JPS6133664B2 - - Google Patents
Info
- Publication number
- JPS6133664B2 JPS6133664B2 JP57081977A JP8197782A JPS6133664B2 JP S6133664 B2 JPS6133664 B2 JP S6133664B2 JP 57081977 A JP57081977 A JP 57081977A JP 8197782 A JP8197782 A JP 8197782A JP S6133664 B2 JPS6133664 B2 JP S6133664B2
- Authority
- JP
- Japan
- Prior art keywords
- hard
- cleaning
- abrasive
- cerium oxide
- mineral acid
- 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.)
- Expired
Links
- 238000004140 cleaning Methods 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 19
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 15
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 15
- 239000011521 glass Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 8
- 239000011707 mineral Substances 0.000 claims description 8
- 239000003082 abrasive agent Substances 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 241000283070 Equus zebra Species 0.000 claims description 3
- 238000010899 nucleation Methods 0.000 claims description 2
- 238000005498 polishing Methods 0.000 claims description 2
- -1 ferrous compound Chemical class 0.000 claims 1
- 239000002245 particle Substances 0.000 description 4
- 238000005530 etching Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 241000511976 Hoya Species 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000002783 friction material Substances 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 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
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
- C03C23/0075—Cleaning of glass
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Grinding And Polishing Of Tertiary Curved Surfaces And Surfaces With Complex Shapes (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Detergent Compositions (AREA)
- Grinding-Machine Dressing And Accessory Apparatuses (AREA)
Description
この発明は硬ゼイ材料の洗浄方法に関し、硬ゼ
イ材料の研摩面に残る酸化セリウム（CeO2）を、
研摩面の潜傷を堀り起こすことなく溶解し、研摩
剤粒子、洗浄液中のゴミ等（以下異物と言う）の
付着もなく、キズもない研摩面を有する硬ゼイ材
料を得るための、硬ゼイ材料の洗浄方法を提供せ
んとするものである。
酸化セリウムは化学的に安定である為、従来よ
り研摩表面に残る酸化セリウムは、研摩表面をあ
る程度エツチングすることにより、表面より遊離
させて取り除くか、あるいは物理的に表面を摩擦
することにより取り除くことが行なわれていた。
どちらの場合も表面より完全に酸化セリウムを取
り除くことが困難であり、しかも、表面にキズを
残ることが多かつた。
例えば硬ゼイ材料としてガラスを洗浄する場
合、洗浄液に弗酸系あるいはリン酸系の洗浄液を
用い、洗浄表面には超音波揺動をかけることが行
なわれた。またスポンジ、ブラシ等の摩擦材料に
よつて力学的に表面上の酸化セリウムを取り除く
ことも行なわれている。
従来、ガラスを酸化セリウムを含有する研摩剤
で研摩すると、ガラス表面には酸化セリウムが付
着することが知られている。比較的ガラス表面に
強固に研摩剤が付着している場合には、ガラス表
面をわずかにエツチングする方法が効果的である
が、この場合には潜傷を堀り起こしてしまい、ガ
ラス表面が細かいキズの多い面となつてしまう。
また、一度洗浄液中に酸化セリウム粒子が遊離し
たとしても、ガラス表面に再付着する可能性があ
る。ブラシ等で研摩面をこすつて研摩剤を落す方
法の場合でも同様の弊害をもつている。
本発明においては、ガラスは化学的にエツチン
グされることなく、付着している酸化セリウムを
溶解することが可能である。よつてガラス表面に
潜傷を発生させることなく研摩剤を落すことがで
き、またこの際に使用する洗浄液中には酸化セリ
ウム粒子も残らないので、異物の付着の少ない清
浄な研摩面を得るための洗浄を行なうことができ
る。
すなわち、本発明の硬ゼイ材料の洗浄方法は、
酸化セリウムを含有する研摩剤で硬ゼイ材料を研
摩する場合において、前記硬ゼイ材料表面に付着
した研摩剤を、還元剤を含む鉱酸溶液により溶解
することを特徴とするものである。
本発明の適用可能な硬ゼイ材料としては、IC
用フオトマスク用基板として使われているガラス
基板（LE株式会社保谷電子製）が挙げられ、そ
の他IC用の基板として使われているソーダライ
ム系のガラス、また最近使われ始めた石英ガラス
についても十分効果がある。
鉱酸濃度についてもいくら濃くしてもかまわな
いし、処理温度ももつと高くしてもかまわない
が、作業性、安全性からみて鉱酸濃度として望ま
しい値は１規定〜２規定、温度としては40〜50℃
である。
また還元剤としては、塩化第１鉄のみならず塩
化第１スズも有効である。
具体例を挙げてより詳細に説明する。洗浄液の
構成をH2SO4＋FeCl2とし、H2SO4を０〜2N、
FeCl2を０〜4wt％とした上記洗浄液中に、酸化
セリウムを主成分とする研摩剤（ルミノツクス）
を分散させ、50℃に保ち、10分間超音波揺動をか
けたときの研摩剤の溶解度を表−１に示す。この
とき超音波強度は117キヤビンで、超音波発振子
には25kHz、0.5kwのものを用いた。このときに
用いた研摩剤の組成を表−２に示す。
The present invention relates to a method for cleaning hard-zeitic materials, which removes cerium oxide (CeO 2 ) remaining on the polished surface of hard-zeitic materials.
In order to dissolve latent scratches on the polished surface without digging them up, to obtain a hardened material that has a scratch-free polished surface without the adhesion of abrasive particles, dirt in the cleaning solution, etc. (hereinafter referred to as foreign matter), The purpose of the present invention is to provide a method for cleaning zey material. Since cerium oxide is chemically stable, conventionally the cerium oxide remaining on the polished surface can be removed by etching the polished surface to some extent to release it from the surface, or by physically rubbing the surface. was being carried out.
In both cases, it was difficult to completely remove cerium oxide from the surface, and moreover, scratches often remained on the surface. For example, when cleaning glass as a hard gelatinous material, a hydrofluoric acid-based or phosphoric acid-based cleaning liquid is used as the cleaning liquid, and ultrasonic vibration is applied to the cleaning surface. Additionally, cerium oxide on the surface is mechanically removed using a friction material such as a sponge or brush. Conventionally, it has been known that when glass is polished with an abrasive containing cerium oxide, cerium oxide adheres to the glass surface. If the abrasive is relatively firmly attached to the glass surface, slightly etching the glass surface is effective, but in this case, latent scratches will be dug up and the glass surface will become fine It becomes a surface with many scratches.
Moreover, even if cerium oxide particles are once liberated in the cleaning liquid, there is a possibility that they will re-adhere to the glass surface. A method of removing the abrasive by rubbing the abrasive surface with a brush or the like has similar disadvantages. In the present invention, it is possible to dissolve adhering cerium oxide without chemically etching the glass. Therefore, the abrasive can be removed without causing latent scratches on the glass surface, and since no cerium oxide particles remain in the cleaning solution used at this time, it is possible to obtain a clean polished surface with less adhesion of foreign matter. can be cleaned. That is, the method for cleaning hard zeitic materials of the present invention is as follows:
When polishing a hard zebra material with an abrasive agent containing cerium oxide, the abrasive agent adhering to the surface of the hard zeitic material is dissolved by a mineral acid solution containing a reducing agent. As the hard-zealous material to which the present invention can be applied, IC
Glass substrates (manufactured by LE Hoya Electronics Co., Ltd.) used as photomask substrates, soda lime glass used as IC substrates, and quartz glass that has recently begun to be used are also covered. effective. It doesn't matter how high the mineral acid concentration is, and it doesn't matter how high the processing temperature is, but from the viewpoint of workability and safety, the desirable mineral acid concentration is 1N to 2N, and the temperature is 40 ~50℃
It is. Furthermore, as a reducing agent, not only ferrous chloride but also stannous chloride is effective. This will be explained in more detail by giving a specific example. The composition of the cleaning solution is H 2 SO 4 + FeCl 2 , H 2 SO 4 is 0 to 2N,
An abrasive agent whose main component is cerium oxide (Luminox) is added to the above cleaning solution containing 0 to 4 wt% FeCl2 .
Table 1 shows the solubility of the abrasive when the abrasive was dispersed, kept at 50°C, and subjected to ultrasonic shaking for 10 minutes. At this time, the ultrasonic intensity was 117 cabins, and the ultrasonic oscillator was 25kHz and 0.5kw. The composition of the abrasive used at this time is shown in Table 2.
【表】
時間
[Table] Time
【表】
上記表−１において、洗浄液中のFeCl2が０％
のときは、鉱酸のみの効果により研摩剤中の酸化
ランタン（La2O3）の溶解が起きたものと解釈で
きる。上記洗浄液に超音波をかけたときの第２鉄
イオン濃度を調べてみると、研摩剤の溶解度とと
もに増加していることがわかつた。したがつて以
下のような反応により、酸化セリウムの溶解が起
きているものと解釈される。
H2SO4＋Fe2＋CeO2
→H2SO4＋Fe3＋第１セリウム化合物
表−２に示された1NのH2SO4、2wt％のFeCl2
を含む洗浄液を用いた場合でも、板ガラス、IC
用フオトマスク用ガラス基板、石英ガラス等の表
面を全く侵すことなく表面に付着した研摩剤を溶
解でき、精密な洗浄面を作成できることがわか
る。
以下本発明の硬ゼイ材料の洗浄方法を、実施例
に基いて詳細に説明する。
実施例
LEガラス基板（株式会社保谷電子製）を、酸
化セリウム系の研摩剤ルミノツクス（清美化学株
式会社製）で研摩し、別途鉱酸として1N−
H2SO4を、還元剤として1wt％のFeCl2を含む洗
浄液を40℃に加熱したものに浸漬して、超音波を
かけながら２分間洗浄した。またこの基板に金属
クロムをスパツターした際に、200培の顕微鏡で
見える表面異物を数えた結果を表−３に示す。比
較例として従来行なわれている0.1％のHF溶液で
上記基板を洗浄した。本発明による方法でガラス
を洗浄すると、従来行なわれている方法によるも
のよりも極めて清浄な研摩面が得られることがわ
かる。[Table] In Table 1 above, FeCl 2 in the cleaning solution is 0%.
When , it can be interpreted that lanthanum oxide (La 2 O 3 ) in the abrasive was dissolved due to the effect of the mineral acid alone. When the ferric ion concentration was examined when ultrasonic waves were applied to the cleaning solution, it was found that it increases with the solubility of the abrasive. Therefore, it is interpreted that the following reaction causes the dissolution of cerium oxide. H 2 SO 4 +Fe 2 +CeO 2 →H 2 SO 4 +Fe 3 + Cerous compound 1N H 2 SO 4 and 2wt% FeCl 2 shown in Table-2
Even when using a cleaning solution containing
It can be seen that the abrasive adhering to the surface of photomask glass substrates, quartz glass, etc. can be dissolved without damaging the surface at all, and a precisely cleaned surface can be created. Hereinafter, the method for cleaning hard zeitic materials of the present invention will be explained in detail based on Examples. Example: An LE glass substrate (manufactured by Hoya Electronics Co., Ltd.) was polished with Luminox (manufactured by Seibi Kagaku Co., Ltd.), a cerium oxide-based abrasive, and separately treated with 1N- as a mineral acid.
The H 2 SO 4 was immersed in a cleaning solution containing 1 wt % FeCl 2 as a reducing agent heated to 40° C. and cleaned for 2 minutes while applying ultrasonic waves. Furthermore, when metallic chromium was sputtered onto this substrate, Table 3 shows the results of counting the number of foreign particles visible on the surface using a 200-microscope. As a comparative example, the above substrate was cleaned with a 0.1% HF solution, which is conventionally used. It can be seen that cleaning glass with the method according to the invention results in a much cleaner polished surface than with conventional methods.
【表】
てカウント
以上のように本発明の硬ゼイ材料の洗浄方法に
よれば、極めて高精度な表面品質を要求される超
LS1用マスク基板の洗浄が可能で、高品質のもの
が得られる。[Table] As described above, according to the method of cleaning hard-seeding materials of the present invention, ultra-high-quality materials that require extremely high precision surface quality can be
The mask substrate for LS1 can be cleaned and high quality products can be obtained.
Claims (1)
を研摩する場合において、前記硬ゼイ材料表面に
付着した研摩剤を、還元剤を含む鉱酸溶液によつ
て溶解することを特徴とする硬ゼイ材料の洗浄方
法。 ２ 硬ゼイ材料が、ガラス基板である特許請求の
範囲第１項記載の硬ゼイ材料の洗浄方法。 ３ 還元剤が、第１鉄化合物である特許請求の範
囲第１項または第２項記載の硬ゼイ材料の洗浄方
法。 ４ 鉱酸が、温度30℃〜50℃の2.0規定程度の鉱
酸である、特許請求の範囲第１項乃至第３項のい
ずれかに記載の硬ゼイ材料部品洗浄方法。[Scope of Claims] 1. When polishing a hard zebra material with an abrasive agent containing cerium oxide, the abrasive agent adhering to the surface of the hard oxide material is dissolved by a mineral acid solution containing a reducing agent. Characteristic cleaning method for hard-seeding materials. 2. The method for cleaning a hard zeitges material according to claim 1, wherein the hard zek material is a glass substrate. 3. The method for cleaning a hard zeal material according to claim 1 or 2, wherein the reducing agent is a ferrous compound. 4. The method for cleaning hard zebra material parts according to any one of claims 1 to 3, wherein the mineral acid is about 2.0N mineral acid at a temperature of 30°C to 50°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57081977A JPS58198599A (en) | 1982-05-14 | 1982-05-14 | Hard brittle material cleaning method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57081977A JPS58198599A (en) | 1982-05-14 | 1982-05-14 | Hard brittle material cleaning method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58198599A JPS58198599A (en) | 1983-11-18 |
| JPS6133664B2 true JPS6133664B2 (en) | 1986-08-04 |
Family
ID=13761544
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57081977A Granted JPS58198599A (en) | 1982-05-14 | 1982-05-14 | Hard brittle material cleaning method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58198599A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4326825B2 (en) * | 2002-03-27 | 2009-09-09 | Ｈｏｙａ株式会社 | Method for producing chemically strengthened glass substrate and method for producing glass substrate for information recording medium |
-
1982
- 1982-05-14 JP JP57081977A patent/JPS58198599A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58198599A (en) | 1983-11-18 |
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