JP2007186347A - Method for producing silica-titania glass having no stria - Google Patents
Method for producing silica-titania glass having no stria Download PDFInfo
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- JP2007186347A JP2007186347A JP2005372535A JP2005372535A JP2007186347A JP 2007186347 A JP2007186347 A JP 2007186347A JP 2005372535 A JP2005372535 A JP 2005372535A JP 2005372535 A JP2005372535 A JP 2005372535A JP 2007186347 A JP2007186347 A JP 2007186347A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/14—Other methods of shaping glass by gas- or vapour- phase reaction processes
- C03B19/1453—Thermal after-treatment of the shaped article, e.g. dehydrating, consolidating, sintering
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/14—Other methods of shaping glass by gas- or vapour- phase reaction processes
- C03B19/1469—Means for changing or stabilising the shape or form of the shaped article or deposit
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B29/00—Reheating glass products for softening or fusing their surfaces; Fire-polishing; Fusing of margins
- C03B29/02—Reheating glass products for softening or fusing their surfaces; Fire-polishing; Fusing of margins in a discontinuous way
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- 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
- C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
- C03B2201/40—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with transition metals other than rare earth metals, e.g. Zr, Nb, Ta or Zn
- C03B2201/42—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with transition metals other than rare earth metals, e.g. Zr, Nb, Ta or Zn doped with titanium
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- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
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- Preparing Plates And Mask In Photomechanical Process (AREA)
Abstract
Description
本発明は、波長１３．５ｎｍの超短波長紫外線を光源とするＥＵＶリソグラフィー（Extreme Ultra-Violet Lithography）の反射光学系を構成するミラー基板や反射型マスクの基板に好適な均質で脈理のないチタニアを含有するシリカガラス（以下、チタニアを含有するシリカガラスをシリカ・チタニアガラスと称する）の製造方法及び一方向あるいは三方向に脈理の存在しないシリカ・チタニアガラスに関する。 The present invention is a homogeneous and striatile titania suitable for a mirror substrate or a reflective mask substrate constituting a reflection optical system of EUV lithography (Extreme Ultra-Violet Lithography) using an ultrashort wavelength ultraviolet ray having a wavelength of 13.5 nm as a light source. The present invention relates to a method for producing silica glass containing silica (hereinafter, silica glass containing titania is referred to as silica-titania glass) and silica-titania glass having no striae in one or three directions.
半導体素子の製造技術開発は留まることを知らないが、線幅が４５ｎｍよりも細い、次々世代の露光技術として、波長１３．５ｎｍのＥＵＶ光を用いたＥＵＶリソグラフィー技術が最も有力視されている。このような超短波長の光は適切な透過材料が存在しないため、光学系は全て反射系で構成され、また、マスク材料も反射型マスクが用いられると考えられている。 Although it is not known that development of manufacturing technology for semiconductor elements will remain, EUV lithography technology using EUV light with a wavelength of 13.5 nm is regarded as the most promising as a next-generation exposure technology whose line width is narrower than 45 nm. Since there is no appropriate transmission material for such ultrashort wavelength light, it is considered that the optical system is entirely composed of a reflection system, and that the mask material is a reflection type mask.
このような光学ミラー及びマスク基板の材料は露光操作中に熱膨張等で変形しては困るために、使用温度範囲での線膨張係数が極めて小さい超低膨張ガラスが必要とされる。また、これらの基板面はサブナノメーターのオーダーで平面もしくは球面、非球面に研磨できなければならない。このような超低膨張ガラスとしては、特許文献１に示されるようにＴｉＯ２濃度が６〜８質量％程度、残部がＳｉＯ２で構成されるシリカ・チタニアガラスが挙げられ、該シリカ・チタニアガラスは約２０〜３５℃の間で約±２０ｐｐｂ／℃の範囲の一様な線膨張係数を有する。 Since such optical mirror and mask substrate materials are difficult to be deformed by thermal expansion or the like during the exposure operation, ultra-low expansion glass having an extremely small linear expansion coefficient in the operating temperature range is required. In addition, these substrate surfaces must be able to be polished into a flat, spherical, or aspherical surface on the order of sub-nanometers. As such ultra-low expansion glass, as shown in Patent Document 1, silica-titania glass having a TiO 2 concentration of about 6 to 8% by mass and the balance being SiO 2 can be mentioned. Has a uniform coefficient of linear expansion between about 20-35 ° C. and in the range of about ± 20 ppb / ° C.
このようなシリカ・チタニアガラスを製造する方法としては、シリカ原料である揮発性珪素化合物（四塩化珪素や環状シロキサン等）とチタニア原料である揮発性チタン化合物（四塩化チタンやチタンアルコキシド）をバーナー火炎中に導入して、回転する基体上に、原料の火炎加水分解によって生じるシリカ微粒子とチタニア微粒子を同時に堆積、溶融して製造する直接法が一般的である。 As a method for producing such silica-titania glass, a volatile silicon compound (silicon tetrachloride, cyclic siloxane, etc.) as a silica raw material and a volatile titanium compound (titanium tetrachloride or titanium alkoxide) as a titania raw material are burners. A direct method is generally used in which silica fine particles and titania fine particles generated by flame hydrolysis of raw materials are simultaneously deposited and melted on a rotating substrate introduced into a flame.
この方法は所謂合成シリカガラスを製造する方法と同一であるが、得られるシリカ・チタニアガラスの高温での粘度がシリカガラスの粘度に比べて１０〜２０％低いため、得られるガラスを横向きに保持する横型直接法によって成長させることは困難で、下から上に徐々にガラスを成長させる縦型法が主たる方法である。このような縦型直接法によって製造されたシリカ・チタニアガラスはガラス成長中の基体の回転に伴う成長縞が層状の脈理を形成する。 This method is the same as the method for producing the so-called synthetic silica glass, but the obtained silica / titania glass has a viscosity at a high temperature of 10 to 20% lower than that of the silica glass, so that the obtained glass is held sideways. It is difficult to grow by the horizontal direct method, and the vertical method in which the glass is gradually grown from the bottom to the top is the main method. In the silica-titania glass manufactured by such a vertical direct method, the growth streaks accompanying the rotation of the substrate during glass growth form layered striae.
このような脈理部分においては、シリカ・チタニアの構成割合が微妙に変化するために線膨張係数が変化していると考えられる上、硬さも微妙に異なるため、高精度な研磨を施した場合、脈理部分だけ凹凸が出来るという不具合が生じ、ＥＵＶリソグラフィー用光学系に要求されるサブナノメーターオーダーの平坦面を形成するには甚だ不都合である。 In such striae, the linear expansion coefficient is considered to change due to a slight change in the composition ratio of silica and titania, and the hardness is also slightly different. However, there is a problem that only the striae are uneven, which is very inconvenient for forming a flat surface of the sub-nanometer order required for an optical system for EUV lithography.
このような不都合を解消するために特許文献２ではシリカ・チタニアガラス成長時の温度条件を極めて均一に設定し、存在する脈理を屈折率差で１０−７以下と極めて”薄く”することで解決しようとしているが、本発明は温度条件等を均一に成長させるのではなく、機械的に脈理を除去することによって完全に脈理を消滅させることを目的としている。 In order to eliminate such inconveniences, Patent Document 2 sets the temperature condition during the growth of silica / titania glass to be extremely uniform, and makes the existing striae extremely thin as 10 −7 or less in refractive index difference. Although it is going to solve, it is an object of the present invention to completely eliminate the striae by mechanically removing the striae, rather than uniformly growing temperature conditions and the like.
また、このような脈理は成長面に平行に形成されるものであるから、平面状に加工して使用される平面ミラーやマスク材料としては使用することが可能であると思われるが、実際には成長面は完全には平行ではなく、若干の凹凸を持った面であることが多く、そのような場合には、完全な平面を形成した場合に、凹凸部分が切り出され、脈理として観察され、不具合を生じることがある。
本発明は、シリカ・チタニアガラス基板においてＥＵＶリソグラフィー用の光学系に許されない脈理を一方向あるいは三方向に除去し、シリカ・チタニアガラスの均質性を向上させることができるシリカ・チタニアガラスの製造方法及び一方向あるいは三方向に脈理の存在しないシリカ・チタニアガラスを提供することを目的としている。 The present invention eliminates striae unacceptable for an optical system for EUV lithography in a silica-titania glass substrate in one or three directions, and produces silica-titania glass capable of improving the homogeneity of silica-titania glass. It is an object of the present invention to provide a method and a silica-titania glass having no striae in one or three directions.
シリカ・チタニアガラスの持つ脈理を完全に除去するために、発明者らが鋭意検討を加えた結果、脈理を有するシリカガラスの脈理除去、均質化手法である帯域溶融法（例えば、特許文献３に記載された方法）をシリカ・チタニアガラスの脈理方向に適切に施すことによって同様の結果が得られることを見出した。 In order to completely remove the striae of silica-titania glass, the inventors have made intensive investigations. As a result, striae removal of silica glass having striae, zone melting method (for example, patent) It has been found that the same results can be obtained by appropriately applying the method described in Document 3 in the striae direction of silica-titania glass.
即ち、本発明のシリカ・チタニアガラスの製造方法の第１の態様は、一方向に脈理のないシリカ・チタニアガラスの製造方法であって、層状の脈理を有するシリカ・チタニアガラス塊から、脈理と平行な面を有する棒状ガラス体を切り出す工程と、前記棒状ガラス体の両端部を一対の回転可能な保持手段で保持し、前記脈理と平行な軸と垂直な方向にせん断応力が作用するように帯域溶融法を適用して脈理を除去する均質化処理を施す均質化処理工程と、を含むことを特徴とする。 That is, the first aspect of the method for producing silica-titania glass of the present invention is a method for producing silica-titania glass having no striae in one direction, from a silica-titania glass lump having layered striae, A step of cutting a rod-shaped glass body having a plane parallel to the striae, and holding both ends of the rod-shaped glass body by a pair of rotatable holding means, and shear stress is applied in a direction perpendicular to the axis parallel to the striae And a homogenization process step of applying a zone melting method to remove the striae so as to work.
本発明のシリカ・チタニアガラスの製造方法の第２の態様は、一方向に脈理のないシリカ・チタニアガラスの製造方法であって、層状の脈理を有するシリカ・チタニアガラス塊から、長手方向に平行に脈理を有する角柱状の棒状ガラス体を切り出す切り出し工程と、前記棒状ガラス体の角部を面取りする面取り工程と、前記棒状ガラス体の長手方向の両端部を一対の回転可能な保持手段で保持し、バーナーで該ガラス体の一部を加熱しながら該一対の回転可能な保持手段に回転差を与えつつ該バーナーを移動して断面が略円形な棒状ガラス体に成型する第１の成型工程と、前記成型された棒状ガラス体の一部をバーナーで強熱しつつ、前記一対の回転可能な保持手段に大きな回転差を与えながらバーナーを移動させることにより該棒状ガラス体の長軸と垂直な方向にせん断応力を作用させて、脈理を除去し、組成の均一化を図る均質化処理工程と、を含むことを特徴とする。 The second aspect of the method for producing silica-titania glass of the present invention is a method for producing silica-titania glass having no striae in one direction, from a silica-titania glass lump having layered striae in the longitudinal direction. A cutting process for cutting out a prismatic rod-shaped glass body having striae parallel to the surface, a chamfering process for chamfering corners of the rod-shaped glass body, and a pair of rotatable holding portions at both ends in the longitudinal direction of the rod-shaped glass body The glass body is held by a means, and a part of the glass body is heated by a burner, and the burner is moved while giving a rotation difference to the pair of rotatable holding means to form a rod-shaped glass body having a substantially circular cross section. The rod-shaped glass by moving the burner while giving a large rotational difference to the pair of rotatable holding means while burning part of the molded rod-shaped glass body with a burner. The long axis direction perpendicular to the shear stress by the action of, to remove the striae, characterized in that it comprises a homogenization step uniformed composition, the.
前記均質化処理工程後、前記均質化された棒状ガラス体の一部をバーナーで強熱しつつ、前記一対の回転可能な保持手段間の距離を狭めることにより該棒状ガラス体の径を大きくする第２の成型工程を含むことが好ましい。 After the homogenization step, the diameter of the rod-shaped glass body is increased by reducing the distance between the pair of rotatable holding means while igniting a part of the homogenized rod-shaped glass body with a burner. 2 molding steps are preferably included.
前記棒状ガラス体を前記一対の回転可能な保持手段で保持する際、０〜９００℃における線膨張係数が０×１０−７／℃以上６×１０−７／℃以下のガラス支持棒を介して保持することが好適である。 When holding the rod-shaped glass body with the pair of rotatable holding means, through a glass support rod having a linear expansion coefficient at 0 to 900 ° C. of 0 × 10 −7 / ° C. or more and 6 × 10 −7 / ° C. or less. It is preferable to hold.
本発明のシリカ・チタニアガラスの製造方法の第３の態様は、三方向に脈理のないシリカ・チタニアガラスの製造方法であって、層状の脈理を有するシリカ・チタニアガラス塊から、脈理と平行な面を有する棒状ガラス体を切り出す工程と、前記棒状ガラス体の両端部を一対の回転可能な保持手段で保持し、前記脈理と平行な軸と垂直な方向にせん断応力が作用するように帯域溶融法を適用して脈理を除去する第１の均質化処理工程と、前記均質化処理後のガラス体に対し均質化処理軸の方向を変えて帯域溶融法による均質化処理を施す第２の均質化処理工程と、を含むことを特徴とする。前記第１の均質化処理工程における第１の均質化処理軸と前記第２の均質化処理工程における第２の均質化処理軸とが略直交していること、例えば、第１の均質化処理軸と第２の均質化処理軸との成す角が８０度以上１００度以下であることがより効率的である。 A third aspect of the method for producing silica-titania glass according to the present invention is a method for producing silica-titania glass having no striae in three directions, from a silica-titania glass lump having layered striae. A step of cutting a rod-shaped glass body having a plane parallel to the surface, and both ends of the rod-shaped glass body are held by a pair of rotatable holding means, and shear stress acts in a direction perpendicular to the axis parallel to the striae. In this way, the first homogenization processing step of removing the striae by applying the zone melting method, and the homogenization processing by the zone melting method by changing the direction of the homogenization processing axis with respect to the glass body after the homogenization processing And applying a second homogenization treatment step. The first homogenization processing axis in the first homogenization processing step and the second homogenization processing axis in the second homogenization processing step are substantially orthogonal, for example, the first homogenization processing It is more efficient that the angle formed by the axis and the second homogenization processing axis is not less than 80 degrees and not more than 100 degrees.
本発明のシリカ・チタニアガラスの製造方法の第４の態様は、三方向に脈理のないシリカ・チタニアガラスの製造方法であって、層状の脈理を有するシリカ・チタニアガラス塊から、長手方向に平行に脈理を有する角柱状の棒状ガラス体を切り出す切り出し工程と、前記棒状ガラス体の角部を面取りする面取り工程と、前記棒状ガラス体の長手方向の両端部を０〜９００℃における線膨張係数が０×１０−７／℃以上６×１０−７／℃以下であるガラス支持棒を介して一対の回転可能な保持手段で保持し、バーナーで該棒状ガラス体の一部を加熱しながら該一対の回転可能な保持手段に回転差を与えつつ該バーナーを移動して断面が略円形な棒状ガラス体に成型する第１の成型工程と、前記成型された棒状ガラス体の一部をバーナーで強熱しつつ、前記一対の回転可能な保持手段に大きな回転差を与えながら該バーナーを移動させることにより該棒状ガラス体の長軸と垂直な方向にせん断応力を作用させて、脈理を除去し、組成の均一化を図る第１の均質化処理工程と、前記均質化された棒状ガラス体の一部をバーナーで強熱しつつ、前記一対の回転可能な保持手段間の距離を狭めることにより該棒状ガラス体の径を大きくし、球状ガラス体に成型する第２の成型工程と、前記成型された球状ガラス体を前記ガラス支持棒から切り離し、略９０度回転したのち再度ガラス支持棒を取り付ける持ち替え工程と、前記持ち替えた球状ガラス体をバーナーで加熱しつつ前記一対の回転可能な保持手段の間隔を広げることにより延伸する延伸工程と、前記延伸したガラス体に対して、前記一対の回転可能な保持手段に回転差を与えながら、バーナーを移動し、該ガラス体全体を円筒状に成型する第３の成型工程と、前記得られた円筒状ガラス体の一部を強熱しつつ、前記一対の回転可能な保持手段に大きな回転差を与えながらバーナーを移動させることにより該ガラス体の長軸と垂直な方向にせん断応力を作用させて、脈理を除去し、組成の均一化を図る第２の均質化工程と、前記得られたガラス体を成型する第４の成型工程と、を含むことを特徴とする。なお、本発明において、球状とは、円球、楕円球及びそれらに類似する形状を含むものである。 The fourth aspect of the method for producing silica-titania glass of the present invention is a method for producing silica-titania glass having no striae in three directions, from a silica-titania glass lump having layered striae in the longitudinal direction. A step of cutting out a prismatic rod-shaped glass body having striae parallel to the surface, a chamfering process of chamfering corners of the rod-shaped glass body, and a line at 0 to 900 ° C. at both ends in the longitudinal direction of the rod-shaped glass body A glass support rod having an expansion coefficient of 0 × 10 −7 / ° C. or more and 6 × 10 −7 / ° C. or less is held by a pair of rotatable holding means, and a part of the rod-shaped glass body is heated by a burner. A first molding step of forming the rod-shaped glass body having a substantially circular cross section by moving the burner while giving a rotation difference to the pair of rotatable holding means, and a part of the molded rod-shaped glass body Burning with a burner While moving the burner while giving a large rotation difference to the pair of rotatable holding means, a shear stress is applied in a direction perpendicular to the long axis of the rod-shaped glass body, and the striae is removed. A first homogenization treatment step for homogenizing the glass, and reducing the distance between the pair of rotatable holding means while igniting a part of the homogenized rod-shaped glass body with a burner. A second molding step of increasing the diameter of the body and molding it into a spherical glass body; and a holding step of separating the molded spherical glass body from the glass support rod and rotating the glass support rod again after rotating approximately 90 degrees. A stretching step of stretching the held spherical glass body with a burner while widening the gap between the pair of rotatable holding means, and the stretching glass body with respect to the stretched glass body. While giving a rotation difference to the pair of rotatable holding means, the burner is moved, and a third forming step for forming the whole glass body into a cylindrical shape, and a part of the obtained cylindrical glass body is ignited. While moving the burner while giving a large rotation difference to the pair of rotatable holding means, the shear stress is applied in the direction perpendicular to the long axis of the glass body, the striae is removed, and the composition is uniform. Including a second homogenization step for achieving the above-mentioned and a fourth molding step for molding the obtained glass body. In the present invention, the term “spherical” includes a circular sphere, an elliptic sphere, and shapes similar to them.
本発明方法において、前記均質化処理を複数回繰り返すことが好ましい。 In the method of the present invention, the homogenization treatment is preferably repeated a plurality of times.
前記均質化処理工程において前記一対の回転可能な保持手段に大きな回転差を与える方法としては、前記一対の回転可能な保持手段を逆回転することが好適である。 As a method of giving a large rotation difference to the pair of rotatable holding means in the homogenization step, it is preferable to reversely rotate the pair of rotatable holding means.
前記シリカ・チタニアガラスの組成は、チタニア濃度が２質量％以上１５質量％以下で残部がＳｉＯ２であることが好ましい。 The silica-titania glass preferably has a titania concentration of 2% by mass to 15% by mass with the balance being SiO 2 .
前記均質化処理を施す棒状ガラス体の外径が、３０ｍｍ以上１５０ｍｍ以下であることが好ましい。 It is preferable that the outer diameter of the rod-shaped glass body subjected to the homogenization treatment is 30 mm or more and 150 mm or less.
前記一対の回転可能な保持手段としては、旋盤に設けられた左右のチャックを用いることができる。 As the pair of rotatable holding means, left and right chucks provided on a lathe can be used.
本発明のシリカ・チタニアガラスは、本発明方法により製造される一方向又は三方向に脈理のないシリカ・チタニアガラスであって、機械的に脈理が除去されてなることを特徴とする。 The silica-titania glass of the present invention is a silica-titania glass having no striae in one or three directions produced by the method of the present invention, and is characterized in that striae are mechanically removed.
本発明のシリカ・チタニアガラスは、ＥＵＶリソグラフィー用の反射光学材料又は反射型マスク材料として好適に用いられる。 The silica-titania glass of the present invention is suitably used as a reflective optical material or a reflective mask material for EUV lithography.
本発明によれば、ＥＵＶリソグラフィーの反射光学系を構成するミラー基板や反射型マスクの基板に好適な高均質で一方向又は三方向に脈理のないシリカ・チタニアガラスを得ることができる。 ADVANTAGE OF THE INVENTION According to this invention, the silica-titania glass which is suitable for the mirror substrate which comprises the reflective optical system of EUV lithography, and the board | substrate of a reflective mask, and has no striae in one direction or three directions can be obtained.
以下に本発明の実施の形態を添付図面に基づいて説明するが、図示例は例示的に示されるもので、本発明の技術思想から逸脱しない限り種々の変形が可能なことはいうまでもない。 DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below with reference to the accompanying drawings. However, the illustrated examples are illustrative only, and various modifications can be made without departing from the technical idea of the present invention. .
図１は、本発明の一方向に脈理のないシリカ・チタニアガラスの製造方法の手順の大略を示すフローチャートである。図２〜図８は本発明の一方向に脈理のないシリカ・チタニアガラスの製造方法の工程順の一例を原理的に示す概略説明図である。 FIG. 1 is a flowchart showing an outline of a procedure of a method for producing silica-titania glass having no striae in one direction of the present invention. 2 to 8 are schematic explanatory views showing in principle an example of the order of steps in a method for producing silica-titania glass having no striae in one direction of the present invention.
図１に示すように、層状の脈理を有するシリカ・チタニアガラス塊を準備する（ステップ１００）。該シリカ・チタニアガラス塊の形成方法は特に限定されず、公知の方法を適宜選択すればよい。例えば、シリカ原料である揮発性珪素化合物（四塩化珪素や環状シロキサン等）とチタニア原料である揮発性チタン化合物（四塩化チタンやチタンアルコキシド）をバーナー火炎中に導入して、回転する基体上に、原料の火炎加水分解によって生じるシリカ微粒子とチタニア微粒子を同時に堆積、溶融して製造する直接法により得ることができる。 As shown in FIG. 1, a silica-titania glass lump having a layered striae is prepared (step 100). The method for forming the silica-titania glass block is not particularly limited, and a known method may be selected as appropriate. For example, a volatile silicon compound (silicon tetrachloride, cyclic siloxane, etc.) that is a silica raw material and a volatile titanium compound (titanium tetrachloride or titanium alkoxide) that is a titania raw material are introduced into a burner flame and placed on a rotating substrate. The silica fine particles and titania fine particles generated by flame hydrolysis of the raw material can be simultaneously deposited and melted to obtain a direct method.
前記得られたシリカ・チタニアガラスの組成は特に限定されないが、チタニアとＳｉＯ２からなり、チタニア濃度は、好ましくは２質量％以上、より好ましくは４重量％以上、さらに好ましくは６質量％以上、好ましくは１５質量％以下、より好ましくは１３質量％以下、さらに好ましくは８質量％以下である。 The composition of the obtained silica-titania glass is not particularly limited, and is composed of titania and SiO 2. The titania concentration is preferably 2% by mass or more, more preferably 4% by weight or more, and further preferably 6% by mass or more. Preferably it is 15 mass% or less, More preferably, it is 13 mass% or less, More preferably, it is 8 mass% or less.
次に、前記層状の脈理を有するシリカ・チタニアガラス塊から、脈理と平行な面を有する棒状ガラス体を切り出す（ステップ１０２：切り出し工程）。図２は、ステップ１０２を原理的に示す概略説明図であり、１０は層状の脈理を有するシリカ・チタニアガラス塊、１１は脈理、１２は角柱状の棒状ガラス体である。棒状ガラス体の切り出し方法は、該棒状ガラス体が脈理と平行な面を有する状態であれば特に限定はないが、図２に示した如く、層状の脈理１１を有するシリカ・チタニアガラス塊１０から、長手方向に平行に脈理１１を有する角柱状、一般的には四角柱状の棒状ガラス体１２を切り出すことが好ましい。 Next, a rod-shaped glass body having a plane parallel to the striae is cut out from the silica-titania glass block having the layered striae (step 102: cutting step). FIG. 2 is a schematic explanatory diagram showing the principle of step 102, in which 10 is a silica-titania glass lump having a layered striae, 11 is a striae, and 12 is a rod-like rod-shaped glass body. The method for cutting out the rod-shaped glass body is not particularly limited as long as the rod-shaped glass body has a plane parallel to the striae, but as shown in FIG. 2, the silica-titania glass block having the layered striae 11 From 10, it is preferable to cut out a prismatic glass body 12 having a prismatic shape having striae 11 parallel to the longitudinal direction, generally a rectangular columnar shape.
前記切り出された棒状ガラス体に対し、脈理と平行な軸と垂直な方向にせん断応力が作用するように帯域溶融法を適用して脈理を除去する均質化処理を施すことにより、一方向に脈理のないシリカ・チタニアガラスを得ることができるが、具体的には、前記棒状ガラス体の角部を面取りし（ステップ１０４：面取り工程）、断面が略円形な棒状ガラス体に成型した後（ステップ１０６：第１の成型工程）、脈理を除去し、組成の均一化を図る一方向目の均質化処理を実施する（ステップ１０８：第１の均質化処理工程）ことが望ましい。 By applying a homogenization treatment to remove the striae by applying a zone melting method so that a shear stress acts in a direction perpendicular to an axis parallel to the striae on the cut rod-shaped glass body, one direction Silica-titania glass with no striae can be obtained, but specifically, the corners of the rod-shaped glass body are chamfered (step 104: chamfering step) and molded into a rod-shaped glass body having a substantially circular cross section. After (step 106: first molding process), it is desirable to remove the striae and perform a homogenization process in the first direction to make the composition uniform (step 108: first homogenization process).
図３は、ステップ１０４を原理的に示す概略説明図であり、１４は面取りされた棒状ガラス体を示す。図３に示した如く、面取り工程において、角柱状の棒状ガラス体１２の角面が面取りされる。なお、図３においては四角柱状のガラス体を八角柱状のガラス体に面取り加工した場合の例を示したが、面取り加工の形状は特に限定されるものではない。 FIG. 3 is a schematic explanatory view showing step 104 in principle, and 14 shows a chamfered rod-shaped glass body. As shown in FIG. 3, in the chamfering process, the square surface of the prismatic rod-shaped glass body 12 is chamfered. In addition, in FIG. 3, although the example at the time of carrying out the chamfering process of the square columnar glass body to the octagonal columnar glass body was shown, the shape of a chamfering process is not specifically limited.
図４は、ステップ１０６を原理的に示す概略説明図であり、（ａ）は成型工程で用いられる装置を含む概略説明図であり、（ｂ）はステップ１０６による棒状ガラス体の形状の変化を示す概略説明図である。図４に示した如く、前記面取りされた棒状ガラス体１４は、該棒状ガラス体１４の長手方向の両端部を一対の回転可能な保持手段、例えば、旋盤のチャック３２ａ，３２ｂで保持し、バーナー３４で該ガラス体１４の一部を加熱しながら該旋盤の左右のチャック３２ａ，３２ｂに回転差を与え、該棒状ガラス体１４を捻りながら該バーナー３４を移動することにより、断面が略円形な円筒状の棒状ガラス体１６に成型される。 4A and 4B are schematic explanatory views showing the principle of step 106, FIG. 4A is a schematic explanatory view including an apparatus used in the molding process, and FIG. 4B shows the change in the shape of the rod-shaped glass body by step 106. It is a schematic explanatory drawing shown. As shown in FIG. 4, the chamfered rod-shaped glass body 14 has both ends in the longitudinal direction of the rod-shaped glass body 14 held by a pair of rotatable holding means, for example, lathe chucks 32a and 32b. By rotating the burner 34 while twisting the rod-shaped glass body 14 by giving a rotational difference to the left and right chucks 32a, 32b of the lathe while heating a part of the glass body 14 at 34, the cross section is substantially circular. It is formed into a cylindrical rod-shaped glass body 16.
前記棒状ガラス体１４を旋盤のチャック３２ａ，３２ｂで保持する際、０〜９００℃における線膨張係数が０×１０−７／℃以上６×１０−７／℃以下のガラス支持棒３０を介して保持することが好ましい。本発明者らはシリカ・チタニアガラスに帯域溶融法による均質化処理を施す際、旋盤に把持する際の支持棒の線膨張係数が処理物であるシリカ・チタニアガラスの線膨張係数と大きく異なる場合、線膨張係数の不適合によりクラック等が生じることがある為、支持棒の材質についても検討を加えたが、クラックが生じない線膨張係数の範囲として、３．０×１０−７／℃±３．０×１０−７／℃の範囲、即ち、０．０×１０−７／℃以上６．０×１０−７／℃以下の線膨張係数の材料であることが必要であることを見出した。シリカガラスは線膨張係数が０℃〜９００℃の温度領域で５．０×１０−７／℃であるため、ガラス支持棒として特に好ましいものである。 When the rod-shaped glass body 14 is held by lathe chucks 32a and 32b, the glass support rod 30 has a linear expansion coefficient of 0 × 10 −7 / ° C. to 6 × 10 −7 / ° C. at 0 to 900 ° C. It is preferable to hold. When the present inventors perform homogenization processing by zone melting method on silica-titania glass, the linear expansion coefficient of the support rod when gripping on a lathe is greatly different from the linear expansion coefficient of the silica-titania glass being processed In addition, since cracks and the like may occur due to incompatibility of the linear expansion coefficient, the material of the support rod was also examined. However, the range of the linear expansion coefficient where no crack occurs is 3.0 × 10 −7 / ° C. ± 3 .0 × 10 -7 / ℃ range, i.e., it was found that it is necessary that the material of 0.0 × 10 -7 / ℃ least 6.0 × 10 -7 / ℃ less linear expansion coefficient . Silica glass has a linear expansion coefficient of 5.0 × 10 −7 / ° C. in the temperature range of 0 ° C. to 900 ° C., and therefore is particularly preferable as a glass support rod.
加えて、シリカ・チタニアガラスは粘度がシリカガラスよりも１０％程低いことから、帯域溶融法により均質化する際に、均質化径が細すぎると自重による変形が生じ、安定した溶融帯域の保持が困難であることが判った。従って、前記成型された円筒状のガラス体１６の外径を３０ｍｍ以上にすることが重要である。径を太くする場合は特別制限はないが、溶融帯域内に強いせん断応力を生じさせる為には径が太すぎる場合、旋盤のチャックのトルクが過大になりすぎて機械的に大掛かりになりすぎるため、径の最大値は１５０ｍｍ以下であることが好ましい。 In addition, silica-titania glass is about 10% lower in viscosity than silica glass, so when homogenizing by zone melting method, if the homogenized diameter is too thin, deformation will occur due to its own weight, maintaining a stable melting zone Proved difficult. Therefore, it is important that the outer diameter of the molded cylindrical glass body 16 is 30 mm or more. There is no special restriction when increasing the diameter, but if the diameter is too large to generate strong shear stress in the melting zone, the lathe chuck torque becomes excessively large and mechanically too large. The maximum value of the diameter is preferably 150 mm or less.
図５はステップ１０８を原理的に示す概略説明図である。図５に示した如く、前記成型された棒状ガラス体１６の一部をバーナー３４で強熱しつつ、前記左右のチャック３２ａ，３２ｂに大きな回転差を与えながらバーナー３４を移動させることにより該棒状ガラス体１６の長軸と垂直な方向にせん断応力を作用させて、脈理を除去し、組成の均一化を図る均質化処理が行われる。図５において、４２は均質化処理軸である。左右のチャック３２ａ，３２ｂに大きな回転差を与える方法としては、例えば、左右のチャック３２ａ，３２ｂを逆回転することが好適である。この均質化処理は１回以上行えばよいが、２回以上繰り返すことが脈理の除去及び組成の均一化により効果的である。 FIG. 5 is a schematic explanatory view showing step 108 in principle. As shown in FIG. 5, a part of the molded rod-shaped glass body 16 is heated by the burner 34, and the burner 34 is moved while giving a large rotational difference to the left and right chucks 32a, 32b. A homogenization process is performed in which shear stress is applied in a direction perpendicular to the long axis of the body 16 to remove striae and to make the composition uniform. In FIG. 5, reference numeral 42 denotes a homogenization processing axis. As a method of giving a large rotation difference to the left and right chucks 32a and 32b, for example, it is preferable to reversely rotate the left and right chucks 32a and 32b. This homogenization treatment may be performed once or more, but it is more effective to remove striae and make the composition uniform by repeating it twice or more.
前記均質化処理工程後、前記得られたガラス体を加熱しながら成型することにより、円筒状等、所望の形状に成型されたシリカ・チタニアガラス体を得ることができる。図６〜図８は均質化されたガラス体の成型方法の一例を示す概略説明図である。図６に示した如く、前記均質化された棒状ガラス体１８の一部をバーナー３４で強熱しつつ、前記旋盤の両チャック３２ａ，３２ｂ間の距離を狭めることにより、該棒状ガラス体１８の径を大きくし、球状ガラス体２０に成型した後（ステップ１１０：第２の成型工程）、前記成型された球状ガラス体２０を前記ガラス支持棒３０から切り離す。なお、図６においては球状ガラス体として円球状のガラス体を示したが、球状とは円球状のみならず、ラクビーボール型形状等の楕円球形状等の種々の球状形態をも含むものである。 After the homogenization treatment step, the obtained glass body is molded while being heated, whereby a silica / titania glass body molded into a desired shape such as a cylindrical shape can be obtained. 6 to 8 are schematic explanatory views showing an example of a method for forming a homogenized glass body. As shown in FIG. 6, the diameter of the rod-shaped glass body 18 is reduced by reducing the distance between the chucks 32a and 32b of the lathe while heating a part of the homogenized rod-shaped glass body 18 with a burner 34. Is formed into a spherical glass body 20 (step 110: second molding step), and the molded spherical glass body 20 is separated from the glass support rod 30. In FIG. 6, a spherical glass body is shown as the spherical glass body. However, the spherical shape includes not only a spherical shape but also various spherical shapes such as an elliptical spherical shape such as a rugby ball shape.
その後、成型炉３６内の成型用容器４０に前記切り出されたガラス体２０を設置し、加熱成型することにより、所望の形状に成型されたシリカ・チタニアガラス２２が得られる（ステップ１１２）。図７はステップ１１２を原理的に示す概略説明図であり、３６は成型炉、３８は加熱手段、４０は成型用容器である。図８は上記方法により得られた円盤状に成型されたシリカ・チタニアガラス２４の一例を示す模式図である。前記本発明方法により機械的に脈理が除去された一方向に脈理のないシリカ・チタニアガラスを製造することができる。 After that, the cut glass body 20 is placed in the molding container 40 in the molding furnace 36, and is heat-molded to obtain the silica / titania glass 22 molded into a desired shape (step 112). FIG. 7 is a schematic explanatory view showing step 112 in principle, 36 is a molding furnace, 38 is a heating means, and 40 is a molding container. FIG. 8 is a schematic view showing an example of a silica-titania glass 24 formed into a disk shape obtained by the above method. Silica-titania glass having no striae in one direction from which striae has been mechanically removed can be produced by the method of the present invention.
以下、本発明の三方向に脈理のないシリカ・チタニアガラスの製造方法について具体的に説明する。図９は、本発明の三方向に脈理のないシリカ・チタニアガラスの製造方法の手順の大略を示すフローチャートである。図１０〜図１２は本発明の三方向に脈理のないシリカ・チタニアガラスの製造方法の工程順の一例を原理的に示す概略説明図である。 Hereinafter, the method for producing silica-titania glass having no striae in the three directions of the present invention will be specifically described. FIG. 9 is a flowchart showing an outline of the procedure of the method for producing silica-titania glass having no striae in three directions according to the present invention. 10 to 12 are schematic explanatory views showing in principle an example of the order of steps in the method for producing silica-titania glass having no striae in three directions according to the present invention.
本発明の三方向に脈理のないシリカ・チタニアガラスの製造方法は、層状の脈理を有するシリカ・チタニアガラス塊から、脈理と平行な面を有する棒状ガラス体を切り出し、脈理と平行な軸と垂直な方向にせん断応力が作用するように帯域溶融法を適用して脈理を除去する均質化処理を、軸を変えて施すものである。 The method for producing a silica-titania glass having no striae in three directions according to the present invention cuts out a rod-like glass body having a plane parallel to the striae from a silica-titania glass lump having a layered striae, and is parallel to the striae. The homogenization treatment is performed by changing the axis to remove the striae by applying the zone melting method so that the shear stress acts in the direction perpendicular to the axis.
具体的には、図９に示した如く、層状の脈理を有するシリカ・チタニアガラス塊を準備し（ステップ２００）、該層状の脈理を有するシリカ・チタニアガラス塊から、脈理と平行な面を有する棒状ガラス体を切り出した後（ステップ２０２：切り出し工程）、該棒状ガラス体の角部を面取りし（ステップ２０４：面取り工程）、断面が略円形な棒状ガラス体に成型した後（ステップ２０６：第１の成型工程）、脈理を除去し、組成の均一化を図る一方向目の均質化処理を実施する（ステップ２０８：第１の均質化処理工程）。その後、均質化された棒状ガラス体を球状ガラス体に成型し（ステップ２１０：第２の成型工程）、軸を変えるように該球状ガラス体を持ち替えた後（ステップ２１２：持ち替え工程）、該球状ガラス体を加熱しながら延伸し（ステップ２１４：延伸工程）、円筒状のガラス体に成型した後（ステップ２１６）、再度、脈理を除去し、組成の均一化を図る三方向目の均質化処理を実施することにより（ステップ２１８：第２の均質化処理工程）、三方向に脈理のないシリカ・チタニアガラスを得ることができる。 Specifically, as shown in FIG. 9, a silica / titania glass lump having a layered striae is prepared (step 200), and the silica / titania glass lump having the layered striae is parallel to the striae. After cutting out the rod-shaped glass body having a surface (step 202: cutting-out process), the corners of the rod-shaped glass body are chamfered (step 204: chamfering process), and then molded into a rod-shaped glass body having a substantially circular cross section (step) 206: First molding step), the first-direction homogenization process is performed to remove the striae and make the composition uniform (step 208: first homogenization process step). Thereafter, the homogenized rod-shaped glass body is formed into a spherical glass body (step 210: second molding process), and the spherical glass body is changed so as to change the axis (step 212: holding process). The glass body is stretched while being heated (Step 214: Stretching process) and formed into a cylindrical glass body (Step 216), and then the striae is removed again to homogenize the third direction in order to make the composition uniform. By carrying out the treatment (step 218: second homogenization treatment step), a silica-titania glass having no striae in three directions can be obtained.
前記ステップ２００、２０２、２０４、２０６、２０８及び２１０はそれぞれ、一方向に脈理のないシリカ・チタニアガラスの製造方法において前述したステップ１００、１０２、１０４、１０６、１０８及び１１０と同様に行えばよい。 The steps 200, 202, 204, 206, 208 and 210 are respectively performed in the same manner as the steps 100, 102, 104, 106, 108 and 110 described above in the method for producing silica-titania glass having no striae in one direction. Good.
図１０はステップ２１２を原理的に示す概略説明図である。図１０に示した如く、前記成型された球状ガラス体２０を前記ガラス支持棒３０から切り離し、均質化処理軸が変わるように再度ガラス支持棒３０を取り付けることにより、該球状ガラス体２０が持ち替えられる。図１０において、４２ａは第１の均質化処理における均質化処理軸であり、４２ｂは第２の均質化処理における均質化処理軸である。 FIG. 10 is a schematic explanatory view showing step 212 in principle. As shown in FIG. 10, the spherical glass body 20 can be changed by separating the molded spherical glass body 20 from the glass support bar 30 and attaching the glass support bar 30 again so that the homogenization axis changes. . In FIG. 10, 42a is a homogenization processing axis in the first homogenization processing, and 42b is a homogenization processing axis in the second homogenization processing.
持ち替え方法は特に限定されず、軸を変えて均質化処理を施すことにより脈理除去が可能であるが、複数の均質化処理軸の交点において成す角を９０℃に近付けることにより効率を高めることができ、直交する軸に対して均質化処理を行うことが最も効率が良く好適である。具体的には、図１０に示した如く、ガラス支持棒３０から切り離した球状ガラス体２０を、略９０度、例えば、８０度〜１００度の範囲で回転させ、第１の均質化処理軸４２ａと第２の均質化処理軸４２ｂが略直交するように設置することが好ましい。 There is no particular limitation on the change-over method, but striae can be removed by changing the axis to perform homogenization, but the efficiency is improved by bringing the angle formed at the intersection of multiple homogenization axes close to 90 ° C. It is most efficient and preferable to perform a homogenization process on orthogonal axes. Specifically, as shown in FIG. 10, the spherical glass body 20 cut off from the glass support rod 30 is rotated by approximately 90 degrees, for example, in the range of 80 degrees to 100 degrees, and the first homogenization processing shaft 42a. And the second homogenization processing shaft 42b are preferably installed so as to be substantially orthogonal to each other.
図１１はステップ２１４を原理的に示す概略説明図である。図１１に示した如く、前記持ち替えた球状ガラス体２０をバーナー３４で加熱しつつ前記左右のチャック３２ａ，３２ｂ間隔を広げることによりガラス体２１が延伸される。 FIG. 11 is a schematic explanatory view showing step 214 in principle. As shown in FIG. 11, the glass body 21 is stretched by increasing the distance between the left and right chucks 32 a and 32 b while heating the held spherical glass body 20 with a burner 34.
図１２はステップ２１６を原理的に示す概略説明図である。図１２に示した如く、前記延伸したガラス体２１に対して、前記左右のチャック３２ａ，３２ｂの回転数に差分を与えながら、バーナー３４を移動することにより、該ガラス体全体が円筒状に成型され、断面が略円形な棒状ガラス体２３が得られる。 FIG. 12 is a schematic explanatory diagram showing step 216 in principle. As shown in FIG. 12, the entire glass body is formed into a cylindrical shape by moving the burner 34 while giving a difference in the number of rotations of the left and right chucks 32a and 32b with respect to the stretched glass body 21. Thus, a rod-shaped glass body 23 having a substantially circular cross section is obtained.
前記成型された棒状ガラス体２３に対し前記ステップ１０８と同様に均質化処理を施すことにより機械的に脈理が除去された三方向に脈理のないシリカ・チタニアガラスが製造される。図１０〜１２に示した如く、第２の均質化処理における軸４２ｂは第１の均質化処理における軸４２ａとは略直交していることが好ましい。
前記均質化されたガラス体を前記ステップ１１０及びステップ１１２と同様に成型処理することにより（ステップ２２０：第４の成型工程）、円筒状等、所望の形状に成型された三方向に脈理のないシリカ・チタニアガラスが得られる。
By applying a homogenization process to the molded rod-shaped glass body 23 in the same manner as in the step 108, silica-titania glass having no striae in three directions from which striae has been mechanically removed is manufactured. As shown in FIGS. 10-12, it is preferable that the axis | shaft 42b in a 2nd homogenization process is substantially orthogonal to the axis | shaft 42a in a 1st homogenization process.
The homogenized glass body is molded in the same manner as in Step 110 and Step 112 (Step 220: Fourth molding step), so that the three-dimensional striae are molded into a desired shape such as a cylindrical shape. Silica-titania glass is obtained.
前記本発明方法により製造される一方向又は三方向に脈理がないシリカ・チタニアガラスは、非常に均質性が高く且つ機械的に脈理を除去することによって脈理が完全に消滅しており、ＥＵＶリソグラフィー用の反射光学材料又は反射型マスク材料として特に好適である。 Silica-titania glass with no striae in one or three directions produced by the method of the present invention has very high homogeneity, and the striae has completely disappeared by mechanically removing the striae. It is particularly suitable as a reflective optical material or a reflective mask material for EUV lithography.
以下に実施例をあげて本発明をさらに具体的に説明するが、これらの実施例は例示的に示されるもので限定的に解釈されるべきでないことはいうまでもない。 The present invention will be described more specifically with reference to the following examples. However, it is needless to say that these examples are shown by way of illustration and should not be construed in a limited manner.
（実施例１）
四塩化珪素及び四塩化チタンを酸水素バーナー火炎中に導入し回転する皿状基体上に堆積、溶融して直径３００ｍｍ、厚さ４００ｍｍの円盤状シリカ・チタニアガラス塊を得た。なお、シリカ・チタニアガラスを成長する際の四塩化珪素と四塩化チタンの流量割合を調整して、得られるシリカ・チタニアガラスの組成をシリカ分９３質量％、チタニア分７質量％に調整した。円盤状シリカ・チタニアガラス塊の一部を切り出し、脈理構造を調べた結果、円盤の上下面にほぼ平行に０．２ｍｍの周期で層状の脈理が認められた。
Example 1
Silicon tetrachloride and titanium tetrachloride were introduced into an oxyhydrogen burner flame, deposited on a rotating dish-like substrate, and melted to obtain a disk-like silica-titania glass lump having a diameter of 300 mm and a thickness of 400 mm. The flow rate ratio of silicon tetrachloride and titanium tetrachloride when growing the silica / titania glass was adjusted to adjust the composition of the obtained silica / titania glass to 93 mass% for silica and 7 mass% for titania. A part of the disk-like silica / titania glass lump was cut out and the striae structure was examined. As a result, layered striae were observed at a period of 0.2 mm substantially parallel to the upper and lower surfaces of the disk.
この円盤状シリカ・チタニアガラス塊を一辺が内寸５００ｍｍの角型の成型用容器（グラファイト製）内に入れ、全体を１８００℃に加熱して５００ｍｍ×５００ｍｍ×１１０ｍｍの方形状のガラス塊に成型した。得られたシリカ・チタニアガラス塊からサンプルを切り出し、脈理構造を観察したが、ガラス塊の上下面に平行で周期０．１２ｍｍ〜０．１８ｍｍの層状の脈理を認めた。図１４は、円盤の上下面に垂直な面から切り出したサンプル（縦約６ｃｍ×横約４ｃｍ×厚さ１ｃｍ）に対する、後述するシュリーレン装置を用いた脈理のシュリーレン像の観察結果を示す写真である。 This disc-like silica / titania glass lump is placed in a square-shaped molding container (made of graphite) with an inner dimension of 500 mm, and the whole is heated to 1800 ° C. and molded into a rectangular glass lump of 500 mm × 500 mm × 110 mm. did. A sample was cut out from the obtained silica-titania glass lump, and the striae structure was observed, but layered striae parallel to the upper and lower surfaces of the glass lump and having a period of 0.12 mm to 0.18 mm were observed. FIG. 14 is a photograph showing observation results of a schlieren image of striae using a schlieren apparatus described later on a sample (vertical approximately 6 cm × horizontal approximately 4 cm × thickness 1 cm) cut from a surface perpendicular to the upper and lower surfaces of the disk. is there.
この方形状のシリカ・チタニアガラス塊から層状の脈理面と平行な面を有するように８０ｍｍ×８０ｍｍ×５００ｍｍの四角柱状のガラス体を切り出した（切り出し工程）。この四角柱状のガラス体の断面正方形の各頂点に相当する角部４箇所を２０ｍｍずつ面取りを行い、８角形の角柱状に加工した（面取り工程）。 A square columnar glass body of 80 mm × 80 mm × 500 mm was cut out from the rectangular silica-titania glass lump so as to have a plane parallel to the layered striae (cutting step). The four corners corresponding to the apexes of each square of the square columnar glass body were chamfered by 20 mm and processed into an octagonal prism (chamfering step).
前記加工したシリカ・チタニアガラス体の両端に線膨張係数５×１０−７／℃のシリカガラスロッド支持棒を溶接し、支持棒を介して旋盤の両チャックに固定した。旋盤の両チャックを同期させつつ２０ｒｐｍで回転させ、支持棒とシリカ・チタニアガラス体の左側の溶接部分近傍を酸水素バーナーで強熱して、シリカ・チタニアガラス体が溶解した事を確認してから、旋盤の右側のチャックの回転数を４０ｒｐｍに上げ、両チャック間の回転数に差動を与え、角柱状のシリカ・チタニアガラス体をゆっくりと捻ることにより円柱状に成型しつつ、バーナーを１０ｍｍ／分の速度で右側に移動させガラス体全体を捻ることでガラス体全体を直径約φ８０ｍｍの円筒状に成型した（第１の成型工程）。尚、この場合、両チャックの回転方向は同じである。 A silica glass rod support rod having a linear expansion coefficient of 5 × 10 −7 / ° C. was welded to both ends of the processed silica / titania glass body, and fixed to both chucks of the lathe via the support rod. Rotate both lathe chucks at 20 rpm while synchronizing them, and ignite the vicinity of the left side of the support rod and the silica / titania glass body with an oxyhydrogen burner to confirm that the silica / titania glass body was dissolved. Increase the rotation speed of the chuck on the right side of the lathe to 40 rpm, give a differential to the rotation speed between both chucks, and slowly turn the prismatic silica-titania glass body into a cylindrical shape, while the burner is 10 mm The entire glass body was formed into a cylindrical shape with a diameter of about 80 mm by moving the glass body to the right side at a speed of / min (first molding step). In this case, the rotation directions of both chucks are the same.
シリカ・チタニアガラス体の成型が終了した後は左右のチャックの回転数を５０ｒｐｍで同期させて回転しつつ、シリカ・チタニアガラス体の左端にバーナーを戻し、強熱して溶融帯域を形成した。溶融帯域が形成されたことを確認した後、右側の旋盤のチャックの回転を左側のチャックの回転方向と逆回転、６０ｒｐｍで回転させ、強いせん断応力を与えて溶融帯域内を攪拌した。同時にバーナーを右方に１０ｍｍ／分のゆっくりとした速度で移動させる事により溶融帯域を移動させ、シリカ・チタニアガラス体全体の均質化を行った（一方向目の均質化処理）。同様の操作で同方向に再度均質化処理を施し、合計２回の均質化処理を行った。 After completion of the molding of the silica / titania glass body, the burner was returned to the left end of the silica / titania glass body while rotating the left and right chucks at 50 rpm in synchronism with each other and ignited to form a melting zone. After confirming that the melting zone was formed, the rotation of the chuck on the right lathe was rotated at 60 rpm opposite to the rotation direction of the left chuck, and a strong shear stress was applied to stir the melting zone. At the same time, the melting zone was moved by moving the burner to the right at a slow speed of 10 mm / min to homogenize the entire silica-titania glass body (homogenization treatment in the first direction). The homogenization process was again performed in the same direction by the same operation, and the homogenization process was performed twice in total.
前記均質化処理後、両チャックの回転方向を揃え、かつ５０ｒｐｍで同期させて回転させ、バーナーをシリカ・チタニアガラス体の左端に戻し強熱して溶融した。シリカ・チタニアガラス体が溶融したことを確認した後、右側の旋盤のチャックをゆっくりと押し狭めてシリカ・チタニアガラス体を押し潰し、直径約１７０ｍｍの球状に成型した（第２の成型工程）。 After the homogenization treatment, the rotation directions of both chucks were aligned and rotated synchronously at 50 rpm, and the burner was returned to the left end of the silica-titania glass body and ignited to melt. After confirming that the silica-titania glass body was melted, the chuck of the right lathe was slowly pushed and narrowed to crush the silica-titania glass body and molded into a spherical shape having a diameter of about 170 mm (second molding step).
前記成型工程を経た球状のガラス体の両端を支持棒から切り離し、一方の切断面を下にして内径φ２００ｍｍの成型用容器（グラファイト製円筒容器）内に入れ、成型用容器ごと真空炉内に設置し１８００℃にて１０分加熱して（成型用容器内での成型工程）、直径２００ｍｍ、厚さ８０ｍｍのシリカ・チタニアガラス円盤を得た。 Both ends of the spherical glass body that has undergone the molding process are cut off from the support rod, placed in a molding container (graphite cylindrical container) with an inner diameter of φ200 mm with one cut surface down, and the molding container is installed in a vacuum furnace. Then, it was heated at 1800 ° C. for 10 minutes (molding step in a molding container) to obtain a silica / titania glass disk having a diameter of 200 mm and a thickness of 80 mm.
得られた円盤の上下面に対して平行な面及び垂直な面からサンプルを切り出し平行平板に研磨して後、シュリーレン装置（溝尻光学製SCHLIEREN COMPACT 150）によって脈理観察を行った。図１３は、サンプルの切り出し方法を示す概略説明図であり、４２は均質化処理軸、４４は平行面から切り出されたサンプル、４６は垂直面から切り出されたサンプルをそれぞれ示す。平行面から切り出したサンプル（直径約６ｃｍ×厚さ１ｃｍ）に対しては均質化処理軸方向のシュリーレン像を観察し、垂直面から切り出されたサンプル（縦約６ｃｍ×横約４ｃｍ×厚さ１ｃｍ）に対しては均質化処理軸と垂直方向のシュリーレン像を観察した。 A sample was cut out from a plane parallel to the upper and lower surfaces of the obtained disk and a plane perpendicular to the disk, polished to a parallel plate, and then subjected to striae observation using a Schlieren apparatus (SCHLIEREN COMPACT 150, manufactured by Mizoji Optic). FIG. 13 is a schematic explanatory view showing a sample cutting method, in which 42 indicates a homogenization processing axis, 44 indicates a sample cut from a parallel plane, and 46 indicates a sample cut from a vertical plane. For a sample cut out from a parallel plane (diameter about 6 cm × thickness 1 cm), a schlieren image in the homogenization axis direction was observed, and a sample cut out from a vertical plane (about 6 cm long × about 4 cm wide × 1 cm thick) ), A Schlieren image perpendicular to the homogenization axis was observed.
図１５は、平行面から切り出したサンプルの結果を示す写真である。図１５に示した如く、上面のサンプルでは脈理は認められなかったが、垂直面から切り出したサンプルにおいては弱い脈理が観察され（図示せず）、一方向に脈理がない状態であった。なお、一般的に光学ガラスにおける脈理の測定には米軍軍事規格であるMIL-G-174が適用される。即ち、ピンホールから出る光をコリメートレンズで平行光にし、サンプルを照射し、その像を集光レンズで絞り込み、その焦点位置で目視観察する方法であるが、シュリーレン装置による脈理観察はより簡便にこの方法と同等の精度の測定が行えるため、普及している方法である。 FIG. 15 is a photograph showing the result of a sample cut out from a parallel plane. As shown in FIG. 15, no striae was observed in the upper surface sample, but weak striae was observed in the sample cut from the vertical surface (not shown), and there was no striae in one direction. It was. In general, MIL-G-174, which is a US military standard, is applied to measure striae in optical glass. In other words, the light emitted from the pinhole is collimated by a collimator lens, irradiated with a sample, the image is narrowed down by a condenser lens, and visually observed at the focal position, but striae observation with a Schlieren device is easier. In addition, this method is widely used because it can measure with the same accuracy as this method.
また、チタニア濃度が２、６、及び１５質量％であり残部がＳｉＯ２であるシリカ・チタニアガラス塊をそれぞれ作製し、実施例１と同様に一方向の均質化処理を行ったところ、実施例１と同様に一方向に脈理のないシリカ・チタニアガラスが得られることを確認した。 Moreover, when titania concentration 2,6, and the balance is 15 mass% is prepared with different silica-titania glass gob is SiO 2, was subjected to homogenization treatment in one direction in the same manner as in Example 1, Example As in 1, it was confirmed that silica-titania glass having no striae in one direction was obtained.
（実施例２）
実施例１と同じ方法でシリカ分９３質量％、チタニア分７質量％の円盤状シリカ・チタニアガラス塊を作製し、方形状のシリカ・チタニアガラス塊に成型した。このシリカ・チタニアガラス塊を実施例１と同様の方法で、切り出し工程、面取り工程、第１の成型工程、及び２回の一方向目の均質化処理工程（第１の均質化処理工程）を実施した。
(Example 2)
A disk-like silica / titania glass lump having a silica content of 93% by mass and a titania content of 7% by mass was prepared in the same manner as in Example 1, and molded into a square silica / titania glass lump. The silica / titania glass lump is cut out in the same manner as in Example 1, the chamfering step, the chamfering step, the first molding step, and the second homogenization treatment step (first homogenization treatment step). Carried out.
均質化処理後、両チャックの回転方向を揃え、かつ５０ｒｐｍで同期させて回転させ、バーナーをシリカ・チタニアガラス体の左端に戻し強熱して溶融した。シリカ・チタニアガラス体が溶融したことを確認した後、右側の旋盤のチャックをゆっくりと押し狭めてシリカ・チタニアガラス体を押し潰し、直径約１７０ｍｍの球状に成型した（第２の成型工程）。 After the homogenization treatment, the rotation directions of both chucks were aligned and rotated synchronously at 50 rpm, and the burner was returned to the left end of the silica-titania glass body and ignited to melt. After confirming that the silica-titania glass body was melted, the chuck of the right lathe was slowly pushed and narrowed to crush the silica-titania glass body and molded into a spherical shape having a diameter of about 170 mm (second molding step).
切り離した球状シリカ・チタニアガラス体の一方の端面を下にして台上に置き、ガラス体の両側面に再度支持棒を溶接した。切り離したガラス体の両端を結ぶ軸が第１の均質化処理の軸であるから、新たに溶接した両支持棒を繋ぐ軸は第１の均質化の軸と直交していることになる（持ち替え工程）。両支持棒によりガラス体全体を同期させて２０ｒｐｍで回転させながらバーナー火炎でガラス体全体を強加熱し、ガラス体全体を溶融した。ガラス体全体が溶融したことを確認した後、旋盤の両チャックを引き離し、ガラス体を延伸した（延伸工程）。 One end face of the separated spherical silica / titania glass body was placed on a table with the end face down, and support rods were welded again to both side faces of the glass body. Since the axis connecting both ends of the separated glass body is the axis of the first homogenization treatment, the axis connecting the newly welded support rods is perpendicular to the axis of the first homogenization. Process). The entire glass body was strongly heated with a burner flame while rotating the glass body in synchronism with both support bars at 20 rpm, and the entire glass body was melted. After confirming that the entire glass body was melted, both chucks of the lathe were separated to stretch the glass body (stretching step).
延伸した形の不揃いなシリカ・チタニアガラス体を前記第１の成型工程と同様の操作で直径約φ７０ｍｍの円筒状のシリカ・チタニアガラス体に成型した（第３の成型工程）。このシリカ・チタニアガラス体に対し第１の均質化処理と同様の操作で均質化処理を施した（第２の均質化処理工程）。この場合の均質化処理における軸は第１の均質化処理における軸とは直交している。 The stretched irregularly shaped silica / titania glass body was molded into a cylindrical silica / titania glass body having a diameter of about 70 mm by the same operation as in the first molding process (third molding process). The silica / titania glass body was subjected to a homogenization treatment by the same operation as the first homogenization treatment (second homogenization treatment step). The axis in the homogenization process in this case is orthogonal to the axis in the first homogenization process.
第２の均質化処理を終えたシリカ・チタニアガラス体を前記第２の成型工程と同様の操作で球状に成型した後、実施例１の成型用容器内での成型工程と同様の操作により真空炉内で円盤状に成型した（第４の成型工程）。得られたシリカ・チタニアガラス円盤はカットロスもあって実施例１よりは小さく、直径φ２００ｍｍ、厚さ７０ｍｍであった。 The silica-titania glass body that has been subjected to the second homogenization treatment is formed into a spherical shape by the same operation as in the second forming step, and then vacuumed by the same operation as the forming step in the forming container of Example 1. It was molded into a disk shape in the furnace (fourth molding step). The obtained silica-titania glass disk had a cut loss and was smaller than that of Example 1, and had a diameter of 200 mm and a thickness of 70 mm.
得られたシリカ・チタニアガラス円盤から実施例１と同様に平行面及び垂直面からサンプルを切り出し、平行平板に研磨してシュリーレン装置にて脈理観察を行った結果、どちらのサンプルについても脈理を認めず、３方向に脈理がない状態であった。平行面及び垂直面から切り出したサンプルの結果を図１６及び図１７にそれぞれ示す。なお、実施例２において図１３に示したサンプルの均質化処理軸４２は第２の均質化処理における軸である。 Samples were cut out from the parallel and vertical surfaces of the resulting silica-titania glass disk in the same manner as in Example 1, polished to parallel flat plates, and subjected to striae observation with a schlieren apparatus. As a result, both samples were striae. Was not observed, and there was no striae in three directions. The results of the samples cut out from the parallel plane and the vertical plane are shown in FIGS. 16 and 17, respectively. In Example 2, the sample homogenization processing axis 42 shown in FIG. 13 is an axis in the second homogenization processing.
また、チタニア濃度が２、６、８及び１５質量％であり残部がＳｉＯ２であるシリカ・チタニアガラス塊をそれぞれ作製し、実施例２と同様に均質化処理を行ったところ、実施例２と同様に三方向に脈理のないシリカ・チタニアガラスが得られることを確認した。 In addition, silica / titania glass ingots having titania concentrations of 2, 6, 8, and 15% by mass and the balance being SiO 2 were respectively prepared and subjected to homogenization treatment in the same manner as in Example 2. Similarly, it was confirmed that silica-titania glass having no striae in three directions was obtained.
１０：シリカ・チタニアガラス塊、１１：脈理、１２：角柱状の棒状ガラス体、１４：面取りされた棒状ガラス体、１６：成型された棒状ガラス体、１８：均質化されたガラス体、２０：球状ガラス体、２１：延伸されたガラス体、２２：成型されたシリカ・チタニアガラス、２３：成型された棒状ガラス体、２４：円盤状のシリカ・チタニアガラス、３０：ガラス支持棒、３２ａ，３２ｂ：チャック、３４：バーナー、３６：成型炉、３８：過熱手段、４０：成型用容器、４２：均質化処理軸、４２ａ：第１の均質化処理軸、４２ｂ：第２の均質化処理軸、４４：平行面から切り出したサンプル、４６：垂直面から切り出したサンプル。 10: Silica-titania glass lump, 11: Striae, 12: prismatic rod-shaped glass body, 14: chamfered rod-shaped glass body, 16: molded rod-shaped glass body, 18: homogenized glass body, 20 : Spherical glass body, 21: stretched glass body, 22: molded silica-titania glass, 23: molded rod-shaped glass body, 24: disk-shaped silica-titania glass, 30: glass support rod, 32a, 32b: chuck, 34: burner, 36: molding furnace, 38: superheating means, 40: container for molding, 42: homogenization processing axis, 42a: first homogenization processing axis, 42b: second homogenization processing axis 44: Sample cut out from parallel plane, 46: Sample cut out from vertical plane.
Claims (13)
層状の脈理を有するシリカ・チタニアガラス塊から、脈理と平行な面を有する棒状ガラス体を切り出す工程と、
前記棒状ガラス体の両端部を一対の回転可能な保持手段で保持し、前記脈理と平行な軸と垂直な方向にせん断応力が作用するように帯域溶融法を適用して脈理を除去する均質化処理を施す均質化処理工程と、を含むことを特徴とするシリカ・チタニアガラスの製造方法。 A method for producing silica-titania glass having no striae in one direction,
A step of cutting a rod-shaped glass body having a plane parallel to the striae from a silica-titania glass lump having layered striae;
Both ends of the rod-shaped glass body are held by a pair of rotatable holding means, and the striae is removed by applying a zone melting method so that shear stress acts in a direction perpendicular to the axis parallel to the striae. And a homogenization treatment step for performing a homogenization treatment. A method for producing silica-titania glass, comprising:
層状の脈理を有するシリカ・チタニアガラス塊から、長手方向に平行に脈理を有する角柱状の棒状ガラス体を切り出す切り出し工程と、
前記棒状ガラス体の角部を面取りする面取り工程と、
前記棒状ガラス体の長手方向の両端部を一対の回転可能な保持手段で保持し、バーナーで該ガラス体の一部を加熱しながら該一対の回転可能な保持手段に回転差を与えつつ該バーナーを移動して断面が略円形な棒状ガラス体に成型する第１の成型工程と、
前記成型された棒状ガラス体の一部をバーナーで強熱しつつ、前記一対の回転可能な保持手段に大きな回転差を与えながらバーナーを移動させることにより該棒状ガラス体の長軸と垂直な方向にせん断応力を作用させて、脈理を除去し、組成の均一化を図る均質化処理工程と、を含むことを特徴とするシリカ・チタニアガラスの製造方法。 A method for producing silica-titania glass having no striae in one direction,
Cutting out a prismatic rod-shaped glass body having striae parallel to the longitudinal direction from a silica-titania glass lump having layered striae,
A chamfering step of chamfering a corner of the rod-shaped glass body;
Both ends of the rod-shaped glass body in the longitudinal direction are held by a pair of rotatable holding means, and the burner is heated while a part of the glass body is heated by a burner while giving a rotation difference to the pair of rotatable holding means. A first molding step in which a rod-shaped glass body having a substantially circular cross section is moved,
While burning a part of the molded rod-shaped glass body with a burner, moving the burner while giving a large rotation difference to the pair of rotatable holding means, in a direction perpendicular to the long axis of the rod-shaped glass body And a homogenization treatment step for applying a shear stress to remove striae and to make the composition uniform. A method for producing silica-titania glass, comprising:
層状の脈理を有するシリカ・チタニアガラス塊から、脈理と平行な面を有する棒状ガラス体を切り出す工程と、
前記棒状ガラス体の両端部を一対の回転可能な保持手段で保持し、前記脈理と平行な軸と垂直な方向にせん断応力が作用するように帯域溶融法を適用して脈理を除去する均質化処理を施す第１の均質化処理工程と、
前記均質化処理後のガラス体に対し均質化処理軸を変えて帯域溶融法による均質化処理を施す第２の均質化処理工程と、を含むことを特徴とするシリカ・チタニアガラスの製造方法。 A method for producing silica-titania glass with no striae in three directions,
A step of cutting a rod-shaped glass body having a plane parallel to the striae from a silica-titania glass lump having layered striae;
Both ends of the rod-shaped glass body are held by a pair of rotatable holding means, and the striae is removed by applying a zone melting method so that shear stress acts in a direction perpendicular to the axis parallel to the striae. A first homogenization process for applying a homogenization process;
A second homogenization treatment step of subjecting the glass body after the homogenization treatment to a homogenization treatment by a zone melting method while changing the homogenization treatment axis, and a method for producing silica-titania glass.
層状の脈理を有するシリカ・チタニアガラス塊から、長手方向に平行に脈理を有する角柱状の棒状ガラス体を切り出す切り出し工程と、
前記棒状ガラス体の角部を面取りする面取り工程と、
前記棒状ガラス体の長手方向の両端部を０〜９００℃における線膨張係数が０×１０−７／℃以上６×１０−７／℃以下であるガラス支持棒を介して一対の回転可能な保持手段で保持し、バーナーで該棒状ガラス体の一部を加熱しながら該一対の回転可能な保持手段に回転差を与えつつ該バーナーを移動して断面が略円形な棒状ガラス体に成型する第１の成型工程と、
前記成型された棒状ガラス体の一部をバーナーで強熱しつつ、前記一対の回転可能な保持手段に大きな回転差を与えながら該バーナーを移動させることにより該棒状ガラス体の長軸と垂直な方向にせん断応力を作用させて、脈理を除去し、組成の均一化を図る第１の均質化処理工程と、
前記均質化された棒状ガラス体の一部をバーナーで強熱しつつ、前記一対の回転可能な保持手段間の距離を狭めることにより該棒状ガラス体の径を大きくし、球状ガラス体に成型する第２の成型工程と、
前記成型された球状ガラス体を前記ガラス支持棒から切り離し、略９０度回転したのち再度ガラス支持棒を取り付ける持ち替え工程と、
前記持ち替えた球状ガラス体をバーナーで加熱しつつ前記一対の回転可能な保持手段の間隔を広げることにより延伸する延伸工程と、
前記延伸したガラス体に対して、前記一対の回転可能な保持手段に回転差を与えながら、バーナーを移動し、該ガラス体全体を円筒状に成型する第３の成型工程と、
前記得られた円筒状ガラス体の一部を強熱しつつ、前記一対の回転可能な保持手段に大きな回転差を与えながらバーナーを移動させることにより該ガラス体の長軸と垂直な方向にせん断応力を作用させて、脈理を除去し、組成の均一化を図る第２の均質化処理工程と、
前記得られたガラス体の一部をバーナーで加熱しつつ円筒状に成型する第４の成型工程と、を含むことを特徴とするシリカ・チタニアガラスの製造方法。 A method for producing silica-titania glass with no striae in three directions,
Cutting out a prismatic rod-shaped glass body having striae parallel to the longitudinal direction from a silica-titania glass lump having layered striae,
A chamfering step of chamfering a corner of the rod-shaped glass body;
A pair of rotatable holdings at both ends in the longitudinal direction of the rod-shaped glass body through glass support rods having a linear expansion coefficient of 0 × 10 −7 / ° C. to 6 × 10 −7 / ° C. at 0 to 900 ° C. And a part of the rod-shaped glass body is heated by the burner, and the burner is moved to form a rod-shaped glass body having a substantially circular cross section while giving a rotation difference to the pair of rotatable holding means. 1 molding process,
A direction perpendicular to the long axis of the rod-shaped glass body by moving the burner while giving a large rotational difference to the pair of rotatable holding means while burning a part of the molded rod-shaped glass body with a burner A first homogenization treatment step for applying a shear stress to remove striae and homogenizing the composition;
A part of the homogenized rod-shaped glass body is ignited with a burner, and the diameter of the rod-shaped glass body is increased by narrowing the distance between the pair of rotatable holding means, and molded into a spherical glass body. 2 molding processes;
Detach the molded spherical glass body from the glass support bar, a rotation step of attaching the glass support bar again after rotating approximately 90 degrees,
A stretching step of stretching the heated spherical glass body with a burner while widening the gap between the pair of rotatable holding means,
A third molding step of moving the burner while forming a rotational difference between the pair of rotatable holding means with respect to the stretched glass body, and molding the entire glass body into a cylindrical shape;
Shear stress in a direction perpendicular to the long axis of the glass body by moving a burner while giving a large rotation difference to the pair of rotatable holding means while igniting a part of the obtained cylindrical glass body A second homogenization treatment step for removing the striae and achieving a uniform composition;
A fourth molding step of molding a part of the obtained glass body into a cylindrical shape while heating with a burner, and a method for producing silica-titania glass.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006327885A (en) * | 2005-05-27 | 2006-12-07 | Nikon Corp | Molding method of quartz glass and quartz glass |
| JP2014160237A (en) * | 2013-01-22 | 2014-09-04 | Shin Etsu Chem Co Ltd | Member for euv lithography, method for producing the same and titania-doped quartz glass |
| WO2023075975A1 (en) * | 2021-10-26 | 2023-05-04 | Corning Incorporated | Methods and apparatuses for homogenizing glass workpieces |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07267662A (en) * | 1994-03-26 | 1995-10-17 | Shinetsu Quartz Prod Co Ltd | Synthetic quartz glass molding for optical use and its production |
| WO2004092082A1 (en) * | 2003-04-11 | 2004-10-28 | Nikon Corporation | METHOD FOR PRODUCING SiO2-TiO2 BASED GLASS, SiO2-TiO2 BASED GLASS AND EXPOSURE SYSTEM |
| JP2004315351A (en) * | 2003-04-03 | 2004-11-11 | Asahi Glass Co Ltd | SILICA GLASS CONTAINING TiO2 AND OPTICAL MEMBER FOR EUV LITHOGRAPHY |
-
2005
- 2005-12-26 JP JP2005372535A patent/JP4568225B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07267662A (en) * | 1994-03-26 | 1995-10-17 | Shinetsu Quartz Prod Co Ltd | Synthetic quartz glass molding for optical use and its production |
| JP2004315351A (en) * | 2003-04-03 | 2004-11-11 | Asahi Glass Co Ltd | SILICA GLASS CONTAINING TiO2 AND OPTICAL MEMBER FOR EUV LITHOGRAPHY |
| WO2004092082A1 (en) * | 2003-04-11 | 2004-10-28 | Nikon Corporation | METHOD FOR PRODUCING SiO2-TiO2 BASED GLASS, SiO2-TiO2 BASED GLASS AND EXPOSURE SYSTEM |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006327885A (en) * | 2005-05-27 | 2006-12-07 | Nikon Corp | Molding method of quartz glass and quartz glass |
| JP2014160237A (en) * | 2013-01-22 | 2014-09-04 | Shin Etsu Chem Co Ltd | Member for euv lithography, method for producing the same and titania-doped quartz glass |
| EP2757078B1 (en) * | 2013-01-22 | 2020-03-11 | Shin-Etsu Chemical Co., Ltd. | Euv lithography member, making method, and titania-doped quartz glass |
| WO2023075975A1 (en) * | 2021-10-26 | 2023-05-04 | Corning Incorporated | Methods and apparatuses for homogenizing glass workpieces |
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