manufacturing quartz glass member for excimer laser
KR1019930700573A KR0165695B1 (en) 1991-06-29 1992-06-29 Synthetic quartz glass optical member for excimer laser and production thereof
EP92913798A EP0546196B1 (en) 1991-06-29 1992-06-29 Synthetic quartz glass optical member for excimer laser and production thereof
DE199292913798T DE546196T1 (en) 1991-06-29 1992-06-29 SYNTHETIC GLASS OPTICAL ELEMENT FOR EXCIMER LASER AND ITS PRODUCTION.
DE69219445T DE69219445T2 (en) 1991-06-29 1992-06-29 SYNTHETIC OPTICAL ELEMENT MADE OF QUARTZ GLASS FOR EXCIMER LASER AND ITS PRODUCTION
PCT/JP1992/000821 WO1993000307A1 (en) 1991-06-29 1992-06-29 Synthetic quartz glass optical member for excimer laser and production thereof
US07/977,397 US5364433A (en) 1991-06-29 1992-06-29 Optical member of synthetic quartz glass for excimer lasers and method for producing same
US08/286,538 US5523266A (en) 1991-06-29 1994-08-05 Optical member of synthetic quartz glass for excimer lasers and method for producing same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP3182858A JP2835540B2 (en) 1991-06-29 1991-06-29 Method of manufacturing quartz glass member for excimer laser

Publications (2)

Publication Number Publication Date
JPH05186234A JPH05186234A (en) 1993-07-27
JP2835540B2 true JP2835540B2 (en) 1998-12-14

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ID=16125684

Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Status (1)

Country Link
JP (1) JP2835540B2 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2248961T3 (en) * 1998-12-28 2006-03-16 PIRELLI & C. S.P.A. PROCEDURE FOR THE PRODUCTION OF SILICE BY DECOMPOSITION OF AN ORGANOLSILAN.
JP4541708B2 (en) * 2002-03-05 2010-09-08 コーニング インコーポレイテッド Optical member and method for predicting performance of optical member and optical system
JP4826118B2 (en) * 2005-03-29 2011-11-30 旭硝子株式会社 Method for producing synthetic quartz glass and synthetic quartz glass for optical member
US9067814B2 (en) * 2009-01-19 2015-06-30 Shin-Etsu Chemical Co., Ltd. Method of producing synthetic quartz glass for excimer laser
CN114249524A (en) * 2020-09-22 2022-03-29 中天科技精密材料有限公司 Low-hydroxyl high-purity quartz glass and preparation method thereof

Also Published As

Publication number Publication date
JPH05186234A (en) 1993-07-27

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