JPS62256739A - Glass - Google Patents
GlassInfo
- Publication number
- JPS62256739A JPS62256739A JP9734586A JP9734586A JPS62256739A JP S62256739 A JPS62256739 A JP S62256739A JP 9734586 A JP9734586 A JP 9734586A JP 9734586 A JP9734586 A JP 9734586A JP S62256739 A JPS62256739 A JP S62256739A
- Authority
- JP
- Japan
- Prior art keywords
- quartz glass
- sol
- glass
- transmittance
- gel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011521 glass Substances 0.000 title claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000012535 impurity Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 3
- 238000003980 solgel method Methods 0.000 claims abstract description 3
- -1 silicon alkoxide Chemical class 0.000 claims abstract 3
- 229910052710 silicon Inorganic materials 0.000 claims abstract 2
- 239000010703 silicon Substances 0.000 claims abstract 2
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 150000003609 titanium compounds Chemical class 0.000 claims description 2
- 238000002834 transmittance Methods 0.000 abstract description 17
- 239000000758 substrate Substances 0.000 abstract description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract 4
- 229910021529 ammonia Inorganic materials 0.000 abstract 2
- 239000004743 Polypropylene Substances 0.000 abstract 1
- 229920001155 polypropylene Polymers 0.000 abstract 1
- 239000010453 quartz Substances 0.000 abstract 1
- 238000005245 sintering Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 241001474791 Proboscis Species 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/006—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce glass through wet route
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/12—Other methods of shaping glass by liquid-phase reaction processes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacturing & Machinery (AREA)
- Glass Melting And Manufacturing (AREA)
- Glass Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はｒｃフォトマスク基板であるガラス基板の純度
に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to the purity of glass substrates that are RC photomask substrates.
従来のｔＣフォトマスクガラス基板は、無アルカリガラ
スや石英ガラスであった。ところで、半導体産業は最近
では高密度化が進み４Ｍ−ＤＲＡＭも試作されるように
なった。このように高密度化が進むと、フォトリソに使
用する光源としては紫外光のような短波長の光が必要に
なる。無アルカリガラスは紫外光の透過率が低いため使
用できず、今では、紫外光の透過率の高い石英ガラスが
主流を占めるようになっている。一般に、上のような理
由から、石英ガラスのｒｃフォトマスク基板の紫外光の
透過率は、２００ｎｒｎの光で９０％以上（厚み２．６
．）の透過率が求められている。Conventional tC photomask glass substrates have been made of alkali-free glass or quartz glass. Incidentally, the semiconductor industry has recently become more densely packed, and 4M-DRAMs have also been prototyped. As the density increases in this way, short wavelength light such as ultraviolet light is required as a light source for photolithography. Alkali-free glass cannot be used because it has a low transmittance for ultraviolet light, and quartz glass, which has a high transmittance for ultraviolet light, is now the mainstream. Generally, for the above reasons, the ultraviolet light transmittance of a quartz glass RC photomask substrate is 90% or more at 200nrn light (with a thickness of 2.6
．． ) is required.
しかし、前述の石英ガラスは何々の不純物を含んでいる
ために、天然石英ガラスでは、２０１］ｎｍ系外光の透
過率はほぼ８０チ程度で、９０％を超えるものは製造困
難なために、裏通コストが高くつきはとんと使用されて
いない。また、合成石英ガラスは＾純度であるため、２
００ｎｍの透過率はほとんど９０％を超えている。しか
し、非常に高純）ｙにしているため、原料の精製や製造
工程を高度にコントロールしないといけない。そのため
に製造コヌトが高く、合成石英ガラスは天然石英ガラス
よ＃）高コストであるという問題点を有する。However, since the aforementioned quartz glass contains various impurities, the transmittance of natural quartz glass for external light in the 201] nm system is approximately 80 degrees, and it is difficult to manufacture products with a transmittance of more than 90%. It is rarely used due to the high back cost. In addition, since synthetic quartz glass has a purity of 2
The transmittance at 00 nm is almost over 90%. However, since it is made to be extremely pure, the refining of raw materials and the manufacturing process must be highly controlled. Therefore, manufacturing costs are high, and synthetic quartz glass has a problem in that it is more expensive than natural quartz glass.
そこで本発明はこのような問題点を解決するもので、そ
の目的とするところは、安価で、紫外光の透過率が筒い
（２００ｎｍの光の透過率が９０チを超えるような）ガ
ラスを提供するところにある。The present invention is intended to solve these problems, and its purpose is to create a glass that is inexpensive and has a high transmittance for ultraviolet light (transmittance of 200 nm light exceeding 90 cm). It's there to provide.
本発明のガラスは、ガラス中の不純物であるチタン、あ
るいはチタン化合物の量が（ＬＯ５ｐ ｐｒｏ以下であ
ることを％徴とする。The glass of the present invention is characterized by the amount of titanium or titanium compound as an impurity in the glass being less than or equal to (LO5p pro).
また、上記のガラスは石英ガラスであると、さらに、紫
外光の透過率が高くなるので、石英ガラスであることが
望ましく、さらに、一般の製造法によればチタン不ｆ’
Ｊ［物社をコントロールしにくいので、コントロールの
しやすい、金属アルコキシドや微粉末シリカを原料とす
るゾル−ゲル法による石英ガラスであることが望ましい
。In addition, if the above-mentioned glass is quartz glass, the transmittance of ultraviolet light will further increase, so it is preferable to use quartz glass.
Since it is difficult to control the material, it is desirable to use silica glass produced by the sol-gel method using metal alkoxide or finely powdered silica as raw materials, which is easy to control.
紫外光、待に２００ｎｍ程度の波長の吸収については、
ガラスの主成分であるＳＩＯ，ではほとんど吸収はない
と考えられ、主に吸収に起因するのはＴＩ化合′吻の不
純物である。その他の不純物では、少しの吸収は有るか
もしれないが、ｐｐｍオーダーの存在量では透過率ケ大
きく下げるようなことはない。従って、不純物中のＴ１
元素のみ注意して除くことができれば、他の不Ｎ物がｐ
ｐｍオーダーで存在しても２００ｎｍＱ元透ａ’４ｆ９
０％以上にすることはできる。つまり、ガラスの製造の
絵に、原料の精製は、従来のように極端に高利度にする
必璧はなく、ＴＩのみに′ｃＥ意して梢表すれば良いの
で、精製の工程が従来よシ簡略化できるので、製造コス
トを下げることができる。Regarding the absorption of ultraviolet light, especially at a wavelength of about 200 nm,
SIO, which is the main component of glass, is thought to have almost no absorption, and absorption is mainly caused by impurities in the TI compound's proboscis. Other impurities may have some absorption, but their presence on the order of ppm will not significantly reduce the transmittance. Therefore, T1 in the impurity
If only the elements can be removed with care, other non-N substances will be p
Even if it exists in the pm order, it is 200 nm Q original transparent a'4f9
It can be set to 0% or more. In other words, in the picture of glass production, it is not necessary to refine the raw materials at extremely high yields as in the past, but it is sufficient to express the refining process using 'cE' only for TI. Since the process can be simplified, manufacturing costs can be lowered.
ところで、２００ ｎ ｍ （厚み′２．６Ｗ！ＩＡ）
で９０チ以上の透過率￥達成するのに必要なＴ１の不純
物置は、我々の実験によるとほぼ１１０５ｐｐ以下であ
れば良いことが分かつ九。By the way, 200 nm (thickness '2.6W!IA)
According to our experiments, it has been found that the T1 impurity required to achieve a transmittance of 90 cm or higher is approximately 1105 pp or less.
つまシ、ガラス原料のｎ製に２いては、Ｔｉ不純物を１
１０５ｐｐ以下にすれば良い。If the glass raw material is made of N, Ti impurities are added to 1.
It should be 105 pp or less.
実施例１゜
合成石英ガラス原料である市販の５ｌｃｔ、の純度分析
をすると、Ｎ＆：αｌｐｐｍ、Ｔｉα０１ｐｐｍ。Example 1 Purity analysis of commercially available 5lct, which is a raw material for synthetic quartz glass, reveals N&:αlppm, Tiα01ppm.
Ａｔ：５ｐｐｍであった。ＴＩ線純度良かったので、酸
水素バーナーな用い火炎加水分解を行って石英ガラスと
した。At: 5 ppm. Since the TI line purity was good, quartz glass was obtained by flame hydrolysis using an oxyhydrogen burner.
この石英ガラスを厚み２．５１に研磨し２００ｎｍの光
透過率を測定すると９１５％であった。これはｒｃフォ
トマスク基板に十分使用できるものであることが分かっ
た。This quartz glass was polished to a thickness of 2.51 mm and the light transmittance at 200 nm was measured to be 915%. It has been found that this can be fully used as an RC photomask substrate.
比較例１゜
従来の合成石英ガラスの製造方法では、実施例１で用い
た５ｔｃｚ４は、Ａｔ純度が５ｐｐｍ と悪いために
、蒸留により精製してから石英ガラスを合成していた。Comparative Example 1 In the conventional method for producing synthetic quartz glass, 5tcz4 used in Example 1 had a poor At purity of 5 ppm, so it was purified by distillation before synthesizing silica glass.
従って、この蒸留の８Ｍ工程が、実施例１に比較して多
いため、高コストである。Therefore, the number of 8M steps for this distillation is larger than in Example 1, resulting in high cost.
つまり、本発明の実施例１ｆｆ用いれば、低コストでＩ
Ｃフオトマヌク基板とすることができる。In other words, if Embodiment 1ff of the present invention is used, I
It can be a C photomanuk substrate.
実施例２
市販のケイ酸エチルＱｘｃｐにより純度分析を行うと、
ＴＩ：Ｑ、０２ｐｐｎｔ、Ａｔ：α１ｐｐｒｎであった
。Example 2 Purity analysis was performed using commercially available ethyl silicate Qxcp.
TI: Q, 02 ppnt, At: α1 pprn.
精製しないで以下の工程な行った。The following steps were performed without purification.
禾１４ｍの市販のケイ酸エチル４．４ｔにエタノール＆
７６、水１．５ｔ、アンモニア水α１ｔを加え攪拌し、
−伎装置した後、エバポレーターで潰縮し２．５ｔにし
た。（Ａゾル）
一方、未精製のケイ酸エチル１．９ｔに０．０２規定の
塩酸ａ、６ｔをカロえ加水分解した。（バブル）上記Ａ
ゾルとバブルを混合し攪拌してからアンモニア水ｆ＆−
滴下しＰＨを４．５にした。このゾル１．２ｔをボリグ
ロピレン容器に加え、ゲル化し、６０Ｃで１０日間°乾
燥しドライゲルとした。ドライゲルを適当な条件で焼箱
し石英ガラスとした後、１７８０℃で１０分間畠湛処理
し念。得られた石英ガラスを５インチロスα０９インチ
厚の大きさに研磨し、２００ｎｍの光透過率を測定する
と９０％であった。これはＩＣ用フォトマスク基板とし
て十分使用できるものであった。Ethanol & 4.4t of commercially available ethyl silicate with a height of 14m
76. Add 1.5 t of water and 1 t of ammonia water and stir.
- After being heated, it was compressed using an evaporator to a total weight of 2.5 tons. (Sol A) On the other hand, 6 tons of 0.02N hydrochloric acid a was added to 1.9 tons of unrefined ethyl silicate for hydrolysis. (Bubble) A above
Mix the sol and bubbles and stir, then add ammonia water f&-
It was added dropwise to adjust the pH to 4.5. 1.2 t of this sol was added to a polyglopyrene container, gelled, and dried at 60C for 10 days to form a dry gel. The dry gel was made into quartz glass by baking it in a baking box under appropriate conditions, and then it was heated at 1780°C for 10 minutes. The obtained quartz glass was polished to a thickness of 09 inches with a loss of 5 inches, and the light transmittance at 200 nm was measured to be 90%. This could be fully used as a photomask substrate for IC.
また、ＩＣＰ（Ｉｎｄｕｃｔｉｖｅｌｙ Ｃｏｕｐｌｅ
ｄ Ｐｌａａｒｏａ） によシ得られた石英ガラスの
純度分析を行うと、Ｔｌ：［ＬＯ２ｐｐｒｎ、Ａｔ：０
．＋ｐｐｍで原料と同一であった１゜
比較例Ｚ
実施例２と同様の操作を、純度がＴｌ：αＩＰ＋””Ｉ
ＡｔＣＬＯ１ｐ ｐｍのケイ酸エチルヶ用いて行った。In addition, ICP (Inductively Couple
Purity analysis of the quartz glass obtained by dPlaaroa) revealed that Tl:[LO2pprn, At:0
．． +ppm and the same as the raw material 1゜Comparative Example Z
The test was carried out using ethyl silicate at 1 p pm of AtCLO.
得られた石英ガラスの純度は原料と同一でＴＩ：ｌｌｐ
ｐｍであった。このものの２００ｎｍの光透過率（厚さ
２．３ ｍ ）は、７５チであシ、ｒｃ用フォトマスク
には使えないものであった。The purity of the obtained quartz glass is the same as that of the raw material, and TI:llp
It was pm. The light transmittance of this material at 200 nm (thickness: 2.3 m) was 75 cm, and it could not be used as an RC photomask.
以上述べたように、本発明によれば、ＴＩ不純物を０．
Ｏ５ｐｐｍ以下にすることによシ、２００ｎｍの光透過
率を９０％以−ヒ（厚み２．３．）にすることができる
もので、従来よシ原料の精製が容易でい一コストにでき
るという効果を有するものである。As described above, according to the present invention, TI impurities can be reduced to 0.
By reducing the O2 content to 5 ppm or less, the light transmittance at 200 nm can be increased to over 90% (thickness: 2.3 mm), making it easier to purify the raw material and reducing costs compared to conventional methods. It is effective.
ツマ、ｂ、ｒｃ用フォトマスク基板を安価にすることが
できる。It is possible to reduce the cost of photomask substrates for photomask, b, and rc.
Claims (3)
化合物の量が０．０５ｐｐｍ以下であることを特徴とす
るガラス。(1) A glass characterized in that the amount of titanium or a titanium compound as an impurity in the glass is 0.05 ppm or less.
特許請求の範囲第１項記載のガラス。(2) The glass according to claim 1, wherein the glass is quartz glass.
シドや微粉末シリカを原料とするゾル−ゲル法により得
られる石英ガラスであることを特徴とする特許請求の範
囲第２項記載のガラス。(3) The glass according to claim 2, wherein the quartz glass is obtained by a sol-gel method using at least silicon alkoxide or finely powdered silica as raw materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9734586A JPS62256739A (en) | 1986-04-26 | 1986-04-26 | Glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9734586A JPS62256739A (en) | 1986-04-26 | 1986-04-26 | Glass |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62256739A true JPS62256739A (en) | 1987-11-09 |
Family
ID=14189889
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9734586A Pending JPS62256739A (en) | 1986-04-26 | 1986-04-26 | Glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62256739A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015193521A (en) * | 2014-03-19 | 2015-11-05 | 日本電気硝子株式会社 | Ultraviolet transmission glass and production method |
| JPWO2016194780A1 (en) * | 2015-05-29 | 2018-03-15 | 旭硝子株式会社 | UV transmitting glass |
| JPWO2017057375A1 (en) * | 2015-09-30 | 2018-07-19 | 旭硝子株式会社 | UV transmitting glass |
| JP2019147722A (en) * | 2018-02-28 | 2019-09-05 | 日本電気硝子株式会社 | Ultraviolet transmission glass and manufacturing method therefor |
-
1986
- 1986-04-26 JP JP9734586A patent/JPS62256739A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015193521A (en) * | 2014-03-19 | 2015-11-05 | 日本電気硝子株式会社 | Ultraviolet transmission glass and production method |
| JPWO2016194780A1 (en) * | 2015-05-29 | 2018-03-15 | 旭硝子株式会社 | UV transmitting glass |
| JPWO2017057375A1 (en) * | 2015-09-30 | 2018-07-19 | 旭硝子株式会社 | UV transmitting glass |
| JP2019147722A (en) * | 2018-02-28 | 2019-09-05 | 日本電気硝子株式会社 | Ultraviolet transmission glass and manufacturing method therefor |
| WO2019167399A1 (en) * | 2018-02-28 | 2019-09-06 | 日本電気硝子株式会社 | Uv transmitting glass and method for producing same |
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