JP2014091637A - Crystallized glass - Google Patents
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- JP2014091637A JP2014091637A JP2012241308A JP2012241308A JP2014091637A JP 2014091637 A JP2014091637 A JP 2014091637A JP 2012241308 A JP2012241308 A JP 2012241308A JP 2012241308 A JP2012241308 A JP 2012241308A JP 2014091637 A JP2014091637 A JP 2014091637A
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- 239000011521 glass Substances 0.000 title claims abstract description 110
- 239000013078 crystal Substances 0.000 claims abstract description 43
- 229910000500 β-quartz Inorganic materials 0.000 claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 27
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 23
- 229910008556 Li2O—Al2O3—SiO2 Inorganic materials 0.000 claims description 15
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 8
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- 239000004615 ingredient Substances 0.000 claims description 3
- 230000000704 physical effect Effects 0.000 abstract description 10
- 229910052785 arsenic Inorganic materials 0.000 abstract description 7
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052787 antimony Inorganic materials 0.000 abstract description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000243 solution Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 52
- 238000005352 clarification Methods 0.000 description 12
- 238000002425 crystallisation Methods 0.000 description 12
- 230000008025 crystallization Effects 0.000 description 12
- 238000004031 devitrification Methods 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000005498 polishing Methods 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 239000002241 glass-ceramic Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000007670 refining Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000003746 surface roughness Effects 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000001459 lithography Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Chemical compound O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 2
- -1 lanquinite Chemical compound 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910001347 Stellite Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052661 anorthite Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910001597 celsian Inorganic materials 0.000 description 1
- AHICWQREWHDHHF-UHFFFAOYSA-N chromium;cobalt;iron;manganese;methane;molybdenum;nickel;silicon;tungsten Chemical compound C.[Si].[Cr].[Mn].[Fe].[Co].[Ni].[Mo].[W] AHICWQREWHDHHF-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 description 1
- PHGMGTWRSNXLDV-UHFFFAOYSA-N diethyl furan-2,5-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)O1 PHGMGTWRSNXLDV-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- WVMPCBWWBLZKPD-UHFFFAOYSA-N dilithium oxido-[oxido(oxo)silyl]oxy-oxosilane Chemical compound [Li+].[Li+].[O-][Si](=O)O[Si]([O-])=O WVMPCBWWBLZKPD-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229910000174 eucryptite Inorganic materials 0.000 description 1
- 239000006025 fining agent Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052664 nepheline Inorganic materials 0.000 description 1
- 239000010434 nepheline Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052670 petalite Inorganic materials 0.000 description 1
- 239000006064 precursor glass Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- FKHIFSZMMVMEQY-UHFFFAOYSA-N talc Chemical compound [Mg+2].[O-][Si]([O-])=O FKHIFSZMMVMEQY-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052844 willemite Inorganic materials 0.000 description 1
- 229910021493 α-cristobalite Inorganic materials 0.000 description 1
- 229910021489 α-quartz Inorganic materials 0.000 description 1
- 229910021491 α-tridymite Inorganic materials 0.000 description 1
Landscapes
- Glass Compositions (AREA)
Abstract
Description
本発明は、Ｌｉ２Ｏ−Ａｌ２Ｏ３−ＳｉＯ２系の結晶化ガラスに関する。 The present invention relates to a crystallized glass of Li 2 O—Al 2 O 3 —SiO 2 system.
β‐石英及び／又はβ‐石英固溶体を含むＬｉ２Ｏ−Ａｌ２Ｏ３−ＳｉＯ２系の結晶化ガラスは、低い平均膨張係数を有し、高剛性、研磨後の表面の超平滑性など、この系の結晶化ガラス特有の有用な物性を備えている。こういった特性から極端紫外線を光源とする極端紫外線露光技術（ＥＵＶＬ）を利用した次世代半導体製造装置などのミラー基板材やフォトマスク基板材としての使用が検討されている。 Li 2 O—Al 2 O 3 —SiO 2 -based crystallized glass containing β-quartz and / or β-quartz solid solution has a low average expansion coefficient, high rigidity, ultra-smooth surface after polishing, etc. It has useful physical properties peculiar to crystallized glass of this system. Due to these characteristics, use as a mirror substrate material or a photomask substrate material for a next-generation semiconductor manufacturing apparatus using extreme ultraviolet exposure technology (EUVL) using extreme ultraviolet light as a light source has been studied.
一方、Ｌｉ２Ｏ−Ａｌ２Ｏ３−ＳｉＯ２系の結晶化ガラスにおいては、その製造過程における前駆体ガラスの溶解温度は、一般的に１４５０〜１６００℃と高い。この結晶化ガラスは、製造過程の溶解時の均質化及び清澄化の目的で、清澄剤を添加することが行われており、前述の様な高い温度域で効果のある清澄剤として、砒素成分やアンチモン成分が最も頻繁に用いられている。しかし、砒素成分やアンチモン成分は人体及び環境に対して悪影響を及ぼす恐れがあり、かつ環境的に許容されないことから、これらの成分の使用を極力控える要求が高まりつつある。 On the other hand, in the Li 2 O—Al 2 O 3 —SiO 2 -based crystallized glass, the melting temperature of the precursor glass in the production process is generally as high as 1450 to 1600 ° C. In this crystallized glass, a clarifier is added for the purpose of homogenization and clarification at the time of dissolution in the production process. As a clarifier effective in the high temperature range as described above, an arsenic component is added. And antimony components are most frequently used. However, since arsenic components and antimony components may adversely affect the human body and the environment, and are not environmentally acceptable, there is an increasing demand to refrain from using these components as much as possible.
Ｌｉ２Ｏ−Ａｌ２Ｏ３−ＳｉＯ２系の結晶化ガラスが開示されており、Ａｓ２Ｏ３成分、又はＳｂ２Ｏ３成分以外の清澄剤について示唆されている。
特許文献１では希土類酸化物とハロゲンを含有させることでＬｉ２Ｏ−Ａｌ２Ｏ３−ＳｉＯ２系の溶融ガラス時の清澄効果を生み出している。しかし、使用されるＣｌ、並びにＣｌを含む化合物は有毒であり、人体や生産設備への負荷が大きく、また、希土類酸化物は安定的な供給とコストの面で不利である。
特許文献２ではＳｎＯ２とさらなる清澄剤としてＳｂ２Ｏ３、Ｃｌ‐、Ｂｒ‐、ＳＯ４ ２‐を含有させることでＬｉ２Ｏ−Ａｌ２Ｏ３−ＳｉＯ２系の溶融ガラス時の清澄効果を生み出している。しかし、さらなる清澄剤にＣｌ及びＢｒ、並びにＣｌ及びＢｒを含む化合物は有毒であり、人体や生産設備への負荷が大きく、また、Ｓｂ２Ｏ３を使用しているため、不利である。
Li 2 O—Al 2 O 3 —SiO 2 -based crystallized glass has been disclosed, and a refining agent other than the As 2 O 3 component or the Sb 2 O 3 component is suggested.
Has produced Li 2 O-Al 2 O 3 -SiO 2 system refining effect upon molten glass by the inclusion of rare earth oxides in Patent Document 1 and halogen. However, the Cl used and the compounds containing Cl are toxic and have a heavy load on the human body and production facilities, and rare earth oxides are disadvantageous in terms of stable supply and cost.
Sb 2 O 3 and Patent Document 2 SnO 2 as a further refining agents, Cl -, Br -, Li by the inclusion of SO 4 2- 2 O-Al 2 O 3 -SiO 2 system refining effect upon molten glass Has produced. However, Cl and Br, and compounds containing Cl and Br as additional fining agents are toxic, have a heavy load on the human body and production facilities, and are disadvantageous because they use Sb 2 O 3 .
本発明の目的は、Ｌｉ２Ｏ−Ａｌ２Ｏ３−ＳｉＯ２系の結晶化ガラスに特徴のある諸物性を維持しつつ、砒素成分やアンチモン成分を含まない結晶化ガラスを提供することにある。 An object of the present invention is to provide a crystallized glass that does not contain an arsenic component or an antimony component while maintaining various physical properties characteristic of the Li 2 O—Al 2 O 3 —SiO 2 based crystallized glass. .
本発明者は、上記目的を達成するために鋭意試験研究を重ねた結果、ＳｉＯ２及びＡｌ２Ｏ３、Ｌｉ２Ｏの各成分を含有する結晶化ガラスに清澄剤としてＳｎＯ２成分を含有させること、好ましくはこれらの成分の含有量を特定の範囲とすることにより、本発明をなすに至った。
すなわち、本発明の好適な態様は以下の構成で表わすことができる。
（構成１）
ＳｉＯ２、Ａｌ２Ｏ３、及びＬｉ２Ｏの各成分（酸化物換算）を含有し、ＳｎＯ２成分（酸化物換算）を０．０１〜３％含有することを特徴とする、Ｌｉ２Ｏ−Ａｌ２Ｏ３−ＳｉＯ２系結晶化ガラス。
（構成２）
主結晶層としてβ‐石英及び／又はβ‐石英固溶体を含有することを特徴とする、構成１に記載の結晶化ガラス。
（構成３）
主結晶層の平均結晶粒子径が５〜２００ｎｍの範囲であることを特徴とする、構成１または２に記載の結晶化ガラス。
（構成４）
０〜５０℃の温度範囲における平均線膨張係数が０．０±１．０×１０‐７／℃であることを特徴とする、構成１〜３のいずれかの結晶化ガラス。
（構成５）
酸化物換算の質量百分率でＳｉＯ２：４５〜６５％、Ａｌ２Ｏ３：２０〜３０％、Ｌｉ２Ｏ：０．０１〜１０％の範囲の各成分を含有することを特徴とする、構成１〜４のいずれかの結晶化ガラス。
（構成６）
酸化物換算の質量百分率でＴｉＯ２：１〜１０％、ＺｒＯ２：１〜１０％の範囲の各成分を含有することを特徴とする、構成１〜５のいずれかに記載の結晶化ガラス。
（構成７）
酸化物換算の質量百分率でＭｇＯ：０〜５％、ＺｎＯ：０〜５％、ＣａＯ：０〜５％、ＢａＯ：０〜５％、Ｐ２Ｏ５：５〜１５％の範囲の各成分を含有することを特徴とする、構成１〜６のいずれかに記載の結晶化ガラス。
（構成８）
酸化物換算の質量百分率で、Ｐ２Ｏ５成分とＳｉＯ２成分、Ａｌ２Ｏ３成分比がＰ２Ｏ５／ＳｉＯ２＝０．０２〜０．２００、Ｐ２Ｏ５／Ａｌ２Ｏ３＝０．０５９〜０．４４８であることを特徴とする、構成１〜７のいずれかに記載の結晶化ガラス。
（構成９）
酸化物換算の質量百分率で、ＳｉＯ２成分、Ａｌ２Ｏ３成分、Ｐ２Ｏ５成分の含有量ＳｉＯ２＋Ａｌ２Ｏ３＋Ｐ２Ｏ５＝６５．０〜９３．０％であることを特徴とする、構成１〜８のいずれかに記載の結晶化ガラス。
As a result of intensive studies and studies to achieve the above object, the present inventor causes SnO 2 component to be contained as a refining agent in crystallized glass containing each component of SiO 2, Al 2 O 3 and Li 2 O. In particular, the present invention has been achieved by setting the contents of these components within a specific range.
That is, a preferred embodiment of the present invention can be expressed by the following configuration.
(Configuration 1)
It contains each component (as oxide) of SiO 2 , Al 2 O 3 , and Li 2 O, and contains 0.01 to 3% of SnO 2 component (as oxide), Li 2 O -Al 2 O 3 -SiO 2 based crystallized glass.
(Configuration 2)
2. The crystallized glass according to constitution 1, wherein β-quartz and / or β-quartz solid solution is contained as a main crystal layer.
(Configuration 3)
3. The crystallized glass according to Configuration 1 or 2, wherein the main crystal layer has an average crystal particle size in the range of 5 to 200 nm.
(Configuration 4)
The crystallized glass according to any one of constitutions 1 to 3, wherein an average linear expansion coefficient in a temperature range of 0 to 50 ° C. is 0.0 ± 1.0 × 10 −7 / ° C.
(Configuration 5)
SiO 2 in percent by mass of oxide equivalent: 45~65%, Al 2 O 3 : 20~30%, Li 2 O: characterized in that it contains the components of 0.01% to 10% range, structure The crystallized glass in any one of 1-4.
(Configuration 6)
The crystallized glass according to any one of Structures 1 to 5, comprising each component in a range of TiO 2 : 1 to 10% and ZrO 2 : 1 to 10% in terms of mass percentage in terms of oxide.
(Configuration 7)
MgO in percent by mass of oxide equivalent: 0~5%, ZnO: 0~5% , CaO: 0~5%, BaO: 0~5%, P 2 O 5: 5-15% of each ingredient in the range The crystallized glass according to any one of constitutions 1 to 6, wherein the crystallized glass is contained.
(Configuration 8)
In percent by mass of oxide equivalent, P 2 O 5 component and SiO 2 component, Al 2 O 3 component ratio of P 2 O 5 / SiO 2 = 0.02~0.200, P 2 O 5 / Al 2 O 3 = 0.059 to 0.448, The crystallized glass according to any one of the constitutions 1 to 7.
(Configuration 9)
The content of SiO 2 component, Al 2 O 3 component, and P 2 O 5 component is expressed by mass percentage in terms of oxide, and it is characterized by SiO 2 + Al 2 O 3 + P 2 O 5 = 65.0 to 93.0% The crystallized glass according to any one of configurations 1 to 8.
本発明にＬｉ２Ｏ−Ａｌ２Ｏ３−ＳｉＯ２系の結晶化ガラスにおいて、砒素成分やアンチモン成分を含まない組成でも、砒素成分やアンチモン成分と同様の清澄効果を得る事ができ、この系の結晶化ガラスに特徴のある諸物性を維持する事ができる。
さらに、本発明の好ましい態様によれば、Ｌｉ２Ｏ−Ａｌ２Ｏ３−ＳｉＯ２系の結晶化ガラスにおいて、０〜５０℃の温度範囲において平均線膨張係数が０．０±１．０×１０‐７／℃以内である結晶化ガラスを得る事ができる。
さらに、本発明の好ましい態様によれば、平均結晶粒子径が５〜２００ｎｍの微細な結晶粒子であり、ＰｂＯ、Ｎａ２Ｏ、Ｋ２Ｏの各成分のイオンの拡散が無いことを兼ね備えた結晶化ガラスを得る事ができる。
In the Li 2 O—Al 2 O 3 —SiO 2 -based crystallized glass according to the present invention, a clarification effect similar to that of the arsenic component and the antimony component can be obtained even with a composition not containing the arsenic component and the antimony component. Various physical properties characteristic of the crystallized glass can be maintained.
Furthermore, according to a preferred aspect of the present invention, in the Li 2 O—Al 2 O 3 —SiO 2 -based crystallized glass, the average linear expansion coefficient is 0.0 ± 1.0 × in the temperature range of 0 to 50 ° C. Crystallized glass having a temperature within 10 −7 / ° C. can be obtained.
Furthermore, according to a preferred embodiment of the present invention, the crystal is a fine crystal particle having an average crystal particle diameter of 5 to 200 nm and having no diffusion of ions of each component of PbO, Na 2 O, and K 2 O. A glass can be obtained.
Ｌｉ２Ｏ−Ａｌ２Ｏ３−ＳｉＯ２系の結晶化ガラスの特徴のひとつとして、低膨張性が挙げられる。この低膨張性はＬｉ２Ｏ−Ａｌ２Ｏ３−ＳｉＯ２系の結晶化ガラスの組成を特定のものとする事により得る事ができる。半導体製造におけるＥＵＶ光等を使用した次世代リソグラフィー技術に用いられる構成部材には熱的寸法安定性、強度、熱的耐久性、化学的安定性が求められ、特に熱的寸法安定性に必要とされる極低膨張特性が求められており、低膨張性を利用して、Ｌｉ２Ｏ−Ａｌ２Ｏ３−ＳｉＯ２系の結晶化ガラスの前記構成部材への使用が検討されている。
また、好ましい態様であれば、表面の研磨によって次世代リソグラフィーに適用可能な平滑な表面が得られることも、Ｌｉ２Ｏ−Ａｌ２Ｏ３−ＳｉＯ２系の結晶化ガラスの特徴の一つである。
One of the characteristics of the Li 2 O—Al 2 O 3 —SiO 2 -based crystallized glass is low expansion. This low expansibility can be obtained by making the composition of the Li 2 O—Al 2 O 3 —SiO 2 -based crystallized glass specific. Components used in next-generation lithography technology using EUV light in semiconductor manufacturing are required to have thermal dimensional stability, strength, thermal durability, and chemical stability, especially for thermal dimensional stability. Therefore, the use of Li 2 O—Al 2 O 3 —SiO 2 -based crystallized glass for the constituent members has been studied by utilizing the low expansion property.
Also preferred if aspects, also is applicable smooth surface for the next generation lithography obtained by polishing the surface, with one of the characteristics of the crystallized glass of Li 2 O-Al 2 O 3 -SiO 2 system is there.
本発明の結晶化ガラスの好ましい態様について説明する。なお、各成分は特に明記しない限り酸化物換算で表わされた成分であり、各成分の含有量は酸化物換算の質量％で示す。
本発明書において「酸化物換算」とは、本発明の結晶化ガラス構成成分として使用される成分のうち、フッ化物成分、硫酸塩成分、および塩化物成分を除き、それら以外の複合塩等が原ガラス溶融時に全て分解され酸化物へ変化すると仮定した場合に、結晶化ガラス中に含有される各成分を表記する方法である。含有量について表記する場合は、酸化物換算された酸化物の総重量を１００質量％として、結晶化ガラス中に含有される各成分を表記する。
A preferred embodiment of the crystallized glass of the present invention will be described. Each component is a component expressed in terms of oxide unless otherwise specified, and the content of each component is expressed in mass% in terms of oxide.
In the present invention, “oxide conversion” means that, among the components used as the crystallized glass component of the present invention, except for the fluoride component, the sulfate component, and the chloride component, other complex salts, etc. This is a method of noting each component contained in the crystallized glass when it is assumed that all of the raw glass is decomposed and changed into oxides when the raw glass is melted. When describing about content, each component contained in crystallized glass is described by making the total weight of the oxide converted into oxide into 100 mass%.
ＳｉＯ２成分、Ａｌ２Ｏ３成分及びＬｉ２Ｏ成分を含有するＬｉ２Ｏ−Ａｌ２Ｏ３−ＳｉＯ２系の結晶化ガラスにおいて、上述の特徴を維持しつつ、ＳｎＯ２成分を含有させることで、Ａｓ２Ｏ３成分やＳｂ２Ｏ３成分と同様の高い清澄効果を得る事ができる。
前記の特徴を維持しつつ、高い清澄効果を得るためには、ＳｎＯ２成分を含有させることが有用である。ＳｎＯ２成分の含有量の下限は、質量％で０．０１％であることが好ましく、より好ましくは０．１％であり、最も好ましくは０．５％である。また同様に、前記の特徴を維持しつつ、高い清澄効果を得るためには、ＳｎＯ２成分の含有量の上限は、質量％で共に３．０％であることが好ましく、より好ましくは１．５％であり、最も好ましくは１．３５％である。
In a Li 2 O—Al 2 O 3 —SiO 2 -based crystallized glass containing a SiO 2 component, an Al 2 O 3 component, and a Li 2 O component, the SnO 2 component is contained while maintaining the above-mentioned characteristics. Thus, the same high clarification effect as that of the As 2 O 3 component or the Sb 2 O 3 component can be obtained.
In order to obtain a high clarification effect while maintaining the above characteristics, it is useful to contain a SnO 2 component. The lower limit of the content of the SnO 2 component is preferably 0.01% by mass, more preferably 0.1%, and most preferably 0.5%. Similarly, in order to obtain a high refining effect while maintaining the above characteristics, the upper limit of the content of the SnO 2 component is preferably 3.0% by mass%, more preferably 1. 5%, most preferably 1.35%.
本明細書において、「結晶化ガラス」とは、ガラスを熱処理することによりガラス相中に結晶を析出させて得られる材料であり、非晶質固体と結晶からなる材料をいう。 In this specification, “crystallized glass” is a material obtained by precipitating crystals in a glass phase by heat-treating glass, and means a material composed of an amorphous solid and crystals.
本明細書において「ΔＬ／Ｌの最大値−最小値」とは、０℃の時の結晶化ガラスの長さＬ、当該ガラスセラミックスの任意の温度における長さの変化量をΔＬとし、その任意の温度範囲における、ΔＬ／Ｌの値の最大値と最小値の差を示すものである。 In this specification, “maximum value−minimum value of ΔL / L” means the length L of crystallized glass at 0 ° C., and the amount of change in length of the glass ceramic at an arbitrary temperature as ΔL. The difference between the maximum value and the minimum value of ΔL / L in the temperature range is shown.
本明細書において、極低膨張特性とは、０〜５０℃の温度範囲において、平均線膨張係数（α）が０．０±１．０（１０‐７／℃）以内ならびにΔＬ／Ｌの最大値−最小値が１０×１０‐７以内の範囲、好ましくは平均線膨張係数が０．０±０．２（１０‐７／℃）以内ならびにΔＬ／Ｌの最大値−最小値が１０×１０‐７以内の範囲、より好ましくは平均線膨張係数が０．０±０．１（１０‐７／℃）以内ならびにΔＬ／Ｌの最大値−最小値が８×１０‐７以内の範囲の値であることをいう。 In the present specification, the extremely low expansion characteristic means that the average linear expansion coefficient (α) is within 0.0 ± 1.0 (10 −7 / ° C.) and the maximum ΔL / L in the temperature range of 0 to 50 ° C. Value-minimum value within a range of 10 × 10 −7 , preferably within an average linear expansion coefficient of 0.0 ± 0.2 (10 −7 / ° C.) and ΔL / L maximum value—minimum value of 10 × 10 -7 , more preferably average linear expansion coefficient within 0.0 ± 0.1 (10 -7 / ° C) and ΔL / L maximum value-minimum value within 8 × 10 -7 It means that.
本明細書において、主結晶相とは、析出比が比較的大きい結晶相全てを指す。すなわち、Ｘ線回折におけるＸ線チャート（縦軸はＸ線回折強度、横軸は回折角度）において、もっとも析出割合の多い結晶相のメインピーク（最も高いピーク）のＸ線回折強度を１００とした場合、各析出相のメインピーク（各結晶相における最も高いピーク）のＸ線回折強度の比（以下、Ｘ線強度比という）が、３０以上あるもの全てを主結晶相という。なお、主結晶相以外の結晶のＸ線強度比は２０未満が好ましく、更に好ましくは１０未満、最も好ましくは５未満である。 In this specification, the main crystal phase refers to all crystal phases having a relatively large precipitation ratio. That is, in the X-ray chart in X-ray diffraction (the vertical axis is the X-ray diffraction intensity, the horizontal axis is the diffraction angle), the X-ray diffraction intensity of the main peak (highest peak) of the crystal phase with the highest precipitation ratio is 100. In this case, all the crystals having a ratio of X-ray diffraction intensity (hereinafter referred to as X-ray intensity ratio) of the main peak (the highest peak in each crystal phase) of each precipitation phase to 30 or more are referred to as a main crystal phase. The X-ray intensity ratio of the crystals other than the main crystal phase is preferably less than 20, more preferably less than 10, and most preferably less than 5.
平均線膨張係数についてであるが、各種半導体製造装置や超精密部材分野では、高精度化に対応し得る材料の熱膨張特性が要求される。この様な要求を満足するためには０〜５０℃の温度範囲における平均線膨張係数をα＝０．０±０．５（１０‐７／℃）以下とする事が好ましい。より好ましくは、α＝０．０±０．４（１０‐７／℃）以下である。本発明の結晶化ガラスの好適な態様においては、平均線膨張係数及びΔＬ／Ｌの最大値−最小値が上記範囲内の値となる。当該物性に関係する結晶化ガラスの成分の組成を後述する範囲に調整することにより、α＝０．０±０．５（１０‐７／℃）以下の物性が容易に得られやすくなり、更に調整することによりα＝０．０±０．１（１０‐７／℃）以下の物性でも得られやすくなる。
尚、本明細書において平均線膨張係数は、特に注記しない限り（／℃）の単位で表示する。
Regarding the average coefficient of linear expansion, in the fields of various semiconductor manufacturing apparatuses and ultra-precision members, thermal expansion characteristics of materials that can cope with higher precision are required. In order to satisfy such a requirement, it is preferable that the average linear expansion coefficient in the temperature range of 0 to 50 ° C. is α = 0.0 ± 0.5 (10 −7 / ° C.) or less. More preferably, α = 0.0 ± 0.4 (10 −7 / ° C.) or less. In a preferred embodiment of the crystallized glass of the present invention, the average linear expansion coefficient and the maximum value-minimum value of ΔL / L are values within the above range. By adjusting the composition of the components of the crystallized glass related to the physical properties to the range described later, physical properties of α = 0.0 ± 0.5 (10 −7 / ° C.) or less can be easily obtained. By adjusting, it becomes easy to obtain even physical properties of α = 0.0 ± 0.1 (10 −7 / ° C.) or less.
In this specification, the average linear expansion coefficient is expressed in units of (/ ° C.) unless otherwise noted.
また同様に、要求される高精度化に対応し得る材料の熱膨張特性を満足するためには０〜５０℃の温度範囲におけるΔＬ／Ｌの最大値−最小値が１０×１０‐７以内の範囲とする事が好ましい。本発明の結晶化ガラスの好適な態様においては、ΔＬ／Ｌの最大値−最小値が上記範囲内の値となる。より好ましくは、ΔＬ／Ｌの最大値−最小値が９×１０‐７以内である。本発明の結晶化ガラスは結晶化熱処理条件を調整することによりΔＬ／Ｌの最大値−最小値が１０×１０‐７以内の物性が得られやすくなる。さらに結晶化熱処理条件を厳密に調整することにより、ΔＬ／Ｌの最大値−最小値が９×１０‐７以内の物性が得られやすくなり、さらに８×１０‐７以内の物性を得ることもできる。 Similarly, in order to satisfy the thermal expansion characteristics of the material that can meet the required high precision, the maximum value-minimum value of ΔL / L in the temperature range of 0 to 50 ° C. is within 10 × 10 −7 . It is preferable to set the range. In a preferred embodiment of the crystallized glass of the present invention, the maximum value-minimum value of ΔL / L is a value within the above range. More preferably, the maximum value-minimum value of ΔL / L is within 9 × 10 −7 . In the crystallized glass of the present invention, physical properties having a maximum value-minimum value of ΔL / L within 10 × 10 −7 are easily obtained by adjusting the crystallization heat treatment conditions. Furthermore, by strictly adjusting the crystallization heat treatment conditions, it becomes easier to obtain physical properties within the maximum value-minimum value of ΔL / L within 9 × 10 −7 , and further with physical properties within 8 × 10 −7. it can.
次に研磨後の表面粗度ならびに析出結晶径について述べる。各種半導体製造装置や超精密部材分野では、高精度化に対応し得る基板表面の平滑性が重要である。この平滑性を保つために、平均結晶粒子径と表面粗度の関係に注目するべきである。本発明の結晶化ガラスの各種半導体製造装置や超精密部材分野への適用を考慮した場合には研磨後の表面粗度Ｒａは３Å以下が好ましく、２Å以下がより好ましい。この平滑性を容易に得るためには材料の析出結晶の平均結晶粒子径は２００ｎｍ以下が好ましく、より好ましくは９０ｎｍ以下、最も好ましくは８０ｎｍ以下である。一方で、結晶化ガラスの機械的強度を所望のものとするために平均結晶粒子径は５ｎｍ以上が好ましく、より好ましくは５０ｎｍ以上、最も好ましくは６０ｎｍ以上である。析出結晶径に関係する結晶化ガラスの成分の組成を後述する範囲に調整し、結晶化条件を調整することにより、前述の研磨後の表面粗度Ｒａの値、及び平均結晶粒子径の値が得られやすくなる。 Next, the surface roughness after polishing and the precipitated crystal diameter will be described. In the fields of various semiconductor manufacturing equipment and ultra-precision members, the smoothness of the substrate surface that can cope with higher precision is important. In order to maintain this smoothness, attention should be paid to the relationship between the average crystal grain size and the surface roughness. In consideration of application of the crystallized glass of the present invention to various semiconductor manufacturing apparatuses and the field of ultraprecision members, the surface roughness Ra after polishing is preferably 3 mm or less, and more preferably 2 mm or less. In order to easily obtain this smoothness, the average crystal particle diameter of the precipitated crystals of the material is preferably 200 nm or less, more preferably 90 nm or less, and most preferably 80 nm or less. On the other hand, in order to obtain the desired mechanical strength of the crystallized glass, the average crystal particle size is preferably 5 nm or more, more preferably 50 nm or more, and most preferably 60 nm or more. By adjusting the composition of the component of the crystallized glass related to the precipitated crystal diameter to the range described later, and adjusting the crystallization conditions, the value of the surface roughness Ra after polishing and the value of the average crystal particle diameter are It becomes easy to obtain.
本発明の結晶化ガラスにおいて、低膨張特性は、負の平均線膨張係数を有する主結晶相を析出させ、ガラス相が有する正の膨張係数と結晶相が有する負の膨張係数を相殺させることによって得る事ができる。極低膨張特性を得るためには、結晶化ガラスの主結晶相には、β‐石英（β‐ＳｉＯ２）、及び／又はβ‐石英固溶体（β‐ＳｉＯ２固溶体）を含有する事が好ましい。析出する結晶相に関係する結晶化ガラスの成分の組成を後述する範囲に調整し、結晶化条件を調整することにより、極低膨張特性が得られやすくなる。なお、本明細書において、β‐石英固溶体とはβ‐石英にＳｉおよびＯ以外の元素が侵入したもの（ｉｎｔｅｒｓｔｉｔｉａｌ）及び／又は置換したもの（ｓｕｂｓｔｉｔｕｔｉｏｎａｌ）を指す。特に、Ｓｉ４＋がＡｌ３＋と置換されＬｉ＋、Ｍｇ２＋、Ｚｎ２＋原子が添加され平衡を保つ結晶体である事が好ましい。（尚、その代表としてβ‐ユークリプタイトが挙げられる。） In the crystallized glass of the present invention, the low expansion property is obtained by precipitating the main crystal phase having a negative average linear expansion coefficient and canceling out the positive expansion coefficient of the glass phase and the negative expansion coefficient of the crystal phase. I can get it. In order to obtain extremely low expansion characteristics, it is preferable that the main crystal phase of the crystallized glass contains β-quartz (β-SiO 2 ) and / or β-quartz solid solution (β-SiO 2 solid solution). . By adjusting the composition of the components of the crystallized glass related to the crystal phase to be precipitated within the range described later and adjusting the crystallization conditions, it becomes easy to obtain extremely low expansion characteristics. In the present specification, β-quartz solid solution refers to β-quartz in which elements other than Si and O have intruded (interstitial) and / or substituted (substitutive). In particular, it is preferable that Si 4+ is replaced with Al 3+ and Li + , Mg 2+ , and Zn 2+ atoms are added to maintain the equilibrium. (In addition, β-eucryptite is a representative example.)
ＳｉＯ２成分は、原ガラスの熱処理により、主結晶相としてβ‐石英及び／又はβ‐石英固溶体を析出させる場合に関係する成分であるが、その量が４５％以上であると、得られた結晶化ガラスの析出結晶が安定し組織が粗大化しにくく、結果的に機械的強度が向上し、研磨して得られる表面粗度も小さくなる。また、６５％以下であると原ガラスの溶融・成形性が容易であり、均質性が向上する。前記効果をより容易に得るには、成分量の下限は５１％がより好ましく、５３％が最も好ましい。また、成分量の上限は６０％がより好ましく、５８％が最も好ましい。 The SiO 2 component is a component related to the case where β-quartz and / or β-quartz solid solution is precipitated as the main crystal phase by heat treatment of the raw glass, but was obtained when the amount was 45% or more. The precipitated crystal of the crystallized glass is stable and the structure is not easily coarsened. As a result, the mechanical strength is improved and the surface roughness obtained by polishing is also reduced. On the other hand, if it is 65% or less, the melting and moldability of the original glass is easy and the homogeneity is improved. In order to obtain the effect more easily, the lower limit of the component amount is more preferably 51%, and most preferably 53%. Further, the upper limit of the component amount is more preferably 60%, and most preferably 58%.
Ａｌ２Ｏ３成分は、その量が２０％以上であると原ガラスの溶融が容易となり、そのため、得られる結晶化ガラスの均質性が向上し、更に結晶化ガラスの化学的耐久性も良好なものとなる。また、３０％以下であると原ガラスの耐失透性が向上し、耐失透性の低下が原因となって結晶化段階で結晶化ガラスの組織が粗大化することがなくなり、機械的強度が向上する。
前記効果をより容易に得るには、成分量の下限は２０％がより好ましく、２２％が最も好ましい。また、同様に前記効果をより容易に得るには、成分量の上限は２７％がより好ましく、２６％が最も好ましい。
When the amount of the Al 2 O 3 component is 20% or more, the original glass can be easily melted. Therefore, the homogeneity of the obtained crystallized glass is improved, and the chemical durability of the crystallized glass is also good. It will be a thing. Further, if it is 30% or less, the devitrification resistance of the original glass is improved, and the structure of the crystallized glass is not coarsened in the crystallization stage due to the decrease in the devitrification resistance. Will improve.
In order to obtain the effect more easily, the lower limit of the component amount is more preferably 20%, and most preferably 22%. Similarly, in order to obtain the effect more easily, the upper limit of the component amount is more preferably 27%, and most preferably 26%.
Ｐ２Ｏ５成分は、原ガラスの溶融・清澄性を向上させる効果と、熱処理結晶化後の熱膨張を所望の値に安定化させる効果を有し、ＳｉＯ２成分と共存させることによりその効果はより大きくなる。本発明の結晶化ガラスにおいてはＰ２Ｏ５成分の量が１％以上であると前記の効果が飛躍的に向上し、また１３％以下であると、原ガラスの耐失透性が良く、耐失透性の低下が原因となって結晶化段階でガラスセラミックスの組織が粗大化することがなくなり、機械的強度が向上する。前記効果をより容易に得るには、成分量の下限は４％がより好ましく、６％が最も好ましい。また、同様に前記効果をより容易に得るには、成分量の上限は１０％がより好ましく、９％が最も好ましい。 The P 2 O 5 component has the effect of improving the melting and clarifying properties of the original glass and the effect of stabilizing the thermal expansion after the heat treatment crystallization to a desired value, and the effect by coexisting with the SiO 2 component. Becomes bigger. In the crystallized glass of the present invention, when the amount of the P 2 O 5 component is 1% or more, the above effect is remarkably improved, and when it is 13% or less, the devitrification resistance of the original glass is good, Due to the decrease in devitrification resistance, the structure of the glass ceramic is not coarsened in the crystallization stage, and the mechanical strength is improved. In order to obtain the effect more easily, the lower limit of the component amount is more preferably 4%, and most preferably 6%. Similarly, in order to obtain the effect more easily, the upper limit of the component amount is more preferably 10%, and most preferably 9%.
更にＳｉＯ２＋Ａｌ２Ｏ３＋Ｐ２Ｏ５＝６５〜９３％、Ｐ２Ｏ５成分とＳｉＯ２成分質量％の比がＰ２Ｏ５／ＳｉＯ２＝０．０２〜０．２００、Ｐ２Ｏ５成分とＡｌ２Ｏ３成分質量％の比がＰ２Ｏ５／Ａｌ２Ｏ３＝０．０５９〜０．４４８、これらのいずれか、又は２つ以上の条件を満たすと、０〜５０℃の温度範囲において、低膨張特性を著しく向上させ易く、極低膨張特性を容易に得ることができる。より容易に前記効果を得るには、ＳｉＯ２＋Ａｌ２Ｏ３＋Ｐ２Ｏ５の含有量の下限は７５％がより好ましく、８０％が最も好ましい。また同様に、より容易に前記効果を得るには、ＳｉＯ２＋Ａｌ２Ｏ３＋Ｐ２Ｏ５の含有量の上限は９１％がより好ましく、８９％が最も好ましい。
より容易に前記効果を得るには、Ｐ２Ｏ５／ＳｉＯ２の下限は０．０８がより好ましく、０．１２が最も好ましい。また同様に、より容易に前記効果を得るには、Ｐ２Ｏ５／ＳｉＯ２の上限は０．１６がより好ましく、０．１４が最も好ましい。
より容易に前記効果を得るには、Ｐ２Ｏ５／Ａｌ２Ｏ３の下限は０．１５０がより好ましく、０．２５０が最も好ましい。また同様に、より容易に前記効果を得るには、Ｐ２Ｏ５／Ａｌ２Ｏ３の上限は０．４００がより好ましく、０．３５０が最も好ましい。
Furthermore, SiO 2 + Al 2 O 3 + P 2 O 5 = 65 to 93%, the ratio of P 2 O 5 component to SiO 2 component mass% is P 2 O 5 / SiO 2 = 0.02 to 0.200, P 2 O When the ratio of 5 components to 3 % by mass of Al 2 O 3 is P 2 O 5 / Al 2 O 3 = 0.059 to 0.448, one of these, or two or more conditions, 0 to 50 ° C. In this temperature range, the low expansion characteristic can be remarkably improved, and the extremely low expansion characteristic can be easily obtained. In order to obtain the effect more easily, the lower limit of the content of SiO 2 + Al 2 O 3 + P 2 O 5 is more preferably 75%, and most preferably 80%. Similarly, in order to obtain the effect more easily, the upper limit of the content of SiO 2 + Al 2 O 3 + P 2 O 5 is more preferably 91%, and most preferably 89%.
In order to obtain the effect more easily, the lower limit of P 2 O 5 / SiO 2 is more preferably 0.08, and most preferably 0.12. Similarly, in order to obtain the effect more easily, the upper limit of P 2 O 5 / SiO 2 is more preferably 0.16, and most preferably 0.14.
In order to obtain the effect more easily, the lower limit of P 2 O 5 / Al 2 O 3 is more preferably 0.150, and most preferably 0.250. Similarly, in order to obtain the effect more easily, the upper limit of P 2 O 5 / Al 2 O 3 is more preferably 0.400, and most preferably 0.350.
Ｌｉ２Ｏ、ＭｇＯ、ＺｎＯの３成分は、β‐石英固溶体の構成要素となり易い成分であるが、これらの３成分は、前記組成範囲のＳｉＯ２成分およびＰ２Ｏ５成分との共存により、結晶化ガラスの低膨張特性向上や高温時のたわみ量を低減させ易く、更に原ガラスの溶融性、清澄性を著しく向上させるのを容易にする成分である。これらの３成分は前記効果を容易に得たい場合に各々の成分について任意で含有できる。 The three components Li 2 O, MgO, and ZnO are components that are likely to be constituent elements of the β-quartz solid solution, but these three components are coexistent with the SiO 2 component and the P 2 O 5 component in the above composition range, It is a component that makes it easy to improve the low expansion characteristics of crystallized glass and to reduce the amount of deflection at high temperatures, and to further significantly improve the meltability and clarity of the original glass. These three components can be optionally contained for each component when it is desired to easily obtain the above effects.
Ｌｉ２Ｏ成分は、その量が１％以上であると前記効果が飛躍的に向上し、また、原ガラスの溶融性が向上することにより均質性が向上し、さらにβ‐石英又はβ‐石英固溶体の析出が飛躍的に向上するためより好ましい。また８％以下であると低膨張特性が飛躍的に向上し、極低膨張特性を容易に得ることができ、原ガラスの耐失透性がより向上し、耐失透性の低下に起因する結晶化段階後の結晶化ガラス中の析出結晶の粗大化を抑制し、機械的強度が向上する。前記効果をより容易に得るには、成分量の下限は３％が最も好ましい。また、上記の効果をより得やすくするために成分量の上限は６％がより好ましく、５％が最も好ましい。 When the amount of the Li 2 O component is 1% or more, the above-described effect is remarkably improved, and the homogeneity is improved by improving the meltability of the original glass. Further, β-quartz or β-quartz Since precipitation of a solid solution improves remarkably, it is more preferable. Further, if it is 8% or less, the low expansion characteristic is remarkably improved, and the extremely low expansion characteristic can be easily obtained, the devitrification resistance of the original glass is further improved, and the devitrification resistance is lowered. The coarsening of the precipitated crystal in the crystallized glass after the crystallization stage is suppressed, and the mechanical strength is improved. In order to obtain the effect more easily, the lower limit of the component amount is most preferably 3%. Further, in order to make it easier to obtain the above effects, the upper limit of the component amount is more preferably 6%, and most preferably 5%.
ＭｇＯ成分は前記効果を得るために任意で含有させることができる成分である。添加する場合、その量が０．１％以上であると前記効果が飛躍的に向上し、また５％以下であると低膨張特性が飛躍的に向上し、極低膨張特性を得ることができる。前記効果をより容易に得るには、成分量の下限は０．４％がより好ましく、０．５％が最も好ましい。また同様に、前記効果をより容易に得るには、成分量の上限は３％がより好ましく、２％が最も好ましい。 The MgO component is a component that can be optionally contained to obtain the above effect. When added, if the amount is 0.1% or more, the above-mentioned effect is drastically improved, and if it is 5% or less, the low expansion characteristics are drastically improved, and extremely low expansion characteristics can be obtained. . In order to obtain the effect more easily, the lower limit of the component amount is more preferably 0.4%, and most preferably 0.5%. Similarly, in order to obtain the effect more easily, the upper limit of the component amount is more preferably 3%, and most preferably 2%.
ＺｎＯ成分は前記効果を得るために任意で含有させることができる成分である。添加する場合、その量が０．１％以上であると前記効果が飛躍的に向上し、また５．５％以下であると低膨張特性が飛躍的に向上し、極低膨張特性を容易に得ることができる。その他、原ガラスの耐失透性がより向上し、耐失透性の低下に起因する結晶化段階後のガラスセラミックス中の析出結晶の粗大化を抑制し、機械的強度が向上する。前記効果をより容易に得るには、成分量の下限は０．２％がより好ましく、０．３％が最も好ましい、また同様に、前記効果をより容易に得るには、成分量の上限は４％がより好ましく、３％が最も好ましい。 The ZnO component is a component that can be optionally contained in order to obtain the above effect. When added, if the amount is 0.1% or more, the effect is drastically improved, and if it is 5.5% or less, the low expansion characteristic is remarkably improved, and extremely low expansion characteristic is easily achieved. Can be obtained. In addition, the devitrification resistance of the original glass is further improved, and the coarsening of the precipitated crystals in the glass ceramic after the crystallization stage due to the decrease in the devitrification resistance is suppressed, and the mechanical strength is improved. In order to obtain the effect more easily, the lower limit of the component amount is more preferably 0.2%, and most preferably 0.3%. Similarly, in order to obtain the effect more easily, the upper limit of the component amount is 4% is more preferred and 3% is most preferred.
ＣａＯ、ＢａＯの２成分は、基本的にガラス中に析出した結晶以外のガラスマトリックス中に残存し、極低膨張特性および溶融性改善の効果に影響を与えるものであり、結晶相とガラスマトリックス相の相対量の微調整成分として任意に含有させることができる。 The two components of CaO and BaO basically remain in the glass matrix other than the crystals precipitated in the glass, and affect the effect of improving the extremely low expansion characteristics and the meltability. The crystal phase and the glass matrix phase It can be optionally contained as a fine adjustment component of the relative amount.
ＣａＯ成分は前記効果を得るために任意で含有させることができる成分である。その量が０．３％以上で溶融清澄効果が顕著に得られ、７％以下であると低膨張特性が飛躍的に向上し、極低膨張特性を容易に得ることができる。その他、原ガラスの耐失透性がより向上し、耐失透性の低下に起因する結晶化段階後の結晶化ガラス中の析出結晶の粗大化を抑制し、機械的強度が向上する。前記効果をより容易に得るには、成分量の下限は０．５％が最も好ましい。また同様に、前記効果をより容易に得るには、成分量の上限は５％がより好ましく、３％が最も好ましい。 The CaO component is a component that can be optionally contained in order to obtain the effect. When the amount is 0.3% or more, the melt clarification effect is remarkably obtained, and when it is 7% or less, the low expansion characteristic is remarkably improved, and the extremely low expansion characteristic can be easily obtained. In addition, the devitrification resistance of the original glass is further improved, and the coarsening of the precipitated crystals in the crystallized glass after the crystallization stage due to the decrease in the devitrification resistance is suppressed, and the mechanical strength is improved. In order to obtain the effect more easily, the lower limit of the component amount is most preferably 0.5%. Similarly, in order to obtain the effect more easily, the upper limit of the component amount is more preferably 5%, and most preferably 3%.
ＢａＯ成分は前記効果を得るために任意で含有させることができる成分である。その量が０．３％以上、４％以下であると低膨張特性が飛躍的に向上し、極低膨張特性を容易に得ることができる。その他、原ガラスの耐失透性がより向上し、耐失透性の低下に起因する結晶化段階後の結晶化ガラス中の析出結晶の粗大化を抑制し、機械的強度が向上する。
前記効果をより容易に得るには、成分量の下限は０．５％が最も好ましい。また同様に、前記効果をより容易に得るには、成分量の上限は５％がより好ましく、３％が最も好ましい。
The BaO component is a component that can be optionally contained in order to obtain the above effects. When the amount is 0.3% or more and 4% or less, the low expansion characteristic is remarkably improved, and the extremely low expansion characteristic can be easily obtained. In addition, the devitrification resistance of the original glass is further improved, and the coarsening of the precipitated crystals in the crystallized glass after the crystallization stage due to the decrease in the devitrification resistance is suppressed, and the mechanical strength is improved.
In order to obtain the effect more easily, the lower limit of the component amount is most preferably 0.5%. Similarly, in order to obtain the effect more easily, the upper limit of the component amount is more preferably 5%, and most preferably 3%.
ＴｉＯ２成分およびＺｒＯ２成分は、いずれも結晶核形成剤として有用な成分である。これらの成分の量がそれぞれ１％以上であると目的とする結晶相の析出が可能となる。またそれぞれ１０％以下であると不熔物の発生が無くなって原ガラスの溶融性が良好となり均質性が向上する。前記効果をより容易に得るには、ＴｉＯ２の成分量の下限は１．３％がより好ましく、１．５％が最も好ましい。ＺｒＯ２の成分量の下限は１．２％がより好ましく、１．５％が最も好ましい。また同様に、前記効果をより容易に得るには、ＴｉＯ２の成分量の上限は、７％がより好ましく、５％がさらに好ましく、３％が最も好ましい。ＺｒＯ２の成分量の上限は７％がより好ましく、５％がさらに好ましく、３％が最も好ましい。 The TiO 2 component and the ZrO 2 component are both useful components as crystal nucleating agents. When the amount of each of these components is 1% or more, the target crystal phase can be precipitated. Further, when the content is 10% or less, insoluble matter is not generated, the meltability of the original glass is improved, and the homogeneity is improved. In order to obtain the effect more easily, the lower limit of the component amount of TiO 2 is more preferably 1.3%, and most preferably 1.5%. The lower limit of the component amount of ZrO 2 is more preferably 1.2%, and most preferably 1.5%. Similarly, in order to obtain the effect more easily, the upper limit of the component amount of TiO 2 is more preferably 7%, further preferably 5%, and most preferably 3%. The upper limit of the component amount of ZrO 2 is more preferably 7%, further preferably 5%, and most preferably 3%.
Ａｓ２Ｏ３成分やＳｂ２Ｏ３成分は、環境上有害となりうる成分であり、その使用は極力少なくするべきである。本発明の結晶化ガラスはＡｓ２Ｏ３成分やＳｂ２Ｏ３成分を含有しなくても清澄効果を得る事ができるため、環境への影響を軽減するためにＡｓ２Ｏ３成分やＳｂ２Ｏ３成分は含まないことが好ましい。 As 2 O 3 component and Sb 2 O 3 component are components that can be harmful to the environment, and their use should be minimized. Since the crystallized glass of the present invention which can obtain the clarifying effect even without containing As 2 O 3 component and the Sb 2 O 3 component, As 2 O 3 component or Sb 2 in order to reduce the impact on the environment It is preferable that no O 3 component is contained.
尚、上記成分の他に特性の微調整等を目的として、本発明の結晶化ガラスの特性を損なわない範囲で、ＳｒＯ、Ｂ２Ｏ３、Ｆ２、Ｌａ２Ｏ３、Ｂｉ２Ｏ３、ＷＯ３、Ｙ２Ｏ３、Ｇｄ２Ｏ３成分を１種または２種以上の合計量で２％以下、他にもＣｏＯ、ＮｉＯ、ＭｎＯ２、Ｆｅ２Ｏ３、Ｃｒ２Ｏ３等の着色成分を１種または２種以上の合計量で２％以下まで、それぞれ添加し得る。しかし、本発明の結晶化ガラスを高い光線透過率が求められる用途に用いる場合には、前記着色成分は含まない事が好ましい。 In addition to the above components, SrO, B 2 O 3 , F 2 , La 2 O 3 , Bi 2 O 3 , S2O 3 , F 2 , La 2 O 3 , Bi 2 O 3 , as long as the characteristics of the crystallized glass of the present invention are not impaired. WO 3 , Y 2 O 3 , Gd 2 O 3 components are combined in a total amount of 1 or 2% and 2% or less, and other colors such as CoO, NiO, MnO 2 , Fe 2 O 3 , Cr 2 O 3, etc. Ingredients may be added to each of up to 2% or less in a total amount of one or more. However, when the crystallized glass of the present invention is used for applications requiring high light transmittance, it is preferable that the colored component is not included.
フッ化物成分、硫酸塩成分は清澄効果が期待でき、任意で含有できる。また、フッ化物成分は、例えばＭｇＦ２やＣａＦ２として、硫酸塩成分は、例えばＢａＳＯ４等として添加することができる。これらの成分による清澄効果を得る場合には、これらの成分以外の酸化物換算の組成１００重量部に対し、Ｆ２に換算したフッ化物成分、ＳＯ３に換算した硫酸塩成分に換算した塩化物成分の合計の添加量の下限が０．０５重量部であることがより好ましく、０．１５重量部であることが最も好ましい。同様にこれらの成分の合計の含有量の上限としては５重量部で十分であり、２重量部がより好ましく、１．５重量部が最も好ましい。
これらの成分による清澄効果を得る場合のこれらの成分の各々の添加量の下限は０．０５重量部がより好ましく、最も好ましくは０．１５重量部である。また同様に、その効果を得る場合には前記成分の各々の添加量の上限は３重量部であることが好ましく、より好ましくは２重量部、最も好ましくは１．５重量部である。
The fluoride component and sulfate component can be expected to have a clarification effect, and can be optionally contained. Further, the fluoride component, for example, as MgF 2 and CaF 2, sulfate components can be added as for example BaSO 4 and the like. When the clarification effect by these components is obtained, with respect to 100 parts by weight of the oxide conversion composition other than these components, the fluoride component converted to F 2 and the chloride converted to the sulfate component converted to SO 3 The lower limit of the total amount of components added is more preferably 0.05 parts by weight, and most preferably 0.15 parts by weight. Similarly, 5 parts by weight is sufficient as the upper limit of the total content of these components, 2 parts by weight is more preferred, and 1.5 parts by weight is most preferred.
When the clarification effect by these components is obtained, the lower limit of the amount of each of these components added is more preferably 0.05 parts by weight, and most preferably 0.15 parts by weight. Similarly, in order to obtain the effect, the upper limit of the amount of each component added is preferably 3 parts by weight, more preferably 2 parts by weight, and most preferably 1.5 parts by weight.
また、ＣｅＯ２成分、ＭｎＯ２成分、ＷＯ３成分、Ｔａ２Ｏ５成分、Ｎｂ２Ｏ５成分についても清澄効果が期待でき、フッ化物成分、硫酸塩成分と代替で、又はこれらの成分と共に任意で含有できる。
清澄効果を得る場合には、ＣｅＯ２成分、ＭｎＯ２成分、ＷＯ３成分、Ｔａ２Ｏ５成分、Ｎｂ２Ｏ５成分の合計の含有量の下限が０．０５％であることがより好ましく、０．２％であることが最も好ましい。同様にこれらの成分の合計の含有量の上限としては５％で十分であり、３％がより好ましく、１．５％が最も好ましい。清澄効果を得る場合のこれらの成分の各々の含有量の下限は０．０５％がより好ましく、最も好ましくは０．２％である。また同様に、その効果を得る場合には前記成分の各々の含有量の上限は５％であることが好ましく、より好ましくは２％、最も好ましくは１．５％である。
In addition, CeO 2 component, MnO 2 component, WO 3 component, Ta 2 O 5 component, Nb 2 O 5 component can be expected to have a clarification effect, and can be used in place of or in combination with fluoride component and sulfate component. Can be contained.
When obtaining a clarification effect, the lower limit of the total content of CeO 2 component, MnO 2 component, WO 3 component, Ta 2 O 5 component, Nb 2 O 5 component is more preferably 0.05%, Most preferably, it is 0.2%. Similarly, 5% is sufficient as the upper limit of the total content of these components, 3% is more preferable, and 1.5% is most preferable. The lower limit of the content of each of these components when obtaining a clarification effect is more preferably 0.05%, and most preferably 0.2%. Similarly, in order to obtain the effect, the upper limit of the content of each component is preferably 5%, more preferably 2%, and most preferably 1.5%.
本発明の結晶化ガラスにおいて極低膨張特性を得ようとする場合は、負の平均線膨張係数を有する主結晶相を析出させ、正の平均線膨張係数を有するガラスマトリックス相と相まって、全体として極低膨張特性を実現している。このためには正の平均線膨張係数を有する結晶相、すなわち、二珪酸リチウム、珪酸リチウム、α‐石英、α‐クリストバライト、α‐トリジマイト、Ｚｎ‐ペタライトをはじめとするペタライト、ウォラストナイト、フォルステライト、ディオプサイト、ネフェリン、クリノエンスタタイト、アノーサイト、セルシアン、ゲーレナイト、フェルスパー、ウィレマイト、ムライト、コランダム、ランキナイト、ラルナイトおよびこれらの固溶体等を含まないことが好ましく、これらに加えて、良好な機械的強度を維持するためには、Ｈｆ‐タングステン酸塩やＺｒ‐タングステン酸塩をはじめとするタングステン酸塩、チタン酸マグネシウムやチタン酸バリウムやチタン酸マンガンをはじめとするチタン酸塩、ムライト、３ケイ酸２バリウム、Ａｌ２Ｏ３・５ＳｉＯ２およびこれらの固溶体等も含まないことが好ましい。 When trying to obtain extremely low expansion characteristics in the crystallized glass of the present invention, the main crystal phase having a negative average linear expansion coefficient is precipitated, combined with the glass matrix phase having a positive average linear expansion coefficient, as a whole Realizes extremely low expansion characteristics. For this purpose, crystalline phases having a positive average linear expansion coefficient, i.e. lithium disilicate, lithium silicate, α-quartz, α-cristobalite, α-tridymite, Zn-petalite and other wollastonites, wollastonites, It is preferable not to contain stellite, diopsite, nepheline, clinoenstatite, anorthite, celsian, gelenite, felsper, willemite, mullite, corundum, lanquinite, larnite and solid solutions thereof, in addition to these, good In order to maintain high mechanical strength, tungstates including Hf-tungstate and Zr-tungstate, titanates including magnesium titanate, barium titanate and manganese titanate, mullite 3 barium silicates, is preferably free l 2 O 3 · 5SiO 2 and also those solid solutions.
次に、本発明の結晶化ガラスは以下の方法により製造する。まずガラス原料を秤量、調合し、坩堝などに入れ、約１４５０〜１６００℃で溶融し、原ガラスを得る。前述のように原ガラスを熔解した後、金型に鋳込む、および／または熱間成形等の操作により、所望の形状に成形し徐冷する。 Next, the crystallized glass of the present invention is produced by the following method. First, glass raw materials are weighed and prepared, put into a crucible or the like, and melted at about 1450 to 1600 ° C. to obtain an original glass. After the raw glass is melted as described above, it is cast into a mold and / or formed into a desired shape and slowly cooled by an operation such as hot forming.
次に、結晶化ガラスとするための熱処理を行う。まず、６５０〜７５０℃の温度、好ましくは下限が６８０℃及び／又は上限が７２０℃の温度で保持し、核形成を促す。核形成後、７５０〜８５０℃の温度で結晶化する。この温度が７５０℃より低いと主結晶相が十分に成長し難く、８５０℃より高いと原ガラスが軟化変形もしくは再熔解し易くなるため望ましくない。 Next, heat treatment is performed to obtain crystallized glass. First, a temperature of 650 to 750 ° C., preferably a lower limit of 680 ° C. and / or an upper limit of 720 ° C. is maintained to promote nucleation. After nucleation, crystallization occurs at a temperature of 750 to 850 ° C. If this temperature is lower than 750 ° C., the main crystal phase hardly grows sufficiently, and if it is higher than 850 ° C., the original glass tends to soften and deform or remelt, which is not desirable.
さらに前記マスク、光学系反射ミラー、ウエハーステージ、レチクルステージ、精密品用部材は、前記ガラスセラミックスを所望の形状に加工し、必要に応じてラッピング、研磨、膜付け等の加工をすることにより得られる。 Further, the mask, optical system reflection mirror, wafer stage, reticle stage, and precision product member are obtained by processing the glass ceramic into a desired shape and processing such as lapping, polishing, and filming as necessary. It is done.
次に本発明の好適な実施例について説明する。まず、酸化物、炭酸塩、硫化物、硝酸塩等の原料を混合し、これを通常の溶解装置を用いて約１４５０〜１６００℃の温度で溶解し攪拌均質化した後、成形、冷却しガラス成形体を得た。その後これを６５０〜７５０℃で約１〜１５０時間熱処理して結晶核形成後、７５０〜８５０℃で約１〜３００時間時間熱処理結晶化して、結晶化ガラスを得た。 Next, preferred embodiments of the present invention will be described. First, raw materials such as oxides, carbonates, sulfides, and nitrates are mixed, melted at a temperature of about 1450 to 1600 ° C. using a normal melting apparatus, homogenized with stirring, and then molded, cooled, and glass molded. Got the body. Thereafter, this was heat-treated at 650 to 750 ° C. for about 1 to 150 hours to form crystal nuclei, and then crystallized by heat treatment at 750 to 850 ° C. for about 1 to 300 hours to obtain crystallized glass.
表１〜表３に実施例１〜８、および比較例１、２のガラス組成、熔解後のアモルファスガラスの１ｃｍ３当りの残存泡数を示す。この時、泡の数は１ｃｍ３の範囲をアモルファスガラス内で任意の５ヶ所を顕微鏡にて測定し、平均を算出した。１０ｍｍ厚のサンプルで分光透過率５％および８０％を示す最も短い波長（８０％透過率波長、５％透過率波長）、０〜５０℃における平均線膨張係数（α）を示す。なお、各実施例および比較例の組成は質量％で表した。本発明は以下の実施例にのみ限定されるものではない。 Tables 1 to 3 show the glass compositions of Examples 1 to 8 and Comparative Examples 1 and 2, and the number of remaining bubbles per 1 cm 3 of the amorphous glass after melting. At this time, the number of bubbles was measured within a range of 1 cm 3 in an amorphous glass at any five locations with a microscope, and the average was calculated. The shortest wavelength (80% transmittance wavelength, 5% transmittance wavelength) showing spectral transmittances of 5% and 80% in a 10 mm thick sample, and the average linear expansion coefficient (α) at 0 to 50 ° C. are shown. In addition, the composition of each Example and the comparative example was represented by the mass%. The present invention is not limited only to the following examples.
平均線膨張係数はフィゾー干渉式精密膨張率測定装置を用いて測定した。測定試料の形状は直径６ｍｍ、長さ約８０ｍｍの円柱状である。測定方法として、この試料の両端に光学平面板を接触させ、Ｈｅ‐Ｎｅレーザーによる干渉縞が観察できるようにし、温度コントロール可能な炉に入れる。次に測定試料の温度を変化させ、干渉縞の変化を観察することによって、温度による測定試料長さの変化量を測定する。本発明においては、０℃から５０℃の温度範囲において０．５℃／ｍｉｎで昇温あるいは降温させ、５秒毎に測定試料長さの変化量をプロットし、さらに５次の近似曲線を描いたうえで、０℃から５０℃における平均線膨張係数および０℃から５０℃の温度範囲内でのΔＬ／Ｌの最大値−最小値を算出した。なお、平均線膨張係数およびΔＬ／Ｌ−温度曲線の最大値−最小値はいずれも昇温時と降温時の平均値である。 The average linear expansion coefficient was measured using a Fizeau interferometric precise expansion coefficient measuring device. The shape of the measurement sample is a cylindrical shape having a diameter of 6 mm and a length of about 80 mm. As a measurement method, an optical flat plate is brought into contact with both ends of the sample so that interference fringes by a He—Ne laser can be observed, and the sample is placed in a temperature controllable furnace. Next, by changing the temperature of the measurement sample and observing the change in interference fringes, the amount of change in the measurement sample length due to temperature is measured. In the present invention, the temperature is raised or lowered at 0.5 ° C./min in the temperature range from 0 ° C. to 50 ° C., the amount of change in the measured sample length is plotted every 5 seconds, and a fifth order approximate curve is drawn. In addition, the average linear expansion coefficient from 0 ° C. to 50 ° C. and the maximum value-minimum value of ΔL / L within the temperature range of 0 ° C. to 50 ° C. were calculated. Note that the average linear expansion coefficient and the maximum value-minimum value of the ΔL / L-temperature curve are both average values during temperature rise and temperature drop.
表１〜３に示されるとおり、本発明の結晶化ガラスでは熱膨張特性も０℃〜５０℃における平均線膨張係数が０±１．０（１０‐７／℃）以下であった。また、実施例２〜７は、ガラス１ｃｍ３中に含まれる残存泡数が３〜１１個であり、比較例における砒素成分を使用した場合の結果に相当する清澄特性を示している。 As shown in Tables 1 to 3, in the crystallized glass of the present invention, the thermal expansion characteristic was 0 ± 1.0 (10 −7 / ° C.) or less in the average linear expansion coefficient at 0 ° C. to 50 ° C. In Examples 2 to 7, the number of residual bubbles contained in 1 cm 3 of glass is 3 to 11, and clarification characteristics corresponding to the results obtained when the arsenic component in the comparative example is used are shown.
本発明の結晶化ガラスは、極端紫外線露光技術（ＥＵＶＬ）を利用した次世代半導体製造装置などのミラー基板材やフォトマスク基板材として利用が期待されると共に、リソグラフィー用マスク、光学系反射ミラー、ウエハーステージ、レチクルステージ等の半導体製造装置部材、液晶露光装置用部材、大型反射鏡部材、あるいは標準尺・原器用部材、検査装置等の各種精密部材へ活用することができる。また、本発明のガラスセラミックスは透明性が高いため、光フィルター用の基板、リソグラフィー用の透過型マスク等高い光線透過率を求められる用途にも使用できる。その他、あらゆる部材への用途において本発明のガラスセラミックスの持つ機械的強度により、効果的に軽量化加工を施すこともできる。 The crystallized glass of the present invention is expected to be used as a mirror substrate material and a photomask substrate material for next-generation semiconductor manufacturing equipment using extreme ultraviolet exposure technology (EUVL), as well as a lithography mask, an optical reflection mirror, It can be used for semiconductor manufacturing equipment members such as a wafer stage and a reticle stage, liquid crystal exposure equipment members, large reflector members, or standard precision / general equipment members, various precision members such as inspection equipment. In addition, since the glass ceramic of the present invention has high transparency, it can also be used for applications requiring high light transmittance, such as a substrate for an optical filter and a transmission type mask for lithography. In addition, it is possible to effectively reduce the weight by using the mechanical strength of the glass ceramics of the present invention in applications to all members.
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