JP2001098298A - Cleaning liquid for aluminosilicate glass base or ceramic glass base and method for cleaning thereof - Google Patents
Cleaning liquid for aluminosilicate glass base or ceramic glass base and method for cleaning thereofInfo
- Publication number
- JP2001098298A JP2001098298A JP27325199A JP27325199A JP2001098298A JP 2001098298 A JP2001098298 A JP 2001098298A JP 27325199 A JP27325199 A JP 27325199A JP 27325199 A JP27325199 A JP 27325199A JP 2001098298 A JP2001098298 A JP 2001098298A
- Authority
- JP
- Japan
- Prior art keywords
- glass substrate
- cleaning
- aluminosilicate glass
- concentration
- 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.)
- Granted
Links
Landscapes
- Cleaning By Liquid Or Steam (AREA)
- Surface Treatment Of Glass (AREA)
- Detergent Compositions (AREA)
- Manufacturing Of Magnetic Record Carriers (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はアルミノシリケート
ガラス基板又はセラミックガラス基板の洗浄液及び洗浄
方法に係り、特にコンピュータのハードディスクに用い
られる磁気ディスク基板として使用されるガラス基板の
種類のうち、アルミノシリケートガラス基板又はセラミ
ックガラス基板を洗浄する洗浄液及び洗浄方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning solution and a cleaning method for an aluminosilicate glass substrate or a ceramic glass substrate, and more particularly, to aluminosilicate glass among the types of glass substrates used as magnetic disk substrates used for hard disks of computers. The present invention relates to a cleaning liquid and a cleaning method for cleaning a substrate or a ceramic glass substrate.
【０００２】[0002]
【従来の技術】コンピュータのハードディスクに用いら
れる磁気ディスク基板は、アルミニウム合金又はガラス
基板が用いられている。ガラス基板は、アルミニウム合
金と比較して５〜１０倍の強度をもち、また表面粗さが
アルミニウム合金の１／２以下と平滑であることから、
記憶容量の高密度化が可能であり、使用量が増大する傾
向にある。2. Description of the Related Art An aluminum alloy or glass substrate is used as a magnetic disk substrate used for a hard disk of a computer. The glass substrate has 5 to 10 times the strength of the aluminum alloy and the surface roughness is as smooth as 1/2 or less of the aluminum alloy,
It is possible to increase the storage capacity and the amount of usage tends to increase.
【０００３】ガラス基板を用いた磁気ディスクの製造工
程では、ガラス基板の内外径を円盤状に加工し、洗浄
後、表面の研磨処理を行い、最終洗浄後、磁気膜を付加
して磁気ディスク製品とする。ハードディスク装置で
は、この磁気ディスクを所定の回転数で回転させ、磁気
ヘッドをわずかに浮上させて記録・再生動作を行なう。[0003] In the manufacturing process of a magnetic disk using a glass substrate, the inner and outer diameters of the glass substrate are processed into a disk shape, the surface is polished after cleaning, and after the final cleaning, a magnetic film is added to form a magnetic disk product. And In a hard disk drive, the magnetic disk is rotated at a predetermined number of revolutions, and the recording / reproducing operation is performed by slightly floating the magnetic head.
【０００４】しかし、ガラス基板の研磨工程で使用した
研磨剤がガラス基板表面に付着していると、製造した磁
気ディスク表面に凸凹が生じ、正常な記録・再生ができ
なかったり、磁気ヘッドが損傷したりするという問題が
ある。However, if the abrasive used in the polishing step of the glass substrate adheres to the surface of the glass substrate, the surface of the manufactured magnetic disk becomes uneven, so that normal recording / reproduction cannot be performed or the magnetic head is damaged. There is a problem that you do.
【０００５】更に、磁気ディスクの面記録密度は年々増
大しており、それに伴い磁気ヘッドの浮上高さは５０ｎ
ｍ前後から１５〜２５ｎｍまで減少している。Further, the areal recording density of the magnetic disk is increasing year by year, and the flying height of the magnetic head is 50n.
m to 15 to 25 nm.
【０００６】従来より行なわれているガラス基板の洗浄
方法としては、ガラス基板面に純水や洗剤を供給しなが
ら、モータで回転するスポンジローラをガラス基板上に
押圧させて研磨粒子を除去するスクラビング洗浄方法が
一般的である。[0006] As a conventional method of cleaning a glass substrate, scrubbing in which a sponge roller rotated by a motor is pressed onto the glass substrate while supplying pure water or a detergent to the surface of the glass substrate to remove abrasive particles. The cleaning method is common.
【０００７】しかし、このスクラビング洗浄方法は、研
磨砥粒や研磨屑等の粒子径が小さいほど粒子除去が困難
であり、押圧力を強くしても効果的に除去できない。そ
の結果、前述したように、正常な記録・再生ができなか
ったり、磁気ヘッドを損傷してしまう等の問題が生じ
る。[0007] However, in this scrubbing cleaning method, it is difficult to remove particles as the particle size of abrasive grains and polishing dust is smaller, and even if the pressing force is increased, it cannot be effectively removed. As a result, as described above, problems such as a failure to perform normal recording / reproduction and damage to the magnetic head occur.
【０００８】この対策として、特開平８−３２９４５４
号には、ガラス基板面をエッチング（化学的研磨）して
研磨粒子を除去する方法が開示されているが、従来のエ
ッチング洗浄方法は、エッチングむらが生じる等の問題
があることから十分な洗浄効果が得られていなかった。As a countermeasure against this, Japanese Patent Application Laid-Open No. 8-329454 discloses
Discloses a method of removing abrasive particles by etching (chemical polishing) the surface of a glass substrate. However, the conventional etching cleaning method has a problem of insufficient cleaning due to problems such as uneven etching. No effect was obtained.
【０００９】このような背景から、本出願人は、特願平
１０−３１９０１４号において、エッチング洗浄方法の
改良を提案した。この方法は、フッ化水素酸と硫酸等の
酸を混合した洗浄液を用いて、ガラス基板を数十ｎｍエ
ッチングすることにより、エッチング層とともに付着し
た研磨粒子を除去するものである。[0009] From such a background, the present applicant has proposed an improvement in an etching cleaning method in Japanese Patent Application No. 10-319014. In this method, a glass substrate is etched by several tens of nm using a cleaning solution in which an acid such as hydrofluoric acid and sulfuric acid is mixed, thereby removing abrasive particles attached together with an etching layer.
【００１０】[0010]
【発明が解決しようとする課題】しかしながら、特願平
１０−３１９０１４号において提案したエッチングによ
るガラス基板の洗浄方法は、Ｎａ2 Ｏ、ＣａＯ、ＳｉＯ
2 等から成るソーダガラス基板に対しては有効である
が、Ｎａ2 Ｏ、Ａｌ2 Ｏ3 、ＳｉＯ2 等から成るアルミ
ノシリケートガラス基板やセラミックガラス基板では、
化学結合力や含有物組成がソーダガラス基板とは異なる
ために、有効な洗浄ができないという欠点がある。However, the method of cleaning a glass substrate by etching proposed in Japanese Patent Application No. 10-319014 is based on Na 2 O, CaO, SiO 2.
2 is effective for a soda glass substrate made of Na 2 O, Al 2 O 3 , SiO 2, etc.
There is a drawback that effective cleaning cannot be performed because the chemical bonding force and the composition of the components are different from those of the soda glass substrate.
【００１１】本発明はこのような事情に鑑みてなされた
もので、アルミノシリケートガラス基板又はセラミック
ガラス基板に付着残存した研磨粒子を効果的に洗浄除去
することができると共に、エッチングむらも生じないア
ルミノシリケートガラス基板又はセラミックガラス基板
の洗浄液及び洗浄方法を提供することを目的とする。The present invention has been made in view of such circumstances, and it is possible to effectively wash and remove abrasive particles remaining on an aluminosilicate glass substrate or a ceramic glass substrate, and to provide an alumino-silicate film which does not cause uneven etching. An object of the present invention is to provide a cleaning liquid and a cleaning method for a silicate glass substrate or a ceramic glass substrate.
【００１２】[0012]
【課題を解決するための手段】本発明は、前記目的を達
成するために、アルミノシリケートガラス基板又はセラ
ミックガラス基板の表面に付着残存する研磨粒子を洗浄
除去する洗浄液において、前記洗浄液は、０．０５〜
０．１５重量％濃度のフッ化水素酸（ＨＦ）と、０．１
重量％以上で５重量％未満の濃度の硫酸（Ｈ2 ＳＯ4 ）
又は硝酸（ＨＮＯ 3 ）若しくはリン酸（Ｈ3 ＰＯ4 ）と
から成る混酸液であることを特徴とする。The present invention achieves the above object.
Aluminosilicate glass substrate or ceramic
Cleaning of abrasive particles remaining on the surface of the glass substrate
In the cleaning liquid to be removed, the cleaning liquid is 0.05 to
0.15 wt% hydrofluoric acid (HF), 0.1
Sulfuric acid (HTwo SOFour )
Or nitric acid (HNO Three ) Or phosphoric acid (HThree POFour )When
Characterized in that it is a mixed acid solution comprising
【００１３】また、本発明は、前記目的を達成するため
に、アルミノシリケートガラス基板又はセラミックガラ
ス基板の表面に付着残存する研磨粒子を洗浄除去する洗
浄方法において、前記アルミノシリケートガラス基板
を、０．０５〜０．１５重量％濃度のフッ化水素酸（Ｈ
Ｆ）と、０．１重量％以上で５重量％未満の濃度の硫酸
（Ｈ2 ＳＯ4 ）又は硝酸（ＨＮＯ3 ）若しくはリン酸
（Ｈ3 ＰＯ4 ）とから成る混酸液である洗浄液に浸漬す
ると共に、該洗浄液を振動させることを特徴とする。In order to achieve the above object, the present invention provides a cleaning method for cleaning and removing abrasive particles remaining on the surface of an aluminosilicate glass substrate or a ceramic glass substrate. Hydrofluoric acid (H
F) and immersed in a cleaning solution that is a mixed acid solution composed of sulfuric acid (H 2 SO 4 ) or nitric acid (HNO 3 ) or phosphoric acid (H 3 PO 4 ) having a concentration of 0.1% by weight or more and less than 5% by weight. And vibrating the cleaning liquid.
【００１４】また、本発明は、前記目的を達成するため
に、アルミノシリケートガラス基板又はセラミックガラ
ス基板の表面に付着残存する研磨粒子を洗浄除去するガ
ラス基板の洗浄方法において、前記アルミノシリケート
ガラス基板上又はセラミックガラス基板上に、０．０５
〜０．１５重量％濃度のフッ化水素酸（ＨＦ）と、０．
１重量％以上で５重量％未満の濃度の硫酸（Ｈ2 ＳＯ
4 ）又は硝酸（ＨＮＯ3）若しくはリン酸（Ｈ3 ＰＯ
4 ）とから成る混酸液である洗浄液を供給しながら、回
転するブラシローラ又はスポンジローラを前記アルミノ
シリケートガラス基板上又はセラミックガラス基板上に
押しつけることを特徴とする。In order to achieve the above object, the present invention provides a method for cleaning a glass substrate for cleaning and removing abrasive particles remaining on the surface of an aluminosilicate glass substrate or a ceramic glass substrate. Or 0.05 on a ceramic glass substrate
0.15% by weight of hydrofluoric acid (HF);
Sulfuric acid (H 2 SO) having a concentration of 1% by weight or more and less than 5% by weight
4 ) or nitric acid (HNO 3 ) or phosphoric acid (H 3 PO
4 ) The rotating brush roller or the sponge roller is pressed against the aluminosilicate glass substrate or the ceramic glass substrate while supplying the cleaning solution as a mixed acid solution comprising
【００１５】本発明は、ガラス基板の種類によりガラス
基板に付着した研磨粒子の洗浄効果に大きな相違がある
ことに着目してなされたもので、アルミノシリケートガ
ラス基板又はセラミックガラス基板の場合には、０．０
５〜０．１５重量％濃度のフッ化水素酸（ＨＦ）と、
０．１重量％以上で５重量％未満の濃度の硫酸（Ｈ2 Ｓ
Ｏ4 ）又は硝酸（ＨＮＯ3 ）若しくはリン酸（Ｈ3 ＰＯ
4 ）とから成る混酸液を洗浄液として使用するようにし
たので、アルミノシリケートガラス基板面又はセラミッ
クガラス基板面に付着残存した研磨粒子を効果的に洗浄
除去することができ、しかもエッチングむらも生じるこ
とがない。The present invention has been made by focusing on the fact that there is a great difference in the cleaning effect of the abrasive particles attached to the glass substrate depending on the type of the glass substrate. In the case of an aluminosilicate glass substrate or a ceramic glass substrate, 0.0
Hydrofluoric acid (HF) at a concentration of 5 to 0.15% by weight;
Sulfuric acid (H 2 S) having a concentration of 0.1% by weight or more and less than 5% by weight
O 4 ) or nitric acid (HNO 3 ) or phosphoric acid (H 3 PO
4 ) The mixed acid solution consisting of (a) and (b) is used as a cleaning solution, so that the polishing particles remaining on the aluminosilicate glass substrate surface or the ceramic glass substrate surface can be effectively cleaned and removed, and uneven etching may occur. There is no.
【００１６】また、本発明は、前記目的を達成するため
に、研磨処理した後のアルミノシリケートガラス基板又
はセラミックガラス基板を５０〜７０°Ｃの超純水又は
ｐＨ４以下の酸性イオン水により洗浄する予備洗浄工程
と、前記予備洗浄工程後の前記アルミノシリケートガラ
ス基板又はセラミックガラス基板を、請求項２又は請求
項３に記載の洗浄方法により洗浄する薬液洗浄工程と、
前記薬液洗浄工程で前記アルミノシリケートガラス基板
又はセラミックガラス基板に付着した洗浄液を純水で洗
い流すリンス工程と、前記リンス工程でアルミノシリケ
ートガラス基板に付着した水分を乾燥する乾燥工程とか
ら成ることを特徴とする。According to the present invention, in order to achieve the above object, the aluminosilicate glass substrate or the ceramic glass substrate after the polishing treatment is washed with ultrapure water at 50 to 70 ° C. or acidic ion water having a pH of 4 or less. A pre-cleaning step, and a chemical cleaning step of cleaning the aluminosilicate glass substrate or the ceramic glass substrate after the pre-cleaning step by the cleaning method according to claim 2 or 3.
A rinsing step of washing away the cleaning liquid attached to the aluminosilicate glass substrate or the ceramic glass substrate in the chemical liquid washing step with pure water, and a drying step of drying moisture attached to the aluminosilicate glass substrate in the rinsing step. And
【００１７】[0017]
【発明の実施の形態】以下、添付図面に従って本発明の
アルミノシリケートガラス基板又はセラミックガラス基
板の洗浄液及び洗浄方法の好ましい実施の形態について
詳説する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of a cleaning solution and a cleaning method for an aluminosilicate glass substrate or a ceramic glass substrate of the present invention will be described below in detail with reference to the accompanying drawings.
【００１８】先ず、本発明の理論的根拠について説明す
る。First, the theoretical basis of the present invention will be described.
【００１９】一般に、フッ化水素を水に溶解したフッ化
水素酸系の薬液は、ガラスのエッチング液として用いら
れており、エッチングを行うことによる化学的な強度の
改善、またはガラス基板表面に微少な凹凸を適度に形成
させることを目的としている。そして、エッチングを目
的とした場合のフッ化水素酸濃度は、比較的高濃度のも
のを使用している。また、フッ化水素酸系のエッチング
液にガラス基板を浸漬すると、フッ化水素酸（ＨＦ）と
ガラスの強化剤であるＣａＯが反応してフッ化カルシウ
ム（ＣａＦ2 ）のフッ化物塩が生成する。このフッ化物
塩は溶解度が低く、ガラス基板表面に析出して反応を阻
害し、エッチングむらの原因となる。Generally, a hydrofluoric acid-based chemical solution in which hydrogen fluoride is dissolved in water is used as an etching solution for glass. The purpose is to form appropriate irregularities appropriately. The concentration of hydrofluoric acid used for etching is relatively high. When a glass substrate is immersed in a hydrofluoric acid-based etching solution, hydrofluoric acid (HF) reacts with CaO, which is a glass reinforcing agent, to generate a fluoride salt of calcium fluoride (CaF 2 ). . This fluoride salt has low solubility and precipitates on the surface of the glass substrate to inhibit the reaction, which causes uneven etching.
【００２０】この為、ガラス基板面に付着残存した研磨
粒子をエッチングにより洗浄する場合、ソーダガラス基
板のようにＣａＯの含有量が１２〜１３重量％と多く、
エッチング処理した際のフッ化カルシウムの析出量が多
いガラス種類については、特願平１０−３１９０１４号
で示したように、フッ化水素酸に添加する硫酸等の酸濃
度を５〜２０重量％と高くする必要があった。For this reason, when the abrasive particles remaining on the glass substrate surface are washed by etching, the content of CaO is as large as 12 to 13% by weight as in a soda glass substrate.
As shown in Japanese Patent Application No. 10-319014, for a glass type having a large amount of precipitated calcium fluoride upon etching, the acid concentration of sulfuric acid or the like added to hydrofluoric acid is 5 to 20% by weight. Needed to be higher.
【００２１】しかし、ガラス基板の種類のうち、アルミ
ノシリケートガラス基板の場合は、ＣａＯの含有量が２
〜３重量％であり、エッチング処理した際のフッ化カル
シウムの析出量が少ない。従って、フッ化水素酸に添加
する硫酸等の酸濃度はソーダガラス基板の場合に比べて
少なくてよい。また、アルミノシリケートガラス基板
は、Ａｌ2 Ｏ3 の含有量が１２重量％程度であるが、ア
ルミニウム（Ａｌ）は、フッ素イオンとの間で難溶性の
塩を生成しないため、ソーダガラス基板のように添加す
る酸濃度を高くすると、逆に研磨粒子の洗浄効果を悪化
させてしまう傾向があることが分かった。However, among the types of glass substrates, the aluminosilicate glass substrate has a CaO content of 2%.
To 3% by weight, and the amount of precipitated calcium fluoride during the etching treatment is small. Therefore, the acid concentration of sulfuric acid or the like added to hydrofluoric acid may be lower than that of a soda glass substrate. The aluminosilicate glass substrate has a content of Al 2 O 3 of about 12% by weight. However, aluminum (Al) does not form a hardly soluble salt with fluorine ions, and therefore, is similar to a soda glass substrate. It has been found that when the concentration of the acid to be added is increased, the cleaning effect of the abrasive particles tends to be deteriorated.
【００２２】又、セラミックガラス基板の場合にも、ア
ルミノシリケートガラス基板の場合と同様にＣａＯの含
有量が少なく、エッチング処理した際のフッ化カルシウ
ムの析出量が少ないので、ソーダガラス基板のように添
加する酸濃度を高くすると、逆に研磨粒子の洗浄効果を
悪化させてしまう傾向があることが分かった。Also, in the case of a ceramic glass substrate, as in the case of an aluminosilicate glass substrate, the content of CaO is small and the amount of precipitated calcium fluoride during the etching treatment is small. It has been found that when the concentration of the acid added is increased, the cleaning effect of the abrasive particles tends to be deteriorated.
【００２３】そこで、本発明者等は、アルミノシリケー
トガラス基板又はセラミックガラス基板に付着残存する
研磨粒子を除去するために有効な洗浄液として、フッ化
水素酸（ＨＦ）と硫酸等の酸から成る混酸液の適切な濃
度条件を検討した。Therefore, the present inventors have developed a mixed acid comprising hydrofluoric acid (HF) and an acid such as sulfuric acid as a cleaning solution effective for removing abrasive particles remaining on an aluminosilicate glass substrate or a ceramic glass substrate. The appropriate concentration conditions of the solution were examined.
【００２４】図１は、アルミノシリケートガラス基板を
例とした場合で、研磨処理した後にアルミノシリケート
ガラス基板に付着残存する研磨粒子を、フッ化水素酸と
硫酸の混酸液の洗浄液で洗浄する際の洗浄特性におい
て、洗浄液中のフッ化水素酸濃度が除去性能に及ぼす影
響を調べたものである。即ち、硫酸濃度を１重量％に一
定にした状態でフッ化水素酸濃度を０〜０．２重量％ま
で変化させた。また、図２は、上記洗浄特性において、
硫酸濃度が除去性能に及ぼす影響を調べたものであり、
フッ化水素酸濃度を０．１重量％に一定にした状態で硫
酸濃度を０〜１０重量％まで変化させた。研磨粒子を洗
浄する除去性能の評価としては、洗浄液でアルミノシリ
ケートガラス基板を洗浄した後にアルミノシリケートガ
ラス基板から除去されずに残存している０．３μｍ以上
の粒径の研磨粒子の個数を計測した。FIG. 1 shows a case where an aluminosilicate glass substrate is used as an example. Polishing particles remaining on the aluminosilicate glass substrate after polishing are washed with a cleaning solution of a mixed acid solution of hydrofluoric acid and sulfuric acid. In the cleaning characteristics, the effect of the concentration of hydrofluoric acid in the cleaning liquid on the removal performance was examined. That is, the concentration of hydrofluoric acid was changed from 0 to 0.2% by weight while the concentration of sulfuric acid was kept constant at 1% by weight. FIG. 2 shows the cleaning characteristics.
The effect of sulfuric acid concentration on removal performance was investigated.
The sulfuric acid concentration was varied from 0 to 10% by weight while the hydrofluoric acid concentration was kept constant at 0.1% by weight. As the evaluation of the removal performance for cleaning the abrasive particles, the number of abrasive particles having a particle diameter of 0.3 μm or more remaining without being removed from the aluminosilicate glass substrate after cleaning the aluminosilicate glass substrate with the cleaning liquid was measured. .
【００２５】図１から分かるように、フッ化水素酸濃度
を０重量％から０．２重量％の間で変化させた場合、
０．０５〜０．１５重量％の範囲では、残留粒子個数が
２０個／基板以下となり良好な粒子除去性能を示すが、
０．０５重量％未満のフッ化水素酸濃度、及び０．１５
重量％を越えるフッ化水素酸濃度では、粒子除去性能が
急激に悪化した。As can be seen from FIG. 1, when the hydrofluoric acid concentration is changed between 0% by weight and 0.2% by weight,
In the range of 0.05 to 0.15% by weight, the number of residual particles is 20 particles / substrate or less, indicating good particle removal performance.
A hydrofluoric acid concentration of less than 0.05% by weight, and 0.15
At a hydrofluoric acid concentration exceeding the weight percent, the particle removal performance deteriorated rapidly.
【００２６】また、図２から分かるように、フッ化水素
酸濃度を０．１重量％で一定として硫酸濃度を０〜１０
重量％まで変化させると、０．１重量％〜５重量％の範
囲では、残留粒子個数が１０個／基板程度と良好で安定
的な粒子除去性能を示すが、０．１重量％未満の硫酸濃
度、及び５重量％を越える硫酸濃度では、粒子除去性能
が悪化した。As can be seen from FIG. 2, the concentration of hydrofluoric acid is fixed at 0.1% by weight and the concentration of sulfuric acid is 0 to 10%.
In the range of 0.1% by weight to 5% by weight, the number of residual particles is about 10 particles / substrate, indicating a good and stable particle removal performance. When the concentration and the sulfuric acid concentration exceeded 5% by weight, the particle removal performance deteriorated.
【００２７】これら図１及び図２の結果から、フッ化水
素酸と硫酸の混酸液を洗浄液とする場合でも、ソーダガ
ラス基板の洗浄に適切なフッ化水素酸濃度、硫酸濃度
と、アルミノシリケートガラス基板の洗浄に適切なフッ
化水素酸濃度、硫酸濃度とは明らかに異なることが分か
る。この結果は、フッ化水素酸と硝酸の混酸液、又はフ
ッ化水素酸とリン酸の混酸液として調製した洗浄液の場
合にも同様の結果であった。From the results shown in FIGS. 1 and 2, even when a mixed acid solution of hydrofluoric acid and sulfuric acid is used as the cleaning liquid, the hydrofluoric acid concentration, the sulfuric acid concentration, and the aluminosilicate glass suitable for cleaning the soda glass substrate are determined. It can be seen that the concentrations of hydrofluoric acid and sulfuric acid that are appropriate for cleaning the substrate are clearly different. The same result was obtained in the case of a cleaning solution prepared as a mixed acid solution of hydrofluoric acid and nitric acid or a mixed acid solution of hydrofluoric acid and phosphoric acid.
【００２８】即ち、アルミノシリケートガラス基板に付
着した研磨粒子の除去に適したフッ化水素酸についてみ
ると、フッ化水素酸濃度が低すぎるとエッチング量が少
ないためにアルミノシリケートガラス基板に付着残存し
た研磨粒子の除去能力はない。従って、研磨粒子を除去
できるエッチング力を発揮可能なフッ化水素酸濃度の下
限は、図１より０．０５重量％である。逆に、フッ化水
素酸濃度が高すぎると、アルミノシリケートガラス基板
のエッチング速度が速すぎるために研磨粒子が付着して
いないアルミノシリケートガラス基板部分のみを局所的
に深くエッチングしてしまいエッチングむらが発生す
る。従って、深くエッチングされた部分と浅くエッチン
グされた部分とによりアルミノシリケートガラス基板に
凸凹が形成されるので、研磨粒子が除去される前にアル
ミノシリケートガラス基板自体の品質が維持できなくな
る。また、フッ化水素酸濃度が高すぎると、研磨粒子の
除去性能自体も低下する。従って、このような不具合が
生じないフッ化水素酸濃度の上限は、図１より０．１５
重量％である。That is, regarding hydrofluoric acid suitable for removing abrasive particles adhering to the aluminosilicate glass substrate, if the hydrofluoric acid concentration is too low, the etching amount is small, so that the hydrofluoric acid adhered and remained on the aluminosilicate glass substrate. No ability to remove abrasive particles. Therefore, the lower limit of the hydrofluoric acid concentration at which the etching force capable of removing the abrasive particles can be exerted is 0.05% by weight from FIG. Conversely, if the hydrofluoric acid concentration is too high, the etching rate of the aluminosilicate glass substrate is too high, and only the aluminosilicate glass substrate portion on which the abrasive particles are not adhered is locally deeply etched, resulting in uneven etching. appear. Therefore, unevenness is formed on the aluminosilicate glass substrate by the deeply etched portion and the shallowly etched portion, so that the quality of the aluminosilicate glass substrate itself cannot be maintained before the abrasive particles are removed. On the other hand, if the hydrofluoric acid concentration is too high, the removal performance itself of the abrasive particles also decreases. Therefore, the upper limit of the concentration of hydrofluoric acid at which such a problem does not occur is 0.15 from FIG.
% By weight.
【００２９】一方、硫酸濃度についてみると、アルミノ
シリケートガラス基板は、上述したようにＣａＯの含有
量が比較的少ないので、フッ化物塩であるフッ化カルシ
ウムの生成も少なく、硫酸濃度依存性が小さい。しか
し、硫酸濃度が０重量％では、生成したフッ化カルシウ
ムを除去できないので、アルミノシリケートガラス基板
に付着残存した研磨粒子の除去効果が低下する。また、
硫酸濃度を高くしすぎても研磨粒子の洗浄効果を悪化さ
せてしまう。従って、フッ化物塩を溶解可能で、且つ硫
酸がフッ化水素酸のエッチング力に悪影響を与えない硫
酸濃度としては、図２より、下限が０．１重量％であ
り、上限が５重量％である。On the other hand, regarding the sulfuric acid concentration, since the aluminosilicate glass substrate has a relatively small content of CaO as described above, the generation of calcium fluoride as a fluoride salt is small and the sulfuric acid concentration dependency is small. . However, when the sulfuric acid concentration is 0% by weight, the generated calcium fluoride cannot be removed, so that the effect of removing the abrasive particles remaining on the aluminosilicate glass substrate is reduced. Also,
If the sulfuric acid concentration is too high, the cleaning effect of the abrasive particles is deteriorated. Therefore, as shown in FIG. 2, the lower limit of the sulfuric acid concentration at which the fluoride salt can be dissolved and the sulfuric acid does not adversely affect the etching power of hydrofluoric acid is 0.1% by weight and the upper limit is 5% by weight. is there.
【００３０】尚、上記図１、図２はアルミノシリケート
ガラス基板の例であるが、セラミックガラス基板の場合
にも同様であった。Although FIGS. 1 and 2 show examples of an aluminosilicate glass substrate, the same applies to a case of a ceramic glass substrate.
【００３１】このように、ガラス基板に付着残存する研
磨粒子を除去する目的としたフッ化水素酸と硫酸等の酸
の混酸液から成る洗浄液を調製する場合には、ガラス基
板の材質によって含有物と組成が異なるので、材質に適
したフッ化水素酸濃度と硫酸濃度の組み合わせにするこ
とが重要なポイントになる。As described above, when preparing a cleaning solution composed of a mixed acid solution of an acid such as hydrofluoric acid and sulfuric acid for the purpose of removing the polishing particles remaining on the glass substrate, the content of the cleaning solution depends on the material of the glass substrate. Therefore, it is important to make a combination of hydrofluoric acid concentration and sulfuric acid concentration suitable for the material.
【００３２】本発明は、上記知見に基づいて成されたも
ので、アルミノシリケートガラス基板又はセラミックガ
ラス基板の表面に付着残存する研磨粒子を洗浄除去する
洗浄液を、０．０５〜０．１５重量％濃度のフッ化水素
酸（ＨＦ）と、０．１重量％以上で５重量％未満の濃度
の硫酸（Ｈ2 ＳＯ4 ）又は硝酸（ＨＮＯ3 ）若しくはリ
ン酸（Ｈ3 ＰＯ4 ）とから成る混酸液で構成すると共
に、この洗浄液を使用してアルミノシリケートガラス基
板又はセラミックガラス基板を洗浄するようにしたもの
である。The present invention has been made on the basis of the above findings, and a cleaning solution for cleaning and removing abrasive particles remaining on the surface of an aluminosilicate glass substrate or a ceramic glass substrate is 0.05 to 0.15% by weight. And hydrofluoric acid (HF) at a concentration of at least 0.1% by weight and less than 5% by weight of sulfuric acid (H 2 SO 4 ) or nitric acid (HNO 3 ) or phosphoric acid (H 3 PO 4 ). In addition to the cleaning liquid, the cleaning liquid is used to clean an aluminosilicate glass substrate or a ceramic glass substrate.
【００３３】図３は、本発明の洗浄液に、例としてアル
ミノシリケートガラス基板を浸漬させながら洗浄液を振
動させる本発明の洗浄方法を組み込んだ洗浄工程を示し
たものであり、予備洗浄工程、薬液洗浄工程、リンス工
程、乾燥工程の４工程からなっている。尚、セラミック
ガラス基板の場合も同様である。FIG. 3 shows a cleaning step incorporating the cleaning method of the present invention in which the cleaning liquid is vibrated while immersing an aluminosilicate glass substrate in the cleaning liquid of the present invention. It consists of four steps: a process, a rinsing process, and a drying process. The same applies to the case of a ceramic glass substrate.
【００３４】予備洗浄工程では、研磨されたアルミノシ
リケートガラス基板１２を収納した洗浄用カセット１４
が予備洗浄槽１６内の予備洗浄水１７（５０〜７０°Ｃ
の超純水、又は酸性イオン水）に浸漬され、超音波発生
装置１８から予備洗浄水１７に超音波が照射されてアル
ミノシリケートガラス基板１２が予備洗浄される。In the preliminary cleaning step, a cleaning cassette 14 containing the polished aluminosilicate glass substrate 12 is stored.
Is the pre-cleaning water 17 (50-70 ° C) in the pre-cleaning tank 16.
(Ultra-pure water or acidic ionized water), and ultrasonic waves are irradiated from the ultrasonic generator 18 to the pre-cleaning water 17 to pre-clean the aluminosilicate glass substrate 12.
【００３５】薬液洗浄工程では、予備洗浄槽１６から引
き上げられた洗浄用カセット１４が薬液洗浄槽２０内の
本発明の洗浄液２１に浸漬され、超音波発生装置２２か
ら洗浄液２１に超音波が照射されてアルミノシリケート
ガラス基板１２が薬液洗浄される。In the chemical cleaning step, the cleaning cassette 14 pulled up from the preliminary cleaning tank 16 is immersed in the cleaning liquid 21 of the present invention in the chemical cleaning tank 20, and the cleaning liquid 21 is irradiated with ultrasonic waves from the ultrasonic generator 22. Thus, the aluminosilicate glass substrate 12 is washed with a chemical solution.
【００３６】次に、リンス工程では、薬液洗浄槽２０か
ら引き上げられた洗浄用カセット１４が、先ず第１リン
ス槽２４内の純水２５中に浸漬され、超音波発生装置２
７から純水２５中に超音波が照射されてアルミノシリケ
ートガラス基板１２がリンスされる。続いて、洗浄用カ
セット１４が第２リンス槽２６内の純水２５中に浸漬さ
れ、超音波発生装置２８から純水２５中に超音波が照射
されてアルミノシリケートガラス基板１２がリンスされ
る。また、純水２５は、第２リンス槽２６に先ず供給さ
れ、第２リンス槽２６での使用済純水が第１リンス槽２
４に供給される。Next, in the rinsing step, the cleaning cassette 14 pulled up from the chemical cleaning tank 20 is first immersed in pure water 25 in the first rinsing tank 24,
Ultrasonic waves are irradiated from 7 into pure water 25 to rinse the aluminosilicate glass substrate 12. Subsequently, the cleaning cassette 14 is immersed in pure water 25 in the second rinsing tank 26, and ultrasonic waves are irradiated into the pure water 25 from the ultrasonic generator 28 to rinse the aluminosilicate glass substrate 12. The pure water 25 is first supplied to the second rinsing tank 26, and the used pure water in the second rinsing tank 26 is supplied to the first rinsing tank 2.
4 is supplied.
【００３７】乾燥工程では、第２リンス槽２６から引き
上げられた洗浄用カセット１４が、乾燥器３１内に置か
れる。乾燥器３１内の下部には、ヒータ（図示せず）が
設けられており、揮発する有機溶剤の蒸気によりアルミ
ノシリケートガラス基板１２に付着している純水２５が
除去される。この場合、乾燥器３１を真空装置（図示せ
ず）とを接続して乾燥器３１内を減圧すると更に効果的
に純水２５を除去できる。In the drying step, the cleaning cassette 14 pulled up from the second rinsing tank 26 is placed in the dryer 31. A heater (not shown) is provided in the lower part of the drier 31, and the pure water 25 attached to the aluminosilicate glass substrate 12 is removed by the vapor of the volatile organic solvent. In this case, if the inside of the dryer 31 is depressurized by connecting the dryer 31 to a vacuum device (not shown), the pure water 25 can be removed more effectively.
【００３８】尚、予備洗浄工程、薬液洗浄工程、リンス
工程において、超音波発生装置１８、２２、２７、２８
から液に与える超音波の周波数は、１５〜５０ｋＨｚ若
しくは７５０ｋＨｚ以上が好ましい。それ以外の周波数
では、洗浄を促進するキャビテーションが発生しにく
い。若しくは液に十分な加速度が与えられず、アルミノ
シリケートガラス基板１２表面に付着残存した研磨粒子
の洗浄能力が低下する。また、洗浄液の温度は常温でよ
く、特に温度の限定はない。また、図３において、符
号、１９、２３、２９、３０はオーバーフロー液が越流
するトラフである。In the pre-cleaning step, the chemical cleaning step, and the rinsing step, the ultrasonic generators 18, 22, 27, 28
The frequency of the ultrasonic wave to be applied to the liquid is preferably 15 to 50 kHz or 750 kHz or more. At other frequencies, cavitation that promotes cleaning is less likely to occur. Alternatively, sufficient acceleration is not applied to the liquid, and the cleaning ability of the abrasive particles adhered and remaining on the surface of the aluminosilicate glass substrate 12 is reduced. The temperature of the cleaning liquid may be room temperature, and there is no particular limitation on the temperature. In FIG. 3, reference numerals 19, 23, 29, and 30 denote troughs in which the overflow liquid overflows.
【００３９】図４は、例としてアルミノシリケートガラ
ス基板１２上に本発明の洗浄液を供給しながら、回転す
るブラシローラをアルミノシリケートガラス基板１２上
に押しつける本発明の洗浄方法を適用した洗浄装置を示
したものである。尚、セラミックガラス基板の場合にも
同様である。FIG. 4 shows a cleaning apparatus to which the cleaning method of the present invention is applied, in which a rotating brush roller is pressed onto the aluminosilicate glass substrate 12 while supplying the cleaning liquid of the present invention onto the aluminosilicate glass substrate 12 as an example. It is a thing. The same applies to the case of a ceramic glass substrate.
【００４０】図４に示すように、研磨粒子（砥粒）が付
着したアルミノシリケートガラス基板１２の上方には、
該アルミノシリケートガラス基板１２上に洗浄液を供給
する洗浄液ノズル３２が設けられ、０．０５〜０．１５
重量％濃度のフッ化水素酸と、０．１重量％以上で５重
量％未満の濃度の硫酸又は硝酸若しくはリン酸とから成
る混酸液である洗浄液がアルミノシリケートガラス基板
１２上に注がれる。そして、アルミノシリケートガラス
基板１２上に薄く洗浄液の膜が形成された状態で回転さ
せたブラシローラ３４をアルミノシリケートガラス基板
１２上に押しつけながら往復移動させる。これにより、
洗浄液のエッチング力とブラシローラ３４のスクラビン
グ力の両方でアルミノシリケートガラス基板１２に付着
残存する研磨粒子が除去される。この場合、アルミノシ
リケートガラス基板１２上の洗浄液の液膜に超音波を当
てて液膜を振動させると更に研磨粒子の除去性能を向上
させることができる。尚、ブラシローラ３４に代えてス
ポンジローラを使用してもよい。また、ブラシローラ３
４による洗浄後は、図３と同様に、リンス工程、乾燥工
程を行う。As shown in FIG. 4, above the aluminosilicate glass substrate 12 to which the abrasive particles (abrasive particles) have adhered,
A cleaning liquid nozzle 32 for supplying a cleaning liquid is provided on the aluminosilicate glass substrate 12.
A cleaning solution, which is a mixed acid solution composed of hydrofluoric acid at a concentration of 0.1% by weight and sulfuric acid or nitric acid or phosphoric acid at a concentration of 0.1% by weight or more and less than 5% by weight, is poured onto the aluminosilicate glass substrate 12. Then, the brush roller 34 rotated while the thin film of the cleaning liquid is formed on the aluminosilicate glass substrate 12 is reciprocated while pressing the brush roller 34 onto the aluminosilicate glass substrate 12. This allows
Abrasive particles remaining on the aluminosilicate glass substrate 12 are removed by both the etching force of the cleaning liquid and the scrubbing force of the brush roller 34. In this case, if the liquid film of the cleaning liquid on the aluminosilicate glass substrate 12 is irradiated with ultrasonic waves to vibrate the liquid film, the performance of removing the abrasive particles can be further improved. Note that a sponge roller may be used instead of the brush roller 34. Also, the brush roller 3
After the cleaning by step 4, a rinsing step and a drying step are performed as in FIG.
【００４１】[0041]
【実施例】次に、本発明の具体的な実施例を説明する。Next, specific embodiments of the present invention will be described.
【００４２】〔実施例１〕アルミノシリケートガラス基
板を洗浄槽に浸漬して超音波発生装置で洗浄液を振動さ
せる場合の実施例を説明する。Example 1 An example in which an aluminosilicate glass substrate is immersed in a cleaning tank and the cleaning liquid is vibrated by an ultrasonic generator will be described.
【００４３】以下示すようにNo.１〜 ９までの洗浄液を
調製し、アルミノシリケートガラス基板を研磨処理した
後にアルミノシリケートガラス基板に付着残存する研磨
粒子の除去性能を試験した。The cleaning liquids No. 1 to No. 9 were prepared as shown below, and after the aluminosilicate glass substrate was polished, the removal performance of the abrasive particles remaining on the aluminosilicate glass substrate was tested.
【００４４】試験は、先ず、２．５インチの磁気ディス
ク用のアルミノシリケートガラス基板を研磨砥粒として
酸化セリウム（三井金属工業製、ＣｅＯ2 、０．４〜
０．８μｍ）を用い、研磨装置によりテーブル回転数４
０ｒｐｍ、研磨時間２０分間、研磨液の酸化セリウム濃
度１０重量％、押付け圧力７５ｇ／ｃｍ2 の条件で研磨
を行なった。研磨後のアルミノシリケートガラス基板を
６０℃の温純水を用いて予備洗浄を行い、薬液洗浄用の
試験サンプルとした。そして、以下に示した本実施の洗
浄液１〜６と、比較例として調製した比較液１〜２を使
用して以下の条件でアルミノシリケートガラス基板の洗
浄実験を行った。In the test, first, cerium oxide (manufactured by Mitsui Kinzoku Kogyo, CeO 2 , 0.4-0.4 mm) was used as abrasive grains on a 2.5-inch aluminosilicate glass substrate for a magnetic disk.
0.8 μm) and a table rotation speed of 4
Polishing was performed under the conditions of 0 rpm, a polishing time of 20 minutes, a cerium oxide concentration of the polishing liquid of 10% by weight, and a pressing pressure of 75 g / cm 2 . The polished aluminosilicate glass substrate was preliminarily cleaned with hot pure water at 60 ° C. to obtain a test sample for chemical cleaning. Then, an aluminosilicate glass substrate washing experiment was performed under the following conditions using the following washing solutions 1 to 6 of the present embodiment and comparative solutions 1 and 2 prepared as comparative examples.
【００４５】本実施の洗浄液及び比較液ともに、薬液洗
浄槽内の洗浄液の容量を２Ｌ、超音波発生装置の周波数
を４５ｋＨｚとし、薬液洗浄槽に浸漬している洗浄時間
を３分とした。この条件で研磨後のアルミノシリケート
ガラス基板を洗浄した時の研磨粒子の除去性能を比較し
た。For both the cleaning liquid of this embodiment and the comparative liquid, the volume of the cleaning liquid in the chemical liquid cleaning tank was 2 L, the frequency of the ultrasonic wave generator was 45 kHz, and the cleaning time during immersion in the chemical liquid cleaning tank was 3 minutes. Under these conditions, the removal performance of abrasive particles when the aluminosilicate glass substrate after polishing was washed was compared.
【００４６】除去性能の評価は、洗浄後に２００倍の顕
微鏡観察により暗視野で０．３μｍ以上の研磨粒子の個
数を目視でカウントすることにより行った。また、エッ
チングむらがないかについては、アルミノシリケートガ
ラス基板の表面粗さ（Ｒｍａｘ）を調べることにより行
い、先端が０．２μｍ角の触針を有する表面粗さ計（小
坂研究所製）で測定した。The removal performance was evaluated by visually counting the number of abrasive particles having a size of 0.3 μm or more in a dark field under a microscope of 200 times after washing. The unevenness of the etching was determined by examining the surface roughness (Rmax) of the aluminosilicate glass substrate, and was measured with a surface roughness meter (manufactured by Kosaka Laboratory) having a 0.2 μm square stylus tip. did.
【００４７】（洗浄液１）濃度４６％のフッ化水素酸
２．２ｃｃと、濃度９６％の硫酸２ｃｃを、１９９６ｃ
ｃの純水中に攪拌しながら徐々に滴下し、フッ化水素酸
濃度０．０５重量％、硫酸濃度０．１重量％の洗浄液を
調製した。(Cleaning liquid 1) A solution of 2.2 cc of hydrofluoric acid having a concentration of 46% and 2 cc of sulfuric acid having a concentration of 96% was obtained in 1996 c.
The resulting mixture was gradually dropped into pure water c with stirring to prepare a cleaning solution having a hydrofluoric acid concentration of 0.05% by weight and a sulfuric acid concentration of 0.1% by weight.
【００４８】（洗浄液２）濃度４６％のフッ化水素酸
４．４ｃｃと、濃度９６％の硫酸２０ｃｃを、１９９６
ｃｃの純水中に攪拌しながら徐々に滴下し、フッ化水素
酸濃度０．１重量％、硫酸濃度１重量％の洗浄液を調製
した。(Cleaning liquid 2) In 1996, was added 4.4 cc of hydrofluoric acid having a concentration of 46% and 20 cc of sulfuric acid having a concentration of 96%.
The resulting mixture was gradually dropped into cc of pure water while stirring to prepare a cleaning solution having a hydrofluoric acid concentration of 0.1% by weight and a sulfuric acid concentration of 1% by weight.
【００４９】（洗浄液３）濃度４６％のフッ化水素酸
２．２ｃｃと、濃度６０％の硝酸３．３ｃｃを、１９９
４．５ｃｃの純水中に攪拌しながら徐々に滴下し、フッ
化水素酸濃度０．０５重量％、硝酸濃度０．１重量％の
洗浄液を調製した。(Cleaning liquid 3) 2.2 cc of hydrofluoric acid having a concentration of 46% and 3.3 cc of nitric acid having a concentration of 60% were added to 199
The solution was gradually dropped into 4.5 cc of pure water with stirring to prepare a cleaning solution having a hydrofluoric acid concentration of 0.05% by weight and a nitric acid concentration of 0.1% by weight.
【００５０】（洗浄液４）濃度４６％のフッ化水素酸
４．４ｃｃと、濃度６０％の硝酸３３ｃｃを、１９６３
ｃｃの純水中に攪拌しながら徐々に滴下し、フッ化水素
酸濃度０．１重量％、硝酸濃度１重量％の洗浄液を調製
した。(Cleaning liquid 4) 4.4cc of hydrofluoric acid having a concentration of 46% and 33cc of nitric acid having a concentration of 60% were added in 1963.
The resulting mixture was gradually dropped into cc of pure water with stirring to prepare a washing solution having a hydrofluoric acid concentration of 0.1% by weight and a nitric acid concentration of 1% by weight.
【００５１】（洗浄液５）濃度４６％のフッ化水素酸
２．２ｃｃと、濃度８５％のリン酸２．４ｃｃを、１９
９３ｃｃの純水中に攪拌しながら徐々に滴下し、フッ化
水素酸濃度０．０５重量％、リン酸濃度０．１重量％の
洗浄液を調製した。(Cleaning liquid 5) 2.2 cc of hydrofluoric acid having a concentration of 46% and 2.4 cc of phosphoric acid having a concentration of 85% were added to 19
The solution was gradually dropped into 93 cc of pure water with stirring to prepare a washing solution having a hydrofluoric acid concentration of 0.05% by weight and a phosphoric acid concentration of 0.1% by weight.
【００５２】（洗浄液６）濃度４６％のフッ化水素酸
４．４ｃｃと、濃度８５％のリン酸２４ｃｃを、１９７
２ｃｃの純水中に攪拌しながら徐々に滴下し、フッ化水
素酸濃度０．１重量％、リン酸濃度１重量％の洗浄液を
調製した。(Cleaning liquid 6) 4.4 cc of hydrofluoric acid with a concentration of 46% and 24 cc of phosphoric acid with a concentration of 85% were mixed with 197
The solution was gradually dropped into 2 cc of pure water with stirring to prepare a cleaning solution having a hydrofluoric acid concentration of 0.1% by weight and a phosphoric acid concentration of 1% by weight.
【００５３】（比較液１）濃度４６％のフッ化水素酸２
２ｃｃを攪拌しながら１９７８ｃｃの純水中に徐々に滴
下し、フッ化水素酸濃度１重量％の比較液を調製した。(Comparative solution 1) Hydrofluoric acid 2 having a concentration of 46%
While stirring 2 cc, the solution was gradually dropped into 1978 cc of pure water to prepare a comparative solution having a hydrofluoric acid concentration of 1% by weight.
【００５４】（比較液２）濃度４６％のフッ化水素酸
２．２ｃｃと、濃度９６％の硫酸４１７ｃｃを、１５８
１ｃｃの純水中に攪拌しながら徐々に滴下し、フッ化水
素酸濃度０．０５重量％、硫酸濃度２０重量％の洗浄液
を調製した。(Comparative solution 2) 2.2 cc of 46% hydrofluoric acid and 417 cc of 96% sulfuric acid were added to 158
The solution was gradually dropped into 1 cc of pure water while stirring to prepare a cleaning solution having a hydrofluoric acid concentration of 0.05% by weight and a sulfuric acid concentration of 20% by weight.
【００５５】以上の条件で行った試験の結果を表１に示
す。Table 1 shows the results of the tests performed under the above conditions.
【００５６】[0056]
【表１】 表１の結果から明らかなように、本発明の洗浄液を使用
してアルミノシリケートガラス基板を洗浄した場合に
は、アルミノシリケートガラス基板に付着残存する研磨
粒子の個数は全て４０個以下であり、アルミノシリケー
トガラス基板から研磨粒子を効果的に除去することがで
きた。特に、フッ化水素酸濃度０．１重量％と硫酸濃度
１重量％を混合した洗浄液２の除去性能が良かった。ま
た、本発明の洗浄液を使用した場合には、アルミノシリ
ケートガラス基板のＲｍａｘも１０ｎｍ以下であり、エ
ッチングむらも認められなかった。[Table 1] As is clear from the results in Table 1, when the cleaning liquid of the present invention was used to clean the aluminosilicate glass substrate, the number of abrasive particles remaining on the aluminosilicate glass substrate was all 40 or less. The abrasive particles were effectively removed from the silicate glass substrate. In particular, the removal performance of the cleaning solution 2 in which the hydrofluoric acid concentration of 0.1% by weight and the sulfuric acid concentration of 1% by weight were mixed was excellent. When the cleaning solution of the present invention was used, the Rmax of the aluminosilicate glass substrate was 10 nm or less, and no etching unevenness was observed.
【００５７】これに対し、アルミノシリケートガラス基
板を、硫酸濃度が０重量％の比較液１で洗浄した場合に
は、アルミノシリケートガラス基板に付着残存する研磨
粒子の個数は約５００個であり、粒子除去性能が著しく
悪いと共に、Ｒｍａｘが６７ｎｍであり大きなエッチン
グむらも認められた。また、フッ化水素酸濃度は本発明
の範囲内であるが、硫酸濃度が本発明の洗浄液の上限５
重量％よりも大きな２０重量％とした比較液２で洗浄し
た場合は、硫酸を含まない比較液１よりも良いものの、
アルミノシリケートガラス基板に付着残存する研磨粒子
の個数は約１００個であり、粒子除去性能が悪いと共
に、Ｒｍａｘが２５ｎｍでありエッチングむらも認めら
れた。 〔実施例２〕次に、アルミノシリケートガラス基板上
に、洗浄液を供給しながら、スポンジローラでアルミノ
シリケートガラス基板の表面をブラッシングする実施例
を説明する。On the other hand, when the aluminosilicate glass substrate was washed with Comparative Solution 1 having a sulfuric acid concentration of 0% by weight, the number of abrasive particles remaining on the aluminosilicate glass substrate was about 500. The removal performance was remarkably poor, and Rmax was 67 nm, and large uneven etching was observed. Further, the concentration of hydrofluoric acid is within the range of the present invention, but the concentration of sulfuric acid is 5 times the upper limit of the cleaning solution of the present invention.
When washed with Comparative Solution 2 having a weight ratio of 20% by weight larger than that of Comparative Solution 1 containing no sulfuric acid,
The number of abrasive particles adhering to and remaining on the aluminosilicate glass substrate was about 100, and the particle removal performance was poor. Rmax was 25 nm, and uneven etching was observed. [Embodiment 2] Next, an embodiment of brushing the surface of an aluminosilicate glass substrate with a sponge roller while supplying a cleaning liquid onto the aluminosilicate glass substrate will be described.
【００５８】外径６５ｍｍ、内径２０ｍｍ、厚さ０．６
３５ｍｍのドーナツ状のアルミノシリケートガラス基板
を平均粒径０．６μｍの酸化セリウムを主成分とする研
磨砥粒で１０分間研磨した。このアルミノシリケートガ
ラス基板上に、実施例１で説明した洗浄液１〜６、又は
比較液１〜２を供給しながら、ポリビニルホルマール製
のブラシローラを回転数５００ｒｐｍ、押圧力２００ｇ
／ｃｍ2 で１分間ブラシ洗浄した。ブラシ洗浄後のアル
ミノシリケートガラス基板は、オーバーフロー方式で純
水を連続供給しているリンス槽に浸漬し、３分間リンス
洗浄し、その後溶剤蒸気乾燥を行なった。Outer diameter 65 mm, inner diameter 20 mm, thickness 0.6
A 35 mm donut-shaped aluminosilicate glass substrate was polished for 10 minutes with abrasive grains mainly composed of cerium oxide having an average particle diameter of 0.6 μm. While supplying the cleaning liquids 1 to 6 or the comparative liquids 1 to 2 described in Example 1 onto this aluminosilicate glass substrate, a polyvinyl formal brush roller was rotated at 500 rpm and pressed at 200 g.
/ Cm 2 for 1 minute. The aluminosilicate glass substrate after the brush cleaning was immersed in a rinse tank to which pure water was continuously supplied by an overflow method, rinsed for 3 minutes, and then subjected to solvent vapor drying.
【００５９】そして、実施例１で説明した除去性能の評
価と同様の方法で、洗浄液１〜６、比較液１〜２ごとに
アルミノシリケートガラス基板から除去される研磨粒子
の除去性能を評価した。Then, in the same manner as in the evaluation of the removal performance described in Example 1, the removal performance of the abrasive particles removed from the aluminosilicate glass substrate was evaluated for each of the cleaning liquids 1 to 6 and the comparative liquids 1 and 2.
【００６０】この結果、洗浄液１〜６はいずれも実施例
１で説明したと同様に研磨粒子の除去性能がよく、且つ
Ｒｍａｘも小さく、実施例１と同様の効果を得ることが
できた。これに対し、比較液１〜２の場合は、ブラシ洗
浄においても粒子除去性能が悪く、Ｒｍａｘも大きかっ
た。As a result, all of the cleaning liquids 1 to 6 had good abrasive particle removal performance and a small Rmax as described in Example 1, and the same effects as in Example 1 could be obtained. On the other hand, in the case of Comparative Liquids 1 and 2, the particle removal performance was poor even in brush cleaning, and Rmax was large.
【００６１】[0061]
【発明の効果】以上説明したように、本発明のアルミノ
シリケートガラス基板又はセラミックガラス基板の洗浄
液及び洗浄方法によれば、アルミノシリケートガラス基
板又はセラミックガラス基板に適したフッ化水素酸濃度
と硫酸等の酸濃度のものとを混合して洗浄液を調製した
ので、アルミノシリケートガラス基板又はセラミックガ
ラス基板に付着残存した研磨粒子を効果的に洗浄除去で
き、しかもエッチングむらも生じることがない。As described above, according to the cleaning solution and the cleaning method for an aluminosilicate glass substrate or a ceramic glass substrate of the present invention, the concentration of hydrofluoric acid and sulfuric acid suitable for the aluminosilicate glass substrate or the ceramic glass substrate are improved. Since the cleaning solution is prepared by mixing the polishing solution with the acid having the above acid concentration, the abrasive particles remaining on the aluminosilicate glass substrate or the ceramic glass substrate can be effectively removed by cleaning, and no etching unevenness occurs.
【００６２】従って、アルミノシリケートガラス基板自
体又はセラミックガラス基板自体の品質を損なうことな
く、研磨工程においてアルミノシリケートガラス基板又
はセラミックガラス基板に付着残存した研磨粒子を効果
的に除去することができる。Therefore, it is possible to effectively remove the polishing particles remaining on the aluminosilicate glass substrate or the ceramic glass substrate in the polishing step without deteriorating the quality of the aluminosilicate glass substrate itself or the ceramic glass substrate itself.
【図１】アルミノシリケートガラス基板に付着残存する
研磨粒子の除去性能と、フッ化水素酸濃度との関係を説
明する説明図FIG. 1 is an explanatory diagram illustrating the relationship between the performance of removing abrasive particles adhering and remaining on an aluminosilicate glass substrate and the concentration of hydrofluoric acid.
【図２】アルミノシリケートガラス基板に付着残存する
研磨粒子の除去性能と、硫酸濃度との関係を説明する説
明図FIG. 2 is an explanatory diagram illustrating the relationship between the removal performance of abrasive particles adhering and remaining on an aluminosilicate glass substrate and the sulfuric acid concentration.
【図３】本発明の洗浄方法のうち、アルミノシリケート
ガラス基板を洗浄液に浸漬させる洗浄方法を組み込んだ
洗浄工程を説明する説明図FIG. 3 is an explanatory view illustrating a cleaning step in which a cleaning method of dipping an aluminosilicate glass substrate in a cleaning liquid is incorporated in the cleaning method of the present invention.
【図４】本発明の洗浄方法のうち、アルミノシリケート
ガラス基板上に洗浄液を供給しながらブラシローラでブ
ラッシングする洗浄方法を説明する説明図FIG. 4 is an explanatory view illustrating a cleaning method of brushing with a brush roller while supplying a cleaning liquid onto an aluminosilicate glass substrate among cleaning methods of the present invention.
１２…アルミノシリケートガラス基板、１４…洗浄用カ
セット、１６…予備洗浄槽、１７…予備洗浄水、１８、
２２、２７、２８…超音波発生装置、２０…薬液洗浄
槽、２１…洗浄液（ＨＦ＋Ｈ2 ＳＯ4 ）、２４…第１リ
ンス槽、２５…純水、２６…第２リンス槽、３１…乾燥
器12 ... aluminosilicate glass substrate, 14 ... cleaning cassette, 16 ... preliminary cleaning tank, 17 ... preliminary cleaning water, 18,
22,27,28 ... ultrasonic generator, 20 ... chemical cleaning tank, 21 ... washing solution (HF + H 2 SO 4) , 24 ... first rinse tank, 25 ... purified water, 26 ... second rinse tank 31 ... dryer
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 3B201 AA03 BA02 BA08 BA14 BB04 BB05 BB82 BB83 BB89 BB93 BB96 CA01 CC01 CC11 CC15 CC21 4G059 AA08 AC30 4H003 BA12 DA05 DA15 DB01 DC02 DC04 EA03 EA04 EA05 ED02 FA28 5D112 AA02 BA03 GA08 GA15 GA30 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 3B201 AA03 BA02 BA08 BA14 BB04 BB05 BB82 BB83 BB89 BB93 BB96 CA01 CC01 CC11 CC15 CC21 4G059 AA08 AC30 4H003 BA12 DA05 DA15 DB01 DC02 DC04 EA03 EA04 EA05 EA02 GA28 A08 GA08
Claims (4)
ックガラス基板の表面に付着残存する研磨粒子を洗浄除
去する洗浄液において、 前記洗浄液は、０．０５〜０．１５重量％濃度のフッ化
水素酸（ＨＦ）と、０．１重量％以上で５重量％未満の
濃度の硫酸（Ｈ2 ＳＯ4 ）又は硝酸（ＨＮＯ3）若しく
はリン酸（Ｈ3 ＰＯ4 ）とから成る混酸液であることを
特徴とするアルミノシリケートガラス基板又はセラミッ
クガラス基板の洗浄液。1. A cleaning liquid for cleaning and removing abrasive particles adhering and remaining on the surface of an aluminosilicate glass substrate or a ceramic glass substrate, wherein the cleaning liquid has a concentration of 0.05 to 0.15% by weight of hydrofluoric acid (HF). And sulfuric acid (H 2 SO 4 ) or nitric acid (HNO 3 ) or phosphoric acid (H 3 PO 4 ) having a concentration of 0.1% by weight or more and less than 5% by weight. Cleaning liquid for aluminosilicate glass substrate or ceramic glass substrate.
ックガラス基板の表面に付着残存する研磨粒子を洗浄除
去する洗浄方法において、 前記アルミノシリケートガラス基板又はセラミックガラ
ス基板を、０．０５〜０．１５重量％濃度のフッ化水素
酸（ＨＦ）と、０．１重量％以上で５重量％未満の濃度
の硫酸（Ｈ2 ＳＯ4 ）又は硝酸（ＨＮＯ3 ）若しくはリ
ン酸（Ｈ3 ＰＯ 4 ）とから成る混酸液である洗浄液に浸
漬すると共に、該洗浄液を振動させることを特徴とする
アルミノシリケートガラス基板又はセラミックガラス基
板の洗浄方法。2. Aluminosilicate glass substrate or ceramic
Abrasive particles remaining on the surface of the glass substrate
In the cleaning method, the aluminosilicate glass substrate or the ceramic glass
Substrate with a concentration of 0.05 to 0.15% by weight of hydrogen fluoride
Acid (HF) and a concentration of 0.1% by weight or more and less than 5% by weight
Sulfuric acid (HTwo SOFour ) Or nitric acid (HNOThree ) Or
Acid (HThree PO Four Immersion in a cleaning solution that is a mixed acid solution consisting of
It is characterized by vibrating the washing liquid while soaking.
Aluminosilicate glass substrate or ceramic glass base
How to wash the board.
ックガラス基板の表面に付着残存する研磨粒子を洗浄除
去するガラス基板の洗浄方法において、 前記アルミノシリケートガラス基板上又はセラミックガ
ラス基板上に、０．０５〜０．１５重量％濃度のフッ化
水素酸（ＨＦ）と、０．１重量％以上で５重量％未満の
濃度の硫酸（Ｈ2 ＳＯ4 ）又は硝酸（ＨＮＯ3 ）若しく
はリン酸（Ｈ3ＰＯ4 ）とから成る混酸液である洗浄液
を供給しながら、回転するブラシローラ又はスポンジロ
ーラを前記アルミノシリケートガラス基板上又はセラミ
ックガラス基板上に押しつけることを特徴とするアルミ
ノシリケートガラス基板又はセラミックガラス基板の洗
浄方法。3. A method of cleaning a glass substrate for cleaning and removing abrasive particles adhered and remaining on the surface of an aluminosilicate glass substrate or a ceramic glass substrate, comprising: and .15 wt% concentration of hydrofluoric acid (HF), a concentration of less than 5 wt% with 0.1 wt% or more sulfuric acid (H 2 SO 4) or nitric acid (HNO 3) or phosphoric acid (H 3 PO 4 Cleaning the aluminosilicate glass substrate or the ceramic glass substrate, wherein a rotating brush roller or a sponge roller is pressed against the aluminosilicate glass substrate or the ceramic glass substrate while supplying a cleaning solution as a mixed acid solution comprising Method.
ス基板又はセラミックガラス基板を５０〜７０°Ｃの超
純水又はｐＨ４以下の酸性イオン水により洗浄する予備
洗浄工程と、 前記予備洗浄工程後の前記アルミノシリケートガラス基
板又はセラミックガラス基板を、請求項２又は請求項３
に記載の洗浄方法より洗浄する薬液洗浄工程と、 前記薬液洗浄工程で前記アルミノシリケートガラス基板
又はセラミックガラス基板に付着した洗浄液を純水で洗
い流すリンス工程と、 前記リンス工程でアルミノシリケートガラス基板又はセ
ラミックガラス基板に付着した水分を乾燥する乾燥工程
とから成ることを特徴とするアルミノシリケートガラス
基板又はセラミックガラス基板の洗浄方法。4. A pre-cleaning step of cleaning the aluminosilicate glass substrate or the ceramic glass substrate after the polishing treatment with ultrapure water at 50 to 70 ° C. or acidic ion water of pH 4 or less; An aluminosilicate glass substrate or a ceramic glass substrate according to claim 2 or 3.
A chemical cleaning step of cleaning by the cleaning method described in the above, a rinsing step of washing the cleaning liquid attached to the aluminosilicate glass substrate or the ceramic glass substrate in the chemical cleaning step with pure water, and an aluminosilicate glass substrate or ceramic in the rinsing step A drying step of drying water adhered to the glass substrate. A method for cleaning an aluminosilicate glass substrate or a ceramic glass substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27325199A JP3575349B2 (en) | 1999-09-27 | 1999-09-27 | Cleaning solution and cleaning method for aluminosilicate glass substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27325199A JP3575349B2 (en) | 1999-09-27 | 1999-09-27 | Cleaning solution and cleaning method for aluminosilicate glass substrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001098298A true JP2001098298A (en) | 2001-04-10 |
| JP3575349B2 JP3575349B2 (en) | 2004-10-13 |
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| JP27325199A Expired - Fee Related JP3575349B2 (en) | 1999-09-27 | 1999-09-27 | Cleaning solution and cleaning method for aluminosilicate glass substrate |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006027912A (en) * | 2004-07-12 | 2006-02-02 | Nishiyama Stainless Chem Kk | Method for polishing surface of glass plate, glass substrate for flat panel display, and flat panel display |
| JP2006083376A (en) * | 2004-08-18 | 2006-03-30 | Mitsubishi Gas Chem Co Inc | Cleaning liquid and cleaning method |
| JP2006528551A (en) * | 2003-05-22 | 2006-12-21 | アプライド マテリアルズ インコーポレイテッド | Cleaning process chamber components |
| WO2010134185A1 (en) * | 2009-05-21 | 2010-11-25 | ステラケミファ株式会社 | Cleaning liquid and cleaning method |
| KR20130060627A (en) * | 2011-11-30 | 2013-06-10 | 세메스 주식회사 | Apparatus for treating substrate |
| WO2013099729A1 (en) * | 2011-12-28 | 2013-07-04 | コニカミノルタ株式会社 | Production method for glass substrate for information recording medium |
| CN103199006A (en) * | 2013-04-07 | 2013-07-10 | 江西沃格光电科技有限公司 | Washing method for TFT substrate |
| US9488857B2 (en) | 2014-01-10 | 2016-11-08 | Corning Incorporated | Method of strengthening an edge of a glass substrate |
| US10077206B2 (en) * | 2015-06-10 | 2018-09-18 | Corning Incorporated | Methods of etching glass substrates and glass substrates |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4324742B2 (en) | 2006-04-28 | 2009-09-02 | シャープ株式会社 | Manufacturing method of polished glass substrate |
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| JPH02114638A (en) * | 1988-10-25 | 1990-04-26 | Fujitsu Ltd | Cleaning of semiconductor substrate |
| JPH07115077A (en) * | 1993-10-19 | 1995-05-02 | Nippon Steel Corp | Washing solution for silicon semiconductor and silicon oxide |
| JPH0848996A (en) * | 1994-08-05 | 1996-02-20 | Nippon Steel Corp | Cleaning fluid for silicon wafer and silicon oxide |
| JP2000140778A (en) * | 1998-11-10 | 2000-05-23 | Hitachi Plant Eng & Constr Co Ltd | Washing solution and washing of glass substrate |
| JP2001046991A (en) * | 1999-08-05 | 2001-02-20 | Hitachi Plant Eng & Constr Co Ltd | Method for washing glass substrate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH02114638A (en) * | 1988-10-25 | 1990-04-26 | Fujitsu Ltd | Cleaning of semiconductor substrate |
| JPH07115077A (en) * | 1993-10-19 | 1995-05-02 | Nippon Steel Corp | Washing solution for silicon semiconductor and silicon oxide |
| JPH0848996A (en) * | 1994-08-05 | 1996-02-20 | Nippon Steel Corp | Cleaning fluid for silicon wafer and silicon oxide |
| JP2000140778A (en) * | 1998-11-10 | 2000-05-23 | Hitachi Plant Eng & Constr Co Ltd | Washing solution and washing of glass substrate |
| JP2001046991A (en) * | 1999-08-05 | 2001-02-20 | Hitachi Plant Eng & Constr Co Ltd | Method for washing glass substrate |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006528551A (en) * | 2003-05-22 | 2006-12-21 | アプライド マテリアルズ インコーポレイテッド | Cleaning process chamber components |
| JP4668915B2 (en) * | 2003-05-22 | 2011-04-13 | アプライド マテリアルズ インコーポレイテッド | Cleaning process chamber components |
| JP2006027912A (en) * | 2004-07-12 | 2006-02-02 | Nishiyama Stainless Chem Kk | Method for polishing surface of glass plate, glass substrate for flat panel display, and flat panel display |
| JP2006083376A (en) * | 2004-08-18 | 2006-03-30 | Mitsubishi Gas Chem Co Inc | Cleaning liquid and cleaning method |
| WO2010134185A1 (en) * | 2009-05-21 | 2010-11-25 | ステラケミファ株式会社 | Cleaning liquid and cleaning method |
| CN102421886A (en) * | 2009-05-21 | 2012-04-18 | 斯泰拉化工公司 | Cleaning liquid and cleaning method |
| KR20130060627A (en) * | 2011-11-30 | 2013-06-10 | 세메스 주식회사 | Apparatus for treating substrate |
| WO2013099729A1 (en) * | 2011-12-28 | 2013-07-04 | コニカミノルタ株式会社 | Production method for glass substrate for information recording medium |
| JPWO2013099729A1 (en) * | 2011-12-28 | 2015-05-07 | Hoya株式会社 | Manufacturing method of glass substrate for information recording medium |
| CN103199006A (en) * | 2013-04-07 | 2013-07-10 | 江西沃格光电科技有限公司 | Washing method for TFT substrate |
| US9488857B2 (en) | 2014-01-10 | 2016-11-08 | Corning Incorporated | Method of strengthening an edge of a glass substrate |
| US10077206B2 (en) * | 2015-06-10 | 2018-09-18 | Corning Incorporated | Methods of etching glass substrates and glass substrates |
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