JP2008247661A - Method for manufacturing titania-silica glass - Google Patents

Method for manufacturing titania-silica glass Download PDF

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JP2008247661A
JP2008247661A JP2007090355A JP2007090355A JP2008247661A JP 2008247661 A JP2008247661 A JP 2008247661A JP 2007090355 A JP2007090355 A JP 2007090355A JP 2007090355 A JP2007090355 A JP 2007090355A JP 2008247661 A JP2008247661 A JP 2008247661A
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titania
hollow cylindrical
silica glass
glass
plate
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Masanobu Ezaki
正信 江崎
Shinji Kawabata
真司 河端
Sachiko Kato
幸子 加藤
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Coorstek KK
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Covalent Materials Corp
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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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B23/00—Re-forming shaped glass
    • C03B23/04—Re-forming tubes or rods
    • C03B23/051—Re-forming tubes or rods by gravity, e.g. sagging
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
    • Y02P40/57—Improving the yield, e-g- reduction of reject rates

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Preparing Plates And Mask In Photomechanical Process (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Glass Melting And Manufacturing (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing titania-silica glass which is excellent in uniformity of titania concentration in a face direction of a substrate such as a mask or a mirror, has improved uniformity of striae, and can be suitably used as an optical member such as a photomask or mirror material for extreme ultraviolet lithography. <P>SOLUTION: The method for manufacturing the titania-silica glass includes: a process for preparing a columnar sintered compact 1 by heat treating a titania-silica-based soot containing titania in an amount of 0.1-10 wt.%; a process for obtaining a hollow cylindrical body by grinding the outer periphery of the columnar sintered compact 1 and boring the central part of the resulting columnar sintered compact 1 in the axis direction; a process for forming a hollow cylindrical body with a slit 2 by forming the slit 2 in the axis direction of the hollow cylindrical body; and a process for obtaining a plate-like glass body 3 by heat treating the hollow cylindrical body with the slit 2 to make it into transparent glass having a plate-like form. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は、チタニアを含むシリカガラスに関し、特に、半導体・液晶等の製造工程において、超紫外光（Extreme Ultra Violet；以下、ＥＵＶと略称する）リソグラフィ用のフォトマスクまたはミラー材等の光学用部材に好適に用いられるチタニア−シリカガラスの製造方法に関する。   The present invention relates to silica glass containing titania, and in particular, an optical member such as a photomask or mirror material for extreme ultra violet (Extreme Ultra Violet; hereinafter abbreviated as EUV) lithography in the manufacturing process of semiconductors, liquid crystals and the like. It is related with the manufacturing method of the titania-silica glass used suitably for.

近年の半導体集積回路の高集積化において、微細加工技術は、最も重要な役割を担っている。半導体集積回路のさらなる微細化に伴い、光リソグラフィ技術の開発も進んでおり、その一つとして、露光光源にＥＵＶを用いたＥＵＶリソグラフィが注目されている。
このＥＵＶは、波長が１３．５ｎｍ以下であり、あらゆる材料に吸収されるため、反射光学系のリソグラフィシステムが採用されている。 The microfabrication technology plays the most important role in the recent high integration of semiconductor integrated circuits. With further miniaturization of semiconductor integrated circuits, development of optical lithography technology is also progressing. As one of them, EUV lithography using EUV as an exposure light source has attracted attention.
Since this EUV has a wavelength of 13.5 nm or less and is absorbed by any material, a reflection optical lithography system is employed.

ＥＵＶリソグラフィにおいては、フォトマスク基板には、高出力レーザが照射されるため、サブナノメーターオーダーでの熱的安定性が要求される。
したがって、フォトマスク基板の材料としては、従来のフォトリソグラフィに用いられていたシリカガラスよりも、低熱膨張のガラスが必要となる。 In EUV lithography, since the photomask substrate is irradiated with a high-power laser, thermal stability in the sub-nanometer order is required.
Therefore, as a material for the photomask substrate, a glass having a low thermal expansion is required as compared with silica glass used in conventional photolithography.

このような低熱膨張ガラスとしては、例えば、チタニア−シリカガラスが知られている。
このチタニア−シリカガラスの製造方法としては、シリカ前駆体とチタニア前駆体とを蒸気形態として混合したものをバーナーにて酸水素火炎中で加水分解し、回転するターゲット上にチタニア−シリカガラス粒子を堆積させると同時に溶融して製造する、いわゆるＶＡＤ（Vapor-phase Axial Deposition；気相軸付け）法が一般的であった。 For example, titania-silica glass is known as such a low thermal expansion glass.
As a method for producing this titania-silica glass, a mixture of a silica precursor and a titania precursor in a vapor form is hydrolyzed in an oxyhydrogen flame with a burner, and titania-silica glass particles are placed on a rotating target. The so-called VAD (Vapor-phase Axial Deposition) method, which is produced by melting at the same time as depositing, is common.

このＶＡＤ法で製造されたチタニア−シリカガラスは、成長時の回転軸対称にチタニア濃度が不均一な部分が生じやすく、ガラスの成長に伴って形成された成長縞が脈理となる。
また、研磨処理等を施し、フォトマスク基板に加工した際、この脈理に起因した凹凸が基板表面に生じやすくなり、サブナノメーターオーダーでの高度な平坦度が要求されるＥＵＶリソグラフィ用のフォトマスク基板にとって、不都合であった。 In the titania-silica glass manufactured by this VAD method, a portion where the titania concentration is non-uniform is apt to be generated symmetrically with respect to the rotational axis during growth, and the growth stripes formed with the growth of the glass are striae.
In addition, when processed into a photomask substrate after polishing, etc., unevenness due to this striae is likely to occur on the substrate surface, and a photomask for EUV lithography that requires high flatness on the order of sub-nanometers. It was inconvenient for the substrate.

これに対しては、例えば、特許文献１に、ＶＡＤ法で作製したチタニア−シリカガラス体の外周部の濃度不均質部分を除去してから、加熱変形させて成型する方法が開示されている。
特開２００６−２４０９７８号公報 In response to this, for example, Patent Document 1 discloses a method in which a non-uniform concentration portion of an outer peripheral portion of a titania-silica glass body produced by a VAD method is removed and then molded by heating and deforming.
JP 2006-240978 A

しかしながら、上記特許文献１に記載されているような製造方法によっても、成長時の回転軸対称に生じるチタニア濃度のバラツキを完全に解消することは原理的に困難であり、脈理がフォトマスク基板等の板状体の面方向とほぼ平行に存在する状態となるような脈理均質性を有するチタニア−シリカガラスを得ることはできなかった。   However, even with the manufacturing method described in Patent Document 1, it is theoretically difficult to completely eliminate the variation in titania concentration that occurs symmetrically with respect to the rotational axis during growth. It was not possible to obtain titania-silica glass having striae homogeneity that would be in a state of being substantially parallel to the plane direction of the plate-like body.

本発明は、上記技術的課題を解決するためになされたものであり、マスクやミラー等の基板の面方向におけるチタニア濃度の均一性に優れ、脈理の均質性の向上が図られ、ＥＵＶリソグラフィ用のフォトマスクまたはミラー材等の光学用部材として好適に用いることができるチタニア−シリカガラスを製造する方法を提供することを目的とするものである。   The present invention has been made to solve the above technical problem, and is excellent in uniformity of titania concentration in the surface direction of a substrate such as a mask or a mirror, improving the uniformity of striae, and EUV lithography. It is an object of the present invention to provide a method for producing titania-silica glass that can be suitably used as an optical member such as a photomask or a mirror material.

本発明に係るチタニア−シリカガラスの製造方法は、チタニア０．１〜１０重量％を含むチタニア−シリカ質スートを熱処理して、円柱状焼結体を作製する工程と、前記円柱状焼結体の外周面を研削し、かつ、中央部を軸方向に刳り抜き、中空円筒状体とする工程と、前記中空円筒状体の軸方向にスリットを形成し、スリット入り中空円筒状体とする工程と、前記スリット入り中空円筒状体を熱処理して、透明ガラス化および板状化させ、板状ガラス体とする工程とを備えていることを特徴とする。
上記製造方法によれば、チタニア濃度のバラツキよる板状ガラスの面方向における脈理の乱れ、不均質性が抑制されたチタニア−シリカガラスが得られる。 The method for producing a titania-silica glass according to the present invention includes a step of heat-treating titania-siliceous soot containing 0.1 to 10% by weight of titania to produce a cylindrical sintered body, and the cylindrical sintered body. Grinding the outer peripheral surface and rolling out the central portion in the axial direction to form a hollow cylindrical body, and forming a slit in the axial direction of the hollow cylindrical body to obtain a hollow cylindrical body with slits And a step of heat-treating the hollow cylindrical body with slits into a transparent glass and a plate to form a plate-like glass body.
According to the said manufacturing method, the titania-silica glass by which the disorder of the striae in the surface direction of the plate-like glass by the variation of titania density | concentration and the heterogeneity was suppressed was obtained.

本発明においては、前記チタニア−シリカ質スートは、ＯＶＤ（Outside Vapor Deposition；外付け）法により形成されることが好ましい。
ＯＶＤ法は、後の工程で形成される中空円筒状体における脈理方向を、軸を中心とした径方向に均質な年輪状にすることができることから、より好適なスート形成方法である。 In the present invention, the titania-siliceous soot is preferably formed by an OVD (Outside Vapor Deposition) method.
The OVD method is a more suitable soot forming method because the striae direction in the hollow cylindrical body formed in the subsequent step can be made into an annual ring shape that is homogeneous in the radial direction around the axis.

また、前記円柱状焼結体作製工程における熱処理は、より気泡の少ない透明なチタニア−シリカガラスを得るため、ゾーンシンター方式により行われることが好ましい。   In addition, the heat treatment in the columnar sintered body production step is preferably performed by a zone sintering method in order to obtain a transparent titania-silica glass with fewer bubbles.

さらに、前記板状ガラス体形成工程における熱処理は、伝導伝熱方式により行われることが好ましい。
伝導伝熱方式によれば、スリット入り中空円筒状体の焼結体内部にまでガラス化に十分な熱が伝わり、板状ガラス体の面方向における脈理の乱れを生じることなく、無気泡の透明なチタニア−シリカガラスを得ることができる。 Furthermore, it is preferable that the heat treatment in the plate glass body forming step is performed by a conductive heat transfer method.
According to the conduction heat transfer method, heat sufficient for vitrification is transmitted to the inside of the sintered body of the hollow cylindrical body with slits, and there is no bubble without causing disturbance of striae in the surface direction of the plate-like glass body. A transparent titania-silica glass can be obtained.

上述したとおり、本発明に係るチタニア−シリカガラスの製造方法によれば、チタニア濃度の面方向における均一性に優れ、脈理の均質性の向上が図られたチタニア−シリカガラスが得られる。
したがって、本発明に係る方法により製造されたチタニア−シリカガラスは、フォトマスクまたはミラー材等の光学用部材として好適に用いることができ、特に、半導体・液晶等の製造工程におけるＥＵＶリソグラフィにおいて、好適に使用することができ、ひいては、半導体・液晶等の各種処理工程における歩留の向上に寄与し得る。 As described above, according to the method for producing titania-silica glass according to the present invention, a titania-silica glass excellent in uniformity of titania concentration in the surface direction and improved in striae homogeneity can be obtained.
Therefore, the titania-silica glass produced by the method according to the present invention can be suitably used as an optical member such as a photomask or a mirror material, and is particularly suitable for EUV lithography in the production process of semiconductors and liquid crystals. Therefore, it can contribute to the improvement of the yield in various processing steps such as semiconductor and liquid crystal.

以下、本発明について、より詳細に説明する。
本発明に係るチタニア−シリカガラスの製造方法は、チタニア−シリカ質スートからの円柱状焼結体作製工程、中空円筒状体形成工程、スリット入り中空円筒状体形成工程、熱処理による板状ガラス体形成工程を経ることを特徴とするものである。
上記のような製造方法によれば、ＶＡＤ法等における成長時の回転軸対称に生じるチタニア濃度のバラツキよるチタニア−シリカガラスの板状面方向における脈理の乱れ、不均質性を抑制することができる。 Hereinafter, the present invention will be described in more detail.
The method for producing titania-silica glass according to the present invention includes a cylindrical sintered body preparation step from a titania-silica soot, a hollow cylindrical body formation step, a hollow cylindrical body formation step with slits, and a plate-like glass body by heat treatment. It is characterized by undergoing a forming process.
According to the manufacturing method as described above, it is possible to suppress disturbance of striae and inhomogeneity in the direction of the titania-silica glass plate surface due to variations in titania concentration generated symmetrically with the rotation axis during growth in the VAD method or the like. it can.

以下、上記本発明に係る製造方法について、工程順に説明する。
まず、円柱状焼結体の前駆体となるチタニア−シリカ質スートは、既知の方法により形成することができ、具体的には、ＶＡＤ法、ＭＣＶＤ（Modified Chemical Vapor Deposition；内付けＣＶＤ）法、ＯＶＤ法等がある。 Hereinafter, the manufacturing method according to the present invention will be described in the order of steps.
First, titania-siliceous soot as a precursor of a cylindrical sintered body can be formed by a known method, specifically, a VAD method, an MCVD (Modified Chemical Vapor Deposition) method, There is an OVD method.

これらの方法の中でも、本発明においては、ＯＶＤ法を用いることが好ましい。ＯＶＤ法を用いた円柱状焼結体の作製においては、例えば、回転するシリカガラス製中空軸の外周に、チタニア−シリカ質スートを所望の径になるまで外付けした後、熱処理することにより、中空軸を含む状態の円柱状焼結体として得られる。
このようなＯＶＤ法を用いて作製された円柱状焼結体は、これに研削加工等を施して、中空円筒状体とする際、該中空円筒状体における脈理方向を、軸を中心とした径方向に均質な年輪状にすることができるため好ましい。 Among these methods, the OVD method is preferably used in the present invention. In the production of a cylindrical sintered body using the OVD method, for example, by externally attaching titania-siliceous soot to a desired diameter on the outer periphery of a rotating silica glass hollow shaft, by heat treatment, It is obtained as a columnar sintered body including a hollow shaft.
When the cylindrical sintered body produced by using such an OVD method is subjected to grinding or the like to obtain a hollow cylindrical body, the striae direction in the hollow cylindrical body is centered on the axis. It is preferable because it can be formed into a ring shape that is homogeneous in the radial direction.

また、前記スートの熱処理は、ゾーンシンター方式により行われることが好ましい。
このような加熱方式を採用することにより、焼結体中の細孔を、ほとんど残存させることなく除去することができ、より気泡の少ない透明なチタニア−シリカガラスを得ることができる。 The soot heat treatment is preferably performed by a zone sintering method.
By adopting such a heating method, the pores in the sintered body can be removed with almost no remaining, and a transparent titania-silica glass with fewer bubbles can be obtained.

前記チタニア−シリカ質スートのチタニア含有量は、上述したようなＥＵＶリソグラフィにおいて要求されるような低熱膨張ガラスを得るため、０．１〜１０重量％とする。
チタニアの含有量が０．１重量％未満である場合、得られるチタニア−シリカガラスの熱膨張係数が大きくなり、好ましくない。
一方、チタニアの含有量が１０重量％を超える場合は、０〜１００℃の温度範囲において、熱収縮が大きくなる。 The titania content of the titania-siliceous soot is 0.1 to 10% by weight in order to obtain a low thermal expansion glass as required in EUV lithography as described above.
When the titania content is less than 0.1% by weight, the resulting titania-silica glass has a large thermal expansion coefficient, which is not preferable.
On the other hand, when the titania content exceeds 10% by weight, thermal shrinkage increases in a temperature range of 0 to 100 ° C.

図１に、円柱状焼結体を作製した後の中空円筒状体形成工程以降を説明するための概略図を示す。
図１の工程図に示すように、まず、中空円筒状体形成工程においては、上記のようにＯＶＤ法等を用いて作製された円柱状焼結体１の外周面を研削し（図１（ａ）参照）、かつ、円柱状焼結体１の中央部（シリカガラス製中空軸を含む）を、コアドリル等を用いて刳り抜くと同時に、前記シリカガラス製中空軸も除去し、中空円筒状体とする（図１（ｂ）参照）。
次に、この中空円筒状体に、その軸方向に１ヶ所スリット２を形成し、スリット入り中空円筒状体とする（図１（ｃ）参照）。
そして、板状ガラス体形成工程においては、このスリット入り中空円筒状体を熱処理して、透明ガラス化および板状化を同時に行うことにより（図１（ｄ））、板状ガラス体３が得られる（図１（ｅ）参照）。 In FIG. 1, the schematic for demonstrating after the hollow cylindrical body formation process after producing columnar sintered compact is shown.
As shown in the process diagram of FIG. 1, first, in the hollow cylindrical body forming step, the outer peripheral surface of the cylindrical sintered body 1 manufactured by using the OVD method or the like as described above is ground (FIG. 1 ( a)) and the center portion of the cylindrical sintered body 1 (including the silica glass hollow shaft) is hollowed out using a core drill or the like, and at the same time, the silica glass hollow shaft is removed to form a hollow cylindrical shape. A body (see FIG. 1B).
Next, one slit 2 is formed in the hollow cylindrical body in the axial direction to form a hollow cylindrical body with slits (see FIG. 1C).
In the plate-like glass body forming step, this hollow cylindrical body with slits is heat-treated, and transparent vitrification and plate-formation are performed simultaneously (FIG. 1 (d)), thereby obtaining the plate-like glass body 3. (See FIG. 1 (e)).

中空円筒状体の焼結体を、この形状のまま透明ガラス化処理して、中空円筒状体のガラス体とした後に、スリットを形成して板状化させようとすると、前記透明ガラス化処理の際に脈理の方向性が乱れ、得られる板状ガラス体の断面に平行となるように、脈理を均質化することができない。
このため、この板状ガラス体をスライス加工し、研磨加工を施すと、面方向に不均質な脈理がガラス板表面上に存在することから、高い平坦度を得ることができない。
これに対して、本発明では、上記のように、板状ガラス体形成工程において、スリット入り中空円筒状体の焼結体を、板状化させるのと同時に、透明ガラス化させることにより、脈理を板状ガラス体の断面に平行状に均質化することができ、研磨加工した際にも、高い平坦度を得ることができる。 After the hollow cylindrical body is subjected to transparent vitrification treatment in this shape to form a hollow cylindrical glass body, the transparent vitrification treatment is performed when a slit is formed to form a plate. In this case, the striae cannot be homogenized so that the directionality of the striae is disturbed and becomes parallel to the cross section of the obtained sheet glass body.
For this reason, when this plate-like glass body is sliced and polished, a high degree of flatness cannot be obtained because a non-uniform striae exist in the surface direction on the glass plate surface.
On the other hand, in the present invention, as described above, in the plate-like glass body forming step, the sintered body of the slit hollow cylindrical body is made into a transparent glass at the same time as the plate-like shape. The reason can be homogenized in parallel with the cross section of the plate-like glass body, and high flatness can be obtained even when polishing.

前記板状ガラス体形成工程において、透明ガラス化および板状化させるための熱処理は、伝導伝熱方式により行われることが好ましい。
透明ガラス化処理が、輻射伝熱方式のみで行われると、カーボン製治具が高温真空下に曝されることにより、実質的に還元性ガス雰囲気となり、チタニア−シリカ焼結体の表面が還元され、チタニアの還元物である金属チタン等が析出し、該焼結体表面を覆う金属チタン等によって輻射光が反射され、焼結体内部にまで熱が十分に伝わらず、十分にガラス化することが困難である。
これに対して、伝導伝熱方式によれば、焼結体内部にまでガラス化に十分な熱を効率的に伝えることができ、板状ガラス体の面方向における脈理の乱れを生じることなく、無気泡の透明なチタニア−シリカガラスを得ることができる。 In the plate-like glass body forming step, it is preferable that the heat treatment for transparent vitrification and plate-like formation is performed by a conductive heat transfer method.
When the transparent vitrification process is performed only by the radiant heat transfer method, the carbon jig is exposed to a high temperature vacuum, so that a substantially reducing gas atmosphere is obtained, and the surface of the titania-silica sintered body is reduced. Then, titanium titan, which is a reduction product of titania, is deposited, and radiation light is reflected by the metal titanium covering the surface of the sintered body, so that heat is not sufficiently transmitted to the inside of the sintered body, and it is sufficiently vitrified. Is difficult.
On the other hand, according to the conduction heat transfer method, heat sufficient for vitrification can be efficiently transmitted to the inside of the sintered body, without causing disturbance of striae in the surface direction of the plate-like glass body. A bubble-free transparent titania-silica glass can be obtained.

伝導伝熱方式による熱処理においては、具体的には、スリット入り中空円筒状体の焼結体をスリットが上方になるように、カーボン製治具の上に載せ、これを炉内に配置してヒータ加熱する方法を用いることができる。この方法においては、カーボン製治具にチタニア−シリカ焼結体が直接接触するため、伝熱伝導によって前記焼結体に熱を伝えることができる。   Specifically, in the heat treatment by the conduction heat transfer method, a sintered body of a hollow cylindrical body with a slit is placed on a carbon jig so that the slit is on the upper side, and this is placed in a furnace. A heater heating method can be used. In this method, since the titania-silica sintered body is in direct contact with the carbon jig, heat can be transferred to the sintered body by heat conduction.

なお、上記製造方法において得られるチタニア−シリカガラスのサイズは、ＥＵＶリソグラフィ等のフォトマスクまたはミラー材等の光学用部材に適用する観点から、一辺の長さが５０ｍｍ〜２００ｍｍ、厚さ５ｍｍ〜１５ｍｍの板状で得られることが好ましい。   In addition, the size of the titania-silica glass obtained by the above manufacturing method is 50 mm to 200 mm in length on one side and 5 mm to 15 mm in thickness from the viewpoint of applying to a photomask such as EUV lithography or an optical member such as a mirror material. It is preferable to be obtained in the form of a plate.

以下、本発明を実施例に基づきさらに具体的に説明するが、本発明は下記の実施例により制限されるものではない。
［実施例１］
ＯＶＤ法により形成したチタニア含有量７重量％のチタニア−シリカ質スートを、ゾーンシンター方式により１３００〜１５００℃で熱処理し、円柱状焼結体を作製した。
これを、直径１５０ｍｍ、長さ２００ｍｍの円柱状に切断し、外周面を研削後、中央部をコアドリルにて刳り抜き、外径１４５ｍｍ、肉厚１５ｍｍ、長さ２００ｍｍの中空円筒状に加工した。
この中空円筒状体の焼結体の軸方向にスリットを形成し、スリットが上方になるように、カーボン製治具の上に載せ、これを炉内に配置して、真空雰囲気下、１６００〜１８００℃でヒータ加熱することにより、透明ガラス化および板状化させ、１８０ｍｍ×４００ｍｍ、厚さ８ｍｍの板状のチタニア−シリカガラスを得た。
得られたガラスの板状面を目視観察したところ、脈理の存在は認められなかった。
また、レーザ干渉計による観測では、干渉縞が確認されたが、チタニア濃度の面内不均一に起因する脈理による干渉縞の乱れはなかった。 EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not restrict | limited by the following Example.
[Example 1]
A titania-silica soot having a titania content of 7% by weight formed by the OVD method was heat-treated at 1300-1500 ° C. by a zone sintering method to produce a cylindrical sintered body.
This was cut into a columnar shape with a diameter of 150 mm and a length of 200 mm, and after grinding the outer peripheral surface, the center part was hollowed out with a core drill and processed into a hollow cylindrical shape with an outer diameter of 145 mm, a wall thickness of 15 mm, and a length of 200 mm.
A slit is formed in the axial direction of the sintered body of the hollow cylindrical body, and the slit is placed on a carbon jig so that the slit is upward. By heating with a heater at 1800 ° C., transparent vitrification and plate formation were performed, and a plate-like titania-silica glass having a size of 180 mm × 400 mm and a thickness of 8 mm was obtained.
When the plate-like surface of the obtained glass was visually observed, the presence of striae was not recognized.
In the observation with the laser interferometer, interference fringes were confirmed, but there was no disturbance of interference fringes due to striae due to in-plane nonuniformity of the titania concentration.

また、得られたガラスの板状面を鏡面研磨し、白色レーザ干渉式顕微鏡（Zygo社製 New View）にて、測定視野２．１ｍｍ×２．８ｍｍ、空間周波数０．１〜１．０ｍｍの測定条件で、算術平均粗さＲａを測定した。
その結果、チタニア濃度の不均一に起因する脈理によって生じる凹凸は認められず、Ｒａは０．２ｍｍであった。 Further, the plate-like surface of the obtained glass was mirror-polished and measured with a white laser interference microscope (New View manufactured by Zygo) with a measurement visual field of 2.1 mm × 2.8 mm and a spatial frequency of 0.1 to 1.0 mm. Arithmetic average roughness Ra was measured on measurement conditions.
As a result, irregularities caused by striae due to nonuniformity of the titania concentration were not recognized, and Ra was 0.2 mm.

［比較例１］
ＶＡＤ法により形成したチタニア含有量７重量％のチタニア−シリカ質スートを、ゾーンシンター方式により１６００〜１７００℃で熱処理し、焼結および透明ガラス化を連続的に行い、円柱状透明ガラス体を作製した。
これを、直径１５０ｍｍ、長さ２００ｍｍの円柱状に切断し、外周面を研削後、中央部をコアドリルにて刳り抜き、外径１４５ｍｍ、肉厚１０ｍｍ、長さ２００ｍｍの中空円筒状に加工した。
この中空円筒状体のガラス体の軸方向にスリットを形成し、スリットが上方になるように、カーボン製治具の上に載せ、これを炉内に配置して、真空雰囲気下、１６００〜１８００℃でヒータ加熱することにより、板状化させ、２００ｍｍ×４５０ｍｍ、厚さ８ｍｍの板状のチタニア−シリカガラスを得た。
得られたガラスの板状面を目視観察したところ、筋状の脈理が多数存在していた。
また、レーザ干渉計による観測では、干渉縞が確認され、かつ、チタニア濃度の面内不均一に起因する脈理による干渉縞の乱れが認められた。 [Comparative Example 1]
A titania-silica soot with a titania content of 7% by weight formed by the VAD method is heat treated at 1600-1700 ° C. by a zone sintering method, and is continuously sintered and transparent vitrified to produce a cylindrical transparent glass body. did.
This was cut into a columnar shape with a diameter of 150 mm and a length of 200 mm, and after grinding the outer peripheral surface, the center part was hollowed out with a core drill and processed into a hollow cylindrical shape with an outer diameter of 145 mm, a thickness of 10 mm, and a length of 200 mm.
A slit is formed in the axial direction of the glass body of this hollow cylindrical body, and the slit is placed on a carbon jig so that the slit is on the top, and this is placed in a furnace, and 1600-1800 in a vacuum atmosphere. By heating with a heater at 0 ° C., a plate-like titania-silica glass having a size of 200 mm × 450 mm and a thickness of 8 mm was obtained.
When the plate-like surface of the obtained glass was visually observed, many streaks were present.
In the observation with a laser interferometer, interference fringes were confirmed, and disturbance of interference fringes due to striae due to in-plane nonuniformity of titania concentration was recognized.

また、得られたガラスの板状面を鏡面研磨し、実施例１と同様にして、算術平均粗さＲａを測定した結果、チタニア濃度の不均一に起因する脈理によって生じる凹凸が認められ、Ｒａは１．５ｍｍであった。   Moreover, as a result of mirror polishing the plate-like surface of the obtained glass and measuring the arithmetic average roughness Ra in the same manner as in Example 1, irregularities caused by striae due to the nonuniformity of the titania concentration were recognized, Ra was 1.5 mm.

本発明に係る製造方法の製造工程の一例を説明するための概略図である。It is the schematic for demonstrating an example of the manufacturing process of the manufacturing method which concerns on this invention.

符号の説明Explanation of symbols

１ 円柱状焼結体
２ スリット
３ 板状ガラス体 DESCRIPTION OF SYMBOLS 1 Cylindrical sintered body 2 Slit 3 Plate-shaped glass body

Claims (4)

チタニア０．１〜１０重量％を含むチタニア−シリカ質スートを熱処理して、円柱状焼結体を作製する工程と、前記円柱状焼結体の外周面を研削し、かつ、中央部を軸方向に刳り抜き、中空円筒状体とする工程と、前記中空円筒状体の軸方向にスリットを形成し、スリット入り中空円筒状体とする工程と、前記スリット入り中空円筒状体を熱処理して、透明ガラス化および板状化させ、板状ガラス体とする工程とを備えていることを特徴とするチタニア−シリカガラスの製造方法。   A process of preparing a cylindrical sintered body by heat-treating titania-siliceous soot containing 0.1 to 10% by weight of titania, grinding the outer peripheral surface of the cylindrical sintered body, and centering the central portion Punching in the direction to make a hollow cylindrical body, forming a slit in the axial direction of the hollow cylindrical body, and making the hollow cylindrical body with slit, and heat-treating the hollow cylindrical body with slit A method for producing titania-silica glass, comprising: a step of transparent vitrification and plate formation to form a plate-like glass body. 前記チタニア−シリカ質スートが、ＯＶＤ法により形成されることを特徴とする請求項１記載のチタニア−シリカガラスの製造方法。   The method for producing a titania-silica glass according to claim 1, wherein the titania-siliceous soot is formed by an OVD method. 前記円柱状焼結体作製工程における熱処理が、ゾーンシンター方式により行われることを特徴とする請求項１または請求項２記載のチタニア−シリカガラスの製造方法。   The method for producing a titania-silica glass according to claim 1 or 2, wherein the heat treatment in the cylindrical sintered body production step is performed by a zone sintering method. 前記板状ガラス体形成工程における熱処理が、伝導伝熱方式により行われることを特徴とする請求項１から請求項３までのいずれかに記載のチタニア−シリカガラスの製造方法。   The method for producing titania-silica glass according to any one of claims 1 to 3, wherein the heat treatment in the plate-like glass body forming step is performed by a conductive heat transfer method.
JP2007090355A 2007-03-30 2007-03-30 Method for manufacturing titania-silica glass Pending JP2008247661A (en)

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