JP4781003B2 - Silica-titania glass for nanoimprint stamper - Google Patents

Silica-titania glass for nanoimprint stamper Download PDF

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JP4781003B2
JP4781003B2 JP2005132751A JP2005132751A JP4781003B2 JP 4781003 B2 JP4781003 B2 JP 4781003B2 JP 2005132751 A JP2005132751 A JP 2005132751A JP 2005132751 A JP2005132751 A JP 2005132751A JP 4781003 B2 JP4781003 B2 JP 4781003B2
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silica
titania
titania glass
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nanoimprint
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JP2006306674A (en
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朗 藤ノ木
裕幸 西村
哲司 上田
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Shin Etsu Quartz Products Co Ltd
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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

Description

本発明は、半導体リソグラフィー、次世代光ディスク、バイオテクノロジー等で用いられるナノインプリント技術に用いられるスタンパー、特に面積が１００ｃｍ2を超える大面積スタンパーに好適に用いられるシリカ・チタニアガラス（本発明において、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。）に関する。 The present invention relates to a silica-titania glass suitably used for a stamper used in nanoimprint technology used in semiconductor lithography, next-generation optical discs, biotechnology, etc., in particular, a large-area stamper having an area exceeding 100 cm 2 (in the present invention, titania The silica glass contained is referred to as silica-titania glass.

線幅が４０ｎｍ以下の半導体の描画方式については、未だその方式が検討されている段階であるが、波長１３．５ｎｍのＥＵＶ光を用いるＥＵＶリソグラフィー（Extreme Ultra-Violet Lithography）の対抗方式としてスタンパーを用いてパターンを転写するナノインプリント技術が注目を浴びてきている。
これは、ステンシル、テンプレートあるいはスタンパーと呼ばれる微細なパターンを刻印した型を、紫外線硬化型レジストを塗布したウエハー表面に一定の押圧で押し付け、上部から例えば水銀灯のＧ線やＩ線などの紫外線を照射してレジストを感光させてパターン形成を行う手法である。 A semiconductor drawing method with a line width of 40 nm or less is still under investigation, but a stamper is used as a countermeasure for EUV lithography (Extreme Ultra-Violet Lithography) using EUV light with a wavelength of 13.5 nm. Nanoimprint technology that uses it to transfer patterns has attracted attention.
This is because a mold engraved with a fine pattern called a stencil, template or stamper is pressed against the wafer surface coated with an ultraviolet curable resist with a certain amount of pressure and irradiated from the top with ultraviolet rays such as G-rays and I-rays from mercury lamps. Then, the resist is exposed to form a pattern.

ナノインプリント技術の特徴はその応用がリソグラフィーのみに留まらず、例えば転写パターンサイズが１００μｍ程度の次世代光ディスクの製造やＤＮＡチップ等への応用が検討されていて、応用範囲が非常に広いことである。このようなスタンパーは一定の押圧を均等に伝える為に機械的剛性および強度が必要であり、また、直接レジスト等と接触する為に不要な不純物が少ないこと、毎回洗浄が必要である為に化学的な耐久性が高いことが要求される。
このため、スタンパー素材としてはポリカーボネート等の樹脂、ガラス、セラミクスが用いられるが（例えば、特許文献１及び２等参照。）、光硬化型レジストを用いる光ナノインプリント技術では紫外線に対して透明なガラス、好適にはシリカガラスが用いられる。 The feature of the nanoimprint technology is that its application is not limited to lithography, but for example, the production of next-generation optical discs with a transfer pattern size of about 100 μm and the application to DNA chips and the like are being studied, and the application range is very wide. Such a stamper requires mechanical rigidity and strength to transmit a certain amount of pressure evenly, and since there are few unnecessary impurities for direct contact with resist, etc., and cleaning is required every time. High durability is required.
For this reason, resins such as polycarbonate, glass, and ceramics are used as the stamper material (see, for example, Patent Documents 1 and 2). However, in the optical nanoimprint technology using a photocurable resist, glass that is transparent to ultraviolet rays, Silica glass is preferably used.

また、ナノインプリント技術の利点の一つとして大面積の一括転写が挙げられるが、面積が１００ｃｍ2を超えるような大面積の転写に用いられる大型スタンパーにおいては数十ｎｍという微細なパターンの位置精度が極めて重要になってくる。例えば線膨張係数（ＣＴＥ）が５×１０-7／℃（５００ｐｐｂ／℃）の６インチ角のシリカガラススタンパーを用いる場合、スタンパーの対角は約２１０ｍｍであるから、温度が１℃変化するごとに最大０．１μｍ（１００ｎｍ）長さが変化することになる。このような長さ変化は線幅数１０ｎｍのパターンにとっては大きな問題となり、少なくともＣＴＥをシリカガラスの半分以下の±２００ｐｐｂ／℃に抑えることが必要である。
特開２００４−２８８８４５号公報 特開２００４−２８８８０２号公報 One of the advantages of nanoimprint technology is batch transfer of large areas, but large stampers used for large area transfer with an area exceeding 100 cm 2 have a fine pattern positional accuracy of several tens of nanometers. It becomes extremely important. For example, when a 6-inch square silica glass stamper having a coefficient of linear expansion (CTE) of 5 × 10 −7 / ° C. (500 ppb / ° C.) is used, the diagonal of the stamper is about 210 mm. The maximum length changes to 0.1 μm (100 nm). Such a change in length is a big problem for a pattern with a line width of several tens of nm, and at least CTE must be suppressed to ± 200 ppb / ° C., which is half or less of silica glass.
JP 2004-288845 A JP 2004-288802 A

本発明は、ナノインプリント用スタンパー、特に紫外線を用いたナノインプリント用の大型スタンパーで問題となる、温度変化に対する形状の安定性と好適な紫外線透過率とを両立させた素材を提供することを目的とする。即ち、線膨張係数が±２００ｐｐｂ／℃以下と極めて小さく、かつ紫外線透過率の良好な超低膨張ガラスを提供することを目的としている。   It is an object of the present invention to provide a material that has both a shape stability against temperature change and a suitable ultraviolet transmittance, which is a problem in a nanoimprint stamper, particularly a large stamper for nanoimprint using ultraviolet rays. . That is, an object of the present invention is to provide an ultra-low expansion glass having an extremely small linear expansion coefficient of ± 200 ppb / ° C. or less and a good ultraviolet transmittance.

上記課題を解決するために、本発明のナノインプリントスタンパー用シリカ・チタニアガラスは、２質量％以上１５質量％以下のチタニアを含有するシリカ・チタニアガラスであって、２０℃から３５℃の温度範囲における線膨張係数が±２００ｐｐｂ／℃の範囲にあることを特徴とする。   In order to solve the above problems, the silica-titania glass for a nanoimprint stamper of the present invention is a silica-titania glass containing titania of 2% by mass or more and 15% by mass or less, in a temperature range of 20 ° C. to 35 ° C. The linear expansion coefficient is in the range of ± 200 ppb / ° C.

本発明のシリカ・チタニアガラスは、波長３６５ｎｍの紫外線に対する内部透過率が９０％以上であることが好ましい。
また、波長１８５ｎｍの低圧水銀灯を出力２５ｍＷ／ｃｍで５ｃｍの距離で１００時間照射した際の３６５ｎｍの波長における内部透過率の変化ΔＴ％が５％以下であることが好適である。
本発明のシリカ・チタニアガラスが、使用方向に脈理が存在しないことが好ましい。 The silica-titania glass of the present invention preferably has an internal transmittance of 90% or more for ultraviolet rays having a wavelength of 365 nm.
Further, it is preferable that the change ΔT% in internal transmittance at a wavelength of 365 nm when a low-pressure mercury lamp having a wavelength of 185 nm is irradiated at a distance of 5 cm at an output of 25 mW / cm for 100 hours is 5% or less.
The silica-titania glass of the present invention preferably has no striae in the direction of use.

前記ナノインプリント技術が、紫外線硬化方式であることが好ましい。   The nanoimprint technique is preferably an ultraviolet curing method.

本発明によれば、ナノインプリント用スタンパー、特に紫外線を用いたナノインプリント用の大型スタンパーで問題となる、温度変化に対する形状の安定性と好適な紫外線透過率とを両立させた素材、即ち、線膨張係数が±２００ｐｐｂ／℃以下と極めて小さく、かつ紫外線透過率の良好な超低膨張ガラスを提供することができる。   According to the present invention, a nanoimprint stamper, in particular, a large-size stamper for nanoimprint using ultraviolet rays, which is a problem, is a material that has both shape stability against temperature change and suitable ultraviolet transmittance, that is, a linear expansion coefficient. Can be provided as an ultra-low expansion glass having an extremely low UV transmittance of ± 200 ppb / ° C. or less.

以下に本発明の実施の形態を説明するが、これら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。   Embodiments of the present invention will be described below, but these are exemplarily shown, and it goes without saying that various modifications are possible without departing from the technical idea of the present invention.

本発明は、ナノインプリント用スタンパーの素材としてシリカ・チタニアガラスを用いることにより、２０℃〜３５℃の温度範囲における線膨張係数を±２００ｐｐｂ／℃の範囲に抑えることを可能とするものである。
本発明のシリカ・チタニアガラスは、２質量％以上１５質量％以下のチタニアを含有するシリカガラスであり、チタニアとＳｉＯ2の組成からなるものが好ましい。チタニア濃度は、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１３質量％以下、さらに好ましくは８質量％以下である。 The present invention makes it possible to suppress the linear expansion coefficient in a temperature range of 20 ° C. to 35 ° C. to a range of ± 200 ppb / ° C. by using silica-titania glass as a material for a stamper for nanoimprinting.
The silica-titania glass of the present invention is a silica glass containing 2% by mass or more and 15% by mass or less of titania, and is preferably composed of a composition of titania and SiO 2 . The titania concentration is preferably 4% by weight or more, more preferably 6% by weight or more, preferably 13% by weight or less, and more preferably 8% by weight or less.

該シリカ・チタニアガラスの製造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。本発明のシリカ・チタニアガラスは、使用方向に脈理が存在しないことが好ましい為、脈理除去を施されたシリカ・チタニアガラスが特に好適である。   The method for producing the silica / titania glass is not particularly limited, and a known method may be appropriately selected. Since the silica-titania glass of the present invention preferably has no striae in the direction of use, the silica-titania glass from which striae has been removed is particularly suitable.

本発明によれば、更に、波長３６５ｎｍの紫外線に対する内部透過率を９０％以上、即ち９０％以上１００％以下の素材を提供することができる。
また、波長１８５ｎｍの低圧水銀灯を出力２５ｍＷ／ｃｍで、試料との距離を５ｃｍ離して１００時間照射した際の３６５ｎｍの波長における内部透過率の変化ΔＴ％を５％以下にすることができる。 Further, according to the present invention, it is possible to provide a material having an internal transmittance of 90% or more, that is, 90% or more and 100% or less with respect to ultraviolet rays having a wavelength of 365 nm.
Moreover, the change ΔT% in internal transmittance at a wavelength of 365 nm when a low-pressure mercury lamp with a wavelength of 185 nm is irradiated for 100 hours with an output of 25 mW / cm and a distance of 5 cm from the sample can be reduced to 5% or less.

本発明のシリカ・チタニアガラスを用いるナノインプリント技術としては、特に限定されないが、紫外線硬化方式であることが好ましい。   Although it does not specifically limit as a nanoimprint technique using the silica titania glass of this invention, It is preferable that it is an ultraviolet curing system.

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によって得られる酸水素火炎中に導入し垂直に保持され回転している直径３０ｍｍ、長さ１ｍのシリカガラス製基体上に堆積して直径３００ｍｍ、長さ１０００ｍｍ、重量２５ｋｇ弱のシリカ・チタニアガラス多孔質体を得た。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９３．２質量％、チタニア分６．８質量％に調整した。
得られたシリカ・チタニアガラス多孔質体をヘリウムガス雰囲気のゾーン加熱電気炉内をゆっくりと移動させつつ、１５００℃に加熱して透明な直径１００ｍｍ、長さ１３５０ｍｍのシリカ・チタニアガラスインゴットを得た（ＶＡＤ法によるシリカ・チタニアガラスインゴットの作製工程）。 Example 1
Silicon tetrachloride and titanium tetrachloride are introduced into an oxyhydrogen flame obtained by an oxyhydrogen burner and deposited on a silica glass substrate having a diameter of 30 mm and a length of 1 m which is held vertically and rotated, and has a diameter of 300 mm. A porous silica / titania glass having a thickness of 1000 mm and a weight of less than 25 kg was obtained. Adjust the flow rate ratio of silicon tetrachloride and titanium tetrachloride when growing silica / titania glass, and adjust the composition of silica / titania glass to 93.2 mass% for silica and 6.8 mass% for titania. did.
The obtained silica-titania glass porous body was heated to 1500 ° C. while slowly moving in a zone heating electric furnace in a helium gas atmosphere to obtain a transparent silica-titania glass ingot having a diameter of 100 mm and a length of 1350 mm. (Process for producing a silica-titania glass ingot by the VAD method).

前記得られたシリカ・チタニアガラスインゴットから直径６０ｍｍ、厚さ１０ｍｍのサンプルを切り出し、１１５０℃で１００時間保持後３００℃まで１時間当り１℃の割合で徐冷して歪除去を施した後、両端を研磨して干渉計で均質性測定を行ったところ、外周より約５ｍｍに脈理が存在していることが判った。
前記得られたシリカ・チタニアガラスインゴットの両端をそれぞれ７５ｍｍずつカットし、更に外周を深さで５ｍｍ外周研削して、外径９０ｍｍ、長さ１２００ｍｍのシリカ・チタニアガラスインゴットを作製した。このシリカ・チタニアガラスインゴットを半分（長さ６００ｍｍ）に切り、内底面の形状が一辺の長さが１８０ｍｍの正方形で、深さ６００ｍｍのグラファイト型内に端部を下に設置し、グラファイト容器ごと真空炉内に設置して１６００℃まで５時間かけて昇温し、昇温と同時に通電を停止しそのまま炉冷した。
更に得られたシリカ・チタニアガラス角材を大気雰囲気下で１１５０℃で１００時間保持後３００℃まで１時間辺り１℃の割合で徐冷して歪を除去した（徐歪処理工程）。 A sample having a diameter of 60 mm and a thickness of 10 mm was cut out from the obtained silica-titania glass ingot, held at 1150 ° C. for 100 hours, and then gradually cooled to 300 ° C. at a rate of 1 ° C. per hour to remove strain, When both ends were polished and homogeneity was measured with an interferometer, it was found that striae existed about 5 mm from the outer periphery.
Both ends of the silica / titania glass ingot thus obtained were cut by 75 mm, and the outer periphery was further ground by 5 mm to produce a silica / titania glass ingot having an outer diameter of 90 mm and a length of 1200 mm. This silica-titania glass ingot is cut in half (600 mm in length), and the shape of the inner bottom surface is a square with a side length of 180 mm. The end is placed in a graphite mold with a depth of 600 mm. It was installed in a vacuum furnace and the temperature was raised to 1600 ° C. over 5 hours.
Further, the obtained silica-titania glass square was held at 1150 ° C. for 100 hours in an air atmosphere and then slowly cooled to 300 ° C. at a rate of 1 ° C. for 1 hour to remove strain (gradual strain treatment step).

このようにして１辺の長さが１８０ｍｍ、厚さ１２０ｍｍのシリカ・チタニアガラス成型体を得た。得られた成型体の上下面及び側面を１０ｍｍづつカットし、更に寸法だしの精密カット後、上下面に平行に厚さ８ｍｍにスライスし、１５２ｍｍ角の両面を６０２５フォトマスクの仕様（フラットネス２μｍ以下、面粗さＲａ ５Å以下）を満たすように超精密研磨を行って一辺の長さが１５２．０ｍｍ、厚さ６．２５ｍｍの透明な平板状の基板に加工した。   Thus, a silica-titania glass molded body having a side length of 180 mm and a thickness of 120 mm was obtained. Cut the top and bottom and side surfaces of the resulting molded body in 10mm increments, and after further precision cutting, slice into 8mm thickness parallel to the top and bottom surfaces, and both sides of the 152mm square are 6025 photomask specifications (flatness 2μm Then, ultra-precision polishing was performed so as to satisfy a surface roughness Ra of 5 mm or less, and a transparent flat substrate having a side length of 152.0 mm and a thickness of 6.25 mm was processed.

得られたシリカ・チタニアガラス基板の１５２ｍｍ角の面をシュリーレン装置（溝尻光学製 ＳＣＨＬＩＥＲＥＮ ＣＯＭＰＡＣＴ １５０）で脈理観察したが、脈理は認められなかった。
また、得られたシリカ・チタニアガラス基板の紫外線透過率測定を行った。厚さ６．２５ｍｍにおける見かけ透過率スペクトルを図１に示す。図１から求めた波長３６５ｎｍにおける内部透過率は９９．９％であった。 The striae of the obtained 152 mm square surface of the silica-titania glass substrate was observed with a schlieren apparatus (SCHLIEREN COMPACT 150, manufactured by Mizojiri Optics), but no striae was observed.
Further, the ultraviolet transmittance of the obtained silica / titania glass substrate was measured. An apparent transmittance spectrum at a thickness of 6.25 mm is shown in FIG. The internal transmittance at a wavelength of 365 nm determined from FIG. 1 was 99.9%.

また、得られたシリカ・チタニアガラス基板の線膨張係数をレーザー干渉式熱膨張計（ＵＬＶＡＣ理工社製レーザー膨張計 ＬＩＸ−１）を用いて測定した。結果を実施例２、実施例３及び比較例１と併せて表１に示す。   Moreover, the linear expansion coefficient of the obtained silica-titania glass substrate was measured using a laser interference thermal dilatometer (Laser dilatometer LIX-1 manufactured by ULVAC Riko Co., Ltd.). The results are shown in Table 1 together with Example 2, Example 3 and Comparative Example 1.

更に得られたシリカガラス基板に加速試験の目的で使用波長より短い波長１８５ｎｍの低圧水銀灯の紫外線を出力２５ｍＷ／ｃｍにて５ｃｍの距離で１００時間照射して波長３６５ｎｍにおける透過率変化を調べた結果、５％以下であった。   Further, the obtained silica glass substrate was irradiated with ultraviolet rays from a low pressure mercury lamp having a wavelength of 185 nm shorter than the wavelength used for the purpose of an acceleration test for 100 hours at a distance of 5 cm at an output of 25 mW / cm, and the change in transmittance at a wavelength of 365 nm was examined. 5% or less.

（実施例２）
火炎中に導入する四塩化珪素と四塩化チタンの濃度を変化させてシリカ９７．９質量％、チタニア２．１質量％のシリカ・チタニアガラスインゴットを作成した以外は実施例１と同様の方法を用い、同様に一辺の長さが１５２ｍｍ、厚さ６．２５ｍｍの超精密に研磨されたシリカ・チタニアガラス基板を作製した。 (Example 2)
The same method as in Example 1 was used except that silica and titania glass ingots of 97.9% by mass of silica and 2.1% by mass of titania were prepared by changing the concentrations of silicon tetrachloride and titanium tetrachloride introduced into the flame. In the same manner, a silica / titania glass substrate having a length of one side of 152 mm and a thickness of 6.25 mm was polished.

得られたシリカ・チタニアガラス基板について、実施例１と同様に線膨張係数を調べた。結果を表１に示す。
また、得られたシリカ・チタニアガラス基板の１５２ｍｍ角の面についてシュリーレン装置を用いて脈理測定を行ったが脈理は認められなかった。得られたシリカ・チタニアガラス基板の紫外線透過率を測定したところ、３６５ｎｍの内部透過率は９９．９％であった。さらに、実施例１と同様に紫外線照射による透過率変化を調べた結果、５％以下であった。 The linear expansion coefficient of the obtained silica / titania glass substrate was examined in the same manner as in Example 1. The results are shown in Table 1.
Further, striae measurement was performed on a 152 mm square surface of the obtained silica / titania glass substrate using a schlieren apparatus, but no striae was observed. When the ultraviolet transmittance of the obtained silica / titania glass substrate was measured, the internal transmittance at 365 nm was 99.9%. Further, as a result of examining the change in transmittance due to ultraviolet irradiation in the same manner as in Example 1, it was 5% or less.

（実施例３）
火炎中に導入する四塩化珪素と四塩化チタンの濃度を変化させてシリカ８９．８質量％、チタニア１０．２質量％のシリカ・チタニアガラスインゴットを作成した以外は実施例１と同様の方法を用い、同様に一辺の長さが１５２ｍｍ、厚さ６．２５ｍｍの超精密に研磨されたシリカ・チタニアガラス基板を作製した。 (Example 3)
The same method as in Example 1 was performed except that a silica-titania glass ingot of 89.8% by mass of silica and 10.2% by mass of titania was prepared by changing the concentrations of silicon tetrachloride and titanium tetrachloride introduced into the flame. In the same manner, a silica / titania glass substrate having a length of one side of 152 mm and a thickness of 6.25 mm was polished.

得られたシリカ・チタニアガラス基板について、実施例１と同様に線膨張係数を調べた。結果を表１に示す。
また、得られたシリカ・チタニアガラス基板の１５２ｍｍ角の面についてシュリーレン装置を用いて脈理測定を行ったが脈理は認められなかった。得られたシリカ・チタニアガラス基板の紫外線透過率を測定したところ、３６５ｎｍの内部透過率は９９．９％であった。さらに、実施例１と同様に紫外線照射による透過率変化を調べた結果、５％以下であった。 The linear expansion coefficient of the obtained silica / titania glass substrate was examined in the same manner as in Example 1. The results are shown in Table 1.
Further, striae measurement was performed on a 152 mm square surface of the obtained silica / titania glass substrate using a schlieren apparatus, but no striae was observed. When the ultraviolet transmittance of the obtained silica / titania glass substrate was measured, the internal transmittance at 365 nm was 99.9%. Further, as a result of examining the change in transmittance due to ultraviolet irradiation in the same manner as in Example 1, it was 5% or less.

（比較例１）
原料を四塩化珪素のみとした以外は実施例１と同様のＶＡＤによるスート法を用いてシリカガラスインゴットを作製した。更に実施例１と同様に一辺の長さが１５２ｍｍ、厚さ６．２５ｍｍの超精密に研磨されたシリカガラス基板を作製した。
得られたシリカガラス基板の１５２ｍｍ角の面についてシュリーレン装置を用いて脈理測定を行ったが脈理は認められなかった。得られたシリカガラス基板の紫外線透過率を測定したところ、３６５ｎｍの内部透過率は９９．９％であった。実施例１と同様に線膨張係数を調べた。結果を表１に示す。同様に紫外線照射による透過率変化を調べた結果、５％以下であった。 (Comparative Example 1)
A silica glass ingot was produced using the VAD soot method similar to Example 1 except that the raw material was only silicon tetrachloride. Further, in the same manner as in Example 1, a silica glass substrate polished on ultra-precision with a side length of 152 mm and a thickness of 6.25 mm was produced.
Striae measurement was performed on a 152 mm square surface of the obtained silica glass substrate using a schlieren apparatus, but no striae was observed. When the ultraviolet transmittance of the obtained silica glass substrate was measured, the internal transmittance at 365 nm was 99.9%. The linear expansion coefficient was examined in the same manner as in Example 1. The results are shown in Table 1. Similarly, as a result of examining the change in transmittance due to ultraviolet irradiation, it was 5% or less.

Figure 0004781003
Figure 0004781003

表１に示した如く、実施例１〜３の本発明のシリカ・チタニアガラスは線膨張係数が±２００ｐｐｂ／℃以内と極めて小さく、且つ紫外線透過率が良好であり、脈理のない超低膨張ガラスであった。一方、比較例１のシリカガラスは、線膨張係数が２００ｐｐｂ／℃を超えていた。   As shown in Table 1, the silica-titania glasses of Examples 1 to 3 of the present invention have a very low linear expansion coefficient within ± 200 ppb / ° C., a good ultraviolet transmittance, and an ultra-low expansion without striae. It was glass. On the other hand, the silica glass of Comparative Example 1 had a linear expansion coefficient exceeding 200 ppb / ° C.

実施例１の紫外線透過率測定の結果を示すグラフであるIt is a graph which shows the result of the ultraviolet-ray-transmittance measurement of Example 1.

Claims (5)

２質量％以上１５質量％以下のチタニアを含有するシリカ・チタニアガラスであって、２０℃から３５℃の温度範囲における線膨張係数が±２００ｐｐｂ／℃の範囲にあることを特徴とするナノインプリントスタンパー用シリカ・チタニアガラス。   A silica-titania glass containing titania of 2% by mass or more and 15% by mass or less, and having a linear expansion coefficient in a temperature range of 20 ° C. to 35 ° C. within a range of ± 200 ppb / ° C. Silica-titania glass. 波長３６５ｎｍの紫外線に対する内部透過率が９０％以上であることを特徴とする請求項１記載のナノインプリントスタンパー用シリカ・チタニアガラス。 2. The silica / titania glass for a nanoimprint stamper according to claim 1, wherein an internal transmittance for ultraviolet rays having a wavelength of 365 nm is 90% or more. 波長１８５ｎｍの低圧水銀灯を出力２５ｍＷ／ｃｍで５ｃｍの距離で１００時間照射した際の３６５ｎｍの波長における内部透過率の変化ΔＴ％が５％以下であることを特徴とする請求項１又は２記載のナノインプリントスタンパー用シリカ・チタニアガラス。   The change in internal transmittance ΔT% at a wavelength of 365 nm when a low-pressure mercury lamp with a wavelength of 185 nm is irradiated at a distance of 5 cm at an output of 25 mW / cm for 100 hours is 5% or less. Silica-titania glass for nanoimprint stampers. 使用方向に脈理が存在しないことを特徴とする請求項１〜３のいずれか１項記載のナノインプリントスタンパー用シリカ・チタニアガラス。   4. The silica-titania glass for a nanoimprint stamper according to any one of claims 1 to 3, wherein no striae exist in the direction of use. ナノインプリント技術が紫外線硬化方式であることを特徴とする請求項１〜４のいずれか１項記載のナノインプリントスタンパー用シリカ・チタニアガラス。   The silica-titania glass for a nanoimprint stamper according to any one of claims 1 to 4, wherein the nanoimprint technology is an ultraviolet curing method.
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