JPH0712956B2 - Glass substrate cleaning method - Google Patents
Glass substrate cleaning methodInfo
- Publication number
- JPH0712956B2 JPH0712956B2 JP61076476A JP7647686A JPH0712956B2 JP H0712956 B2 JPH0712956 B2 JP H0712956B2 JP 61076476 A JP61076476 A JP 61076476A JP 7647686 A JP7647686 A JP 7647686A JP H0712956 B2 JPH0712956 B2 JP H0712956B2
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- JP
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- Prior art keywords
- cleaning
- glass substrate
- glass
- alkali metal
- film
- Prior art date
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Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明はガラス基板の洗浄方法、特に酸による洗浄方法
に関するものである。TECHNICAL FIELD The present invention relates to a method for cleaning a glass substrate, and more particularly to a method for cleaning with a glass.
［従来の技術］ よく知られているように、ガラスの表面に特定の機能を
もった材料からなる膜等を形成し該ガラスと一体化した
ものを種々の用途に供することが多い。この場合、前記
のガラスをガラス基板と呼ぶことが多い。[Prior Art] As is well known, a film formed of a material having a specific function or the like is formed on the surface of glass, and the film and the like are often used for various purposes. In this case, the glass is often called a glass substrate.
ガラス基板の表面に前記した材料を付与するのに先立っ
て、該ガラス基板に精密洗浄が施される。Prior to applying the above-mentioned material to the surface of the glass substrate, the glass substrate is subjected to precision cleaning.
フォトマスク用ガラス基板について云うと、該ガラス基
板はその精密洗浄工程において、通常初期工程で酸や界
面活性剤により種々の付着異物を除去する為の薬液によ
る前洗浄が行なわれ、その後超純水によるリンス洗浄を
経て最終的にフロン又はIPAの蒸気乾燥により仕上げら
れる。酸洗浄で最も一般的に用いられるのは硝酸水溶液
であるため、成分としてアルカリ金属を含有するガラス
基板に対してはリーチングが起こり、ナトリウムあるい
はカリウムイオン等が基板表面からリーチアウトされ、
ガラス基板表面から深さ100〜2000ÅはSiO2に富む層が
形成される。この表面層は化学的耐久性という観点から
は有利であるが、該表面に金属酸化物、例えば酸化クロ
ム等の膜を形成させた場合、膜と基板の付着力を低下さ
せ、機械的な洗浄に対する耐久性が悪くなる傾向にあ
る。Speaking of a glass substrate for a photomask, in the precision cleaning process, the glass substrate is usually pre-cleaned with a chemical solution to remove various adhered foreign substances with an acid or a surfactant in an initial process, and then ultrapure water is used. After rinsing and washing with chlorofluorocarbon, it is finally finished by steam drying of Freon or IPA. The most commonly used acid cleaning is nitric acid aqueous solution, so leaching occurs to a glass substrate containing an alkali metal as a component, and sodium or potassium ions are reached out from the substrate surface.
A layer rich in SiO 2 is formed at a depth of 100 to 2000 Å from the surface of the glass substrate. This surface layer is advantageous from the viewpoint of chemical durability, but when a film of a metal oxide such as chromium oxide is formed on the surface, the adhesion between the film and the substrate is reduced and mechanical cleaning is performed. Durability tends to deteriorate.
［発明の解決しようとする問題点］ 本発明の目的は、ガラス基板の酸洗浄に於て、酸として
の洗浄効果を維持し、且つガラス基板からのアルカリ金
属イオンの溶出（リーチングとも云う）を抑制・低減さ
せる事によって前述の欠点を解消しようとするものであ
る。[Problems to be Solved by the Invention] An object of the present invention is to maintain the cleaning effect as an acid in acid cleaning of a glass substrate, and to elute alkali metal ions from the glass substrate (also referred to as leaching). It aims to eliminate the above-mentioned drawbacks by suppressing / reducing.
［問題点を解決するための手段］ 本発明は前述の問題点を解決するため、酸水溶液に予め
アルカリ金属イオンを含有させることによりガラス基板
からのアルカリ金属イオンの溶出を低減させる酸洗浄法
を提供するものである。[Means for Solving Problems] In order to solve the above-mentioned problems, the present invention provides an acid cleaning method for reducing the elution of alkali metal ions from a glass substrate by preliminarily containing an alkali metal ion in an acid aqueous solution. It is provided.
ガラス基板の中でも特に高品質の表面洗浄度が要求され
るものにフォトマスク用ガラス基板があり、その中でVL
SI用フォトマスク基板として使用されている低膨張ガラ
ス基板を例に説明する。フォトマスク用ガラス基板を洗
浄後該基板上にスパッタ法等によりクロムあるいはクロ
ム酸化物を1000Å程度の膜厚で成膜したものをフォトマ
スク基板またはマスク基板という。フォトマスクはマス
ク基板上の前記膜をフォトリソグラフィーあるいはEB
（電子線）リソグラフィープロセスを通してパターン化
して得られる。このときガラス基板に研磨剤や塵埃等の
付着異物があるとクロム残りやピンホールが生じパター
ン欠陥となる。また清浄なガラス表面は親水性を呈する
が、雰囲気汚染や油脂分の吸着等によってその表面は疎
水化し、その後工程で成膜される金属膜を金属化合物の
膜との付着力が低下する。このことはクロムマスクブラ
ンクスについても例外でなくガラス基板表面が汚染され
ると膜付着力が低下し、フォトマスクとしての耐久性特
に耐機械的洗浄性が劣化するのでガラス基板とクロム膜
との付着性はフォトマスクの寿命を決定づける非常に重
要な因子である。クロム膜とガラス基板の付着力は以上
のようにガラス基板表面の清浄度に大きく依存するが、
ガラス組成によっても影響も受ける。クロム膜のガラス
基板に対する付着力の評価は、最終的にはフォトマスク
の耐久性を評価する事にあるので種々のマスク洗浄プロ
セスに対する耐久性を試験するのがより実際的である。
従って代表的な物理的洗浄法として高圧水洗浄を例にと
り、膜（マスクパターン）の耐久性とガラス組成につい
て以下に説明する。通常、高圧水によるマスク洗浄は圧
力1000〜2000psiでノズルから発生した高圧ジェット水
を、2000〜3000rpmで回転しているマスク基板に対して
一定速度の往復走査によって該マスク基板全面に数分間
噴射させ、発生するパターン欠陥をマスク検査機を用い
てチェックするが、ここではより簡便な評価法として、
マスク基板及び高圧水ノズルを共に静止させ、前記マス
ク基板の一定領域内に該高圧水を集中噴射し、そこで発
生するパターン欠陥（「パターン欠け」とも云う）を光
学顕微鏡で観察する、所謂一点集中噴射による加速試験
によるチェックを行なった。この方法によれば付着力の
弱い系（ここに、系とは基板組成とクロム膜の組合せを
云う）では1000psiで20秒、付着力の強い系でも1500psi
で60秒程度でパターン欠けは発生する。ガラス基板とし
て合成石英ガラス（以下QZと記す）と低膨張ガラス（以
下LTEと記す）の２種類に対し、前記基板上にスパッタ
法により窒化クロム膜（CrNx）及び酸化クロム膜（CrO
x）を成膜した後、通常のフォトリソプロセスによって
５μｍ角のドットアレイパターンを形成して得られた耐
久性試験用マスク基板に、圧力1000psi及び1500psiの高
圧水を各々30秒間１点集中噴射し、光学顕微鏡でパター
ン欠けや欠落したドットをカウントしたところ第１表に
示すような結果が得られた。The glass substrate for photomasks is one of the glass substrates that requires particularly high surface cleanliness.
A low expansion glass substrate used as a SI photomask substrate will be described as an example. A photomask substrate or a mask substrate is formed by cleaning a glass substrate for a photomask and then depositing chromium or chromium oxide on the substrate to a film thickness of about 1000 Å by a sputtering method or the like. The photomask is formed by photolithography or EB of the film on the mask substrate.
It is obtained by patterning through an (electron beam) lithography process. At this time, if adhered foreign matter such as abrasives or dust is present on the glass substrate, chrome remains and pinholes are generated, resulting in pattern defects. Although the clean glass surface exhibits hydrophilicity, its surface becomes hydrophobic due to atmospheric pollution, adsorption of oil and fats, etc., and the adhesion of the metal film formed in the subsequent step to the metal compound film is reduced. This is true for chrome mask blanks as well, and when the glass substrate surface is contaminated, the film adhesion decreases, and the durability as a photomask, especially the mechanical cleaning resistance, deteriorates. The property is a very important factor that determines the life of the photomask. The adhesion between the chrome film and the glass substrate depends largely on the cleanliness of the glass substrate surface as described above.
It is also affected by the glass composition. Since the evaluation of the adhesion of the chrome film to the glass substrate is ultimately to evaluate the durability of the photomask, it is more practical to test the durability against various mask cleaning processes.
Therefore, the durability of the film (mask pattern) and the glass composition will be described below by taking high pressure water cleaning as an example of a typical physical cleaning method. Normally, in mask cleaning with high-pressure water, high-pressure jet water generated from a nozzle at a pressure of 1000 to 2000 psi is sprayed on the entire surface of the mask substrate for several minutes by reciprocal scanning at a constant speed with respect to the mask substrate rotating at 2000 to 3000 rpm. , Check the generated pattern defects using a mask inspection machine, but here, as a simpler evaluation method,
Both the mask substrate and the high-pressure water nozzle are kept stationary, the high-pressure water is intensively jetted into a certain area of the mask substrate, and pattern defects (also referred to as "pattern defects") generated there are observed with an optical microscope, a so-called one-point concentration. A check was performed by an injection acceleration test. According to this method, a system with weak adhesion (here, the system is a combination of substrate composition and chromium film) is 1000 psi for 20 seconds, and a system with strong adhesion is 1500 psi.
In about 60 seconds, a pattern defect occurs. There are two types of glass substrates, synthetic quartz glass (hereinafter referred to as QZ) and low expansion glass (hereinafter referred to as LTE), on the above-mentioned substrates by sputtering method chromium nitride film (CrNx) and chromium oxide film (CrO).
x) is formed, and then a 5 μm square dot array pattern is formed by a normal photolithography process, and then high-pressure water with a pressure of 1000 psi and 1500 psi is concentrated and sprayed at one point for 30 seconds on the mask substrate for durability test. As a result of counting the pattern defects and the missing dots with an optical microscope, the results shown in Table 1 were obtained.
同じ膜種でQZとLTEを比較すると高圧水洗浄に対する耐
久性はLTEの方が優れる傾向にある。この傾向は他の方
法、例えばサファイアやダイヤモンド針を用いたスクラ
ッチテストによる耐擦傷性試験によっても再現される
が、このことはQZの方がLTEに比べその組成上化学的に
不活性（表面エネルギーが小さい）なため付着力が弱い
ことおよびクロム膜との膨張係数の差がLTEよりも大き
いことなどに起因するものと思われる。第１表に示した
試験において、スパッタ法によりクロム膜を成膜する前
のガラス基板は、前洗浄として１％硝酸槽に２分間28KH
z、250wの超音波照射を行なって浸漬させた後、超純
水、IPAによる精密洗浄を行ない最終的にフロンの蒸気
洗浄乾燥を行なった（以上を１サイクルとする）が、以
上の洗浄工程のサイクル数を増すとLTE基板に対する耐
洗浄性が低下する傾向がCrOx膜の場合に認められる。第
２表に洗浄回数とパターン欠陥数の関係を示す。 Comparing QZ and LTE with the same membrane type, LTE tends to have better durability against high-pressure water washing. This tendency is reproduced by other methods, such as scratch resistance test by scratch test using sapphire or diamond stylus, which shows that QZ is chemically inert (compared to surface energy) in comparison with LTE. It is thought that this is due to the fact that the adhesive strength is weak and the difference in expansion coefficient from the chromium film is larger than that of LTE. In the test shown in Table 1, the glass substrate before forming the chromium film by the sputtering method was precleaned in a 1% nitric acid tank for 2 minutes at 28 KH.
After irradiating with ultrasonic waves of z and 250w for immersion, precision cleaning with ultrapure water and IPA was performed and steam cleaning and drying of CFCs were finally performed (the above is one cycle). When the number of cycles is increased, the cleaning resistance to the LTE substrate tends to decrease in the case of CrOx film. Table 2 shows the relationship between the number of cleanings and the number of pattern defects.
LTE基板とCrOx膜の場合に認められる上記の傾向の原因
は洗浄回数の増加によって、LTEに若干含まれるアルカ
リ金属が抽出される、所謂リーチングがイオン拡散反応
として進行し、ガラス表面の組成がシリカリッチになっ
ただけでなく、リーチングによって構造的にも緻密性が
低下した為と推定され、それが付着力の弱いCrOx膜系に
現われたものであろう。 The cause of the above tendency observed in the case of the LTE substrate and the CrOx film is that the alkali metal contained in the LTE is slightly extracted due to the increase in the number of times of cleaning, so-called leaching proceeds as an ion diffusion reaction, and the composition of the glass surface is silica. It is presumed that not only became rich, but also the densification structurally deteriorated due to leaching, which may have appeared in the CrOx film system with weak adhesion.
本発明は、以上のような多数回に亘る酸洗浄によりリー
チングされたガラス基板の表面に変質層が形成されるこ
とによって前記クロム膜の耐洗浄性が低下する問題点に
対し、酸としての洗浄能力を低下させることなく前記膜
の耐洗浄性を維持するものである。酸によるガラス表面
からのアルカリ金属イオンのリーチングは酸溶液中のプ
ロトン（H+）とのイオン交換反応で起こることは周知の
通りであり、そのドライビングフォースはアルカリ金属
イオンのガラス表面における濃度と媒体（酸溶液）にお
ける濃度との濃度差である。従って実質的にリーチング
を抑制させるには予め媒体中にアルカリ金属イオンを所
定量含有させればよく、更に媒体である酸溶液の酸とし
ての能力を低下させない為、即ちプロトン濃度を低下さ
せない為には該アルカリ金属イオンのソースを塩、望ま
しくは中性塩として選ぶことによって前述した欠点を克
服する事ができる。ガラス基板洗浄に用いられる酸に硝
酸、塩酸、硫酸等の強酸が一般に用いられリーチング抑
制剤として予め加えられる物質はアルカリ金属の水酸化
物と、用いられる酸との中和反応で生成される塩である
事が望ましい。例えば硝酸溶液に対しては硝酸ナトリウ
ム、硝酸カリウム等である。又、酸溶液に予め加えるべ
きアルカリ金属塩はガラス組成に含まれているアルカリ
金属であることが望ましい。更に酸によってガラス表面
から溶出される成分はアルカリ金属の他、アルカリ土類
金属等もあり、これらに対しても予め酸溶液中にそのイ
オンを含有させることによって同様の効果を得ることが
できる。The present invention is directed to the problem that the cleaning resistance of the chromium film is deteriorated by forming an altered layer on the surface of the glass substrate leached by acid cleaning as described above. It is intended to maintain the washing resistance of the film without deteriorating the performance. It is well known that the leaching of alkali metal ions from the glass surface by an acid occurs by an ion exchange reaction with protons (H + ) in an acid solution, and the driving force is the concentration of alkali metal ions on the glass surface and the medium. It is the concentration difference from the concentration in (acid solution). Therefore, in order to substantially suppress leaching, it is only necessary to previously contain a predetermined amount of alkali metal ions in the medium, and further, because the ability of the acid solution as the medium as an acid is not reduced, that is, the proton concentration is not reduced. Can overcome the aforementioned drawbacks by choosing the source of the alkali metal ion as a salt, preferably a neutral salt. A strong acid such as nitric acid, hydrochloric acid or sulfuric acid is generally used as the acid used for cleaning the glass substrate, and a substance added in advance as a leaching inhibitor is a salt formed by a neutralization reaction between an alkali metal hydroxide and the acid used. Is desirable. For example, for nitric acid solution, sodium nitrate, potassium nitrate and the like are used. Further, the alkali metal salt to be added to the acid solution in advance is preferably the alkali metal contained in the glass composition. Further, the components eluted from the glass surface by the acid include alkali metals and alkaline earth metals, and the same effect can be obtained by preliminarily incorporating the ions into the acid solution.
本発明の骨子をまとめれば （１）アルカリ金属を含有するガラス基板を硝酸水溶液
で洗浄することにより種々の付着異物を除去する方法に
おいて、該硝酸水溶液に硝酸リチウム、硝酸ナトリウ
ム、および硝酸カリウムのうち少なくとも１つを予め含
有させること であり、その実施態様は次の如くである。The gist of the present invention is summarized as follows: (1) In a method of removing various adhered foreign substances by washing an alkali metal-containing glass substrate with a nitric acid aqueous solution, the nitric acid aqueous solution contains at least lithium nitrate, sodium nitrate, and potassium nitrate. One of them is contained in advance, and its embodiment is as follows.
（２）前記ガラス基板に含有する主要アルカリ金属がリ
チウムであるとき、硝酸水溶液中に硝酸リチウムを予め
含有させること。(2) When the main alkali metal contained in the glass substrate is lithium, preliminarily contain lithium nitrate in the aqueous nitric acid solution.
（３）前記ガラス基板に含有する主要アルカリ金属がナ
トリウムであるとき、硝酸水溶液中に硝酸ナトリウムを
予め含有させること。(3) When the main alkali metal contained in the glass substrate is sodium, preliminarily contain sodium nitrate in the aqueous nitric acid solution.
（４）前記ガラス基板に含有する主要アルカリ金属がカ
リウムであるとき、硝酸水溶液中に硝酸カリウムを予め
含有させること。(4) When the main alkali metal contained in the glass substrate is potassium, potassium nitrate should be contained in the nitric acid aqueous solution in advance.
（５）前記（１）〜（４）のそれぞれにおいて記載のガ
ラス基板がフォトマスク用ガラス基板であること。(5) The glass substrate described in each of (1) to (4) above is a glass substrate for a photomask.
ガラス基板に対する洗浄剤には純水、酸、アルカリ溶
液、キレート剤、界面活性剤、有機溶剤等があり、洗浄
方法としては加熱や超音波を付与した浸漬処理やブラシ
等のスクラブ洗浄、高圧スプレー洗浄、蒸気洗浄あるい
は紫外線／オゾンやスパッタリング等によるドライ洗浄
がある。以上の洗浄剤や洗浄方法はガラス組成、除去す
べき汚染物質の種類や付着程度、更に洗浄後の使用用途
等によって選択されあるいは組み合わせる事によって洗
浄プロセス条件が決定される。Detergents for glass substrates include pure water, acids, alkaline solutions, chelating agents, surfactants, organic solvents, etc., and as cleaning methods, heating, ultrasonic immersion treatment, scrub cleaning of brushes, etc., high pressure spraying There are cleaning, steam cleaning, and dry cleaning using ultraviolet rays / ozone, sputtering, etc. The above-mentioned cleaning agent and cleaning method are selected or combined depending on the glass composition, the type and degree of adhesion of contaminants to be removed, the intended use after cleaning, and the like, and the cleaning process conditions are determined.
また以上の説明からわかる如く、本願発明におけるガラ
ス基板とは、平板状のガラスに限定されるものではな
く、最終製品から由来する必要な形状のガラスであって
よい。また本願発明の効果は直接にはガラスの形状によ
らない。Further, as will be understood from the above description, the glass substrate in the present invention is not limited to flat glass, and may be glass having a required shape derived from the final product. The effect of the present invention does not depend directly on the shape of glass.
［実施例］ フォトマスク基板グレードで面仕上げ研磨されたLTEガ
ラス基板（化学組成−重量％：R2O４％,RO19％，B2O3４
％，Al2O315％，SiO258％）を用い、洗浄は７槽型精密
洗浄機によった。該洗浄機の第１槽を酸洗浄槽、第２〜
４槽を超純水槽、第５〜６槽をIPA洗浄槽、第７槽をフ
ロン蒸気洗浄槽とし、第１、２、３、４、６槽に超音波
照射（250W,28KHz）した。第１槽〜７槽の一連の洗浄を
１サイクル（洗浄回数が１回）とした。酸洗浄液として
硝酸水溶液、硝酸水溶液＋硝酸ナトリウム、硝酸水溶液
＋硝酸カリウム、硝酸ナトリウム水溶液のみの４種類に
対し洗浄を１〜20サイクル行なった後ガラス基板表面に
スパッタ法によりクロム膜を成膜した。クロム膜はアル
ゴンと窒素の混合ガス雰囲気での反応性スパッタリング
によるCrNx膜とアルゴンと酸素の混合雰囲気によるCrOx
の２種類を膜厚600Åで成膜した後通常のフォトリソグ
ラフィープロセスを通じて５μｍ角のドットアレーパタ
ーンを形成してマスクパターンとした。EXAMPLES surface finish polished LTE glass substrate in the photomask substrate grade (chemical composition - wt%: R 2 O4%, RO19 %, B 2 O 3 4
%, Al 2 O 3 15%, SiO 2 58%), and cleaning was performed by a 7-tank precision cleaning machine. The first tank of the washing machine is an acid cleaning tank,
4 tanks were used as ultrapure water tanks, 5th to 6th tanks were used as IPA cleaning tanks, and 7th tank were used as fluorocarbon steam cleaning tanks, and ultrasonic irradiation (250W, 28KHz) was applied to the 1st, 2nd, 3rd, 4th, and 6th tanks. A series of cleaning of the first tank to the seventh tank was set as one cycle (the number of times of cleaning was once). As the acid cleaning liquid, four kinds of only nitric acid aqueous solution, nitric acid aqueous solution + sodium nitrate, nitric acid aqueous solution + potassium nitrate, and sodium nitrate aqueous solution were washed for 1 to 20 cycles, and then a chromium film was formed on the surface of the glass substrate by a sputtering method. The chromium film is a CrNx film formed by reactive sputtering in a mixed gas atmosphere of argon and nitrogen and CrOx formed by a mixed atmosphere of argon and oxygen.
After forming two kinds of the above with a film thickness of 600 Å, a 5 μm square dot array pattern was formed through a normal photolithography process to form a mask pattern.
耐久性は、高圧水洗浄装置を用い圧力1500psiで30秒間
高圧水を１点集中洗浄法によって噴射し、洗浄領域内の
パターン欠陥部を光学顕微鏡で観察し、カウントして評
価した。尚洗浄領域内の５μｍ角のドットパターン数は
約2000個であった。The durability was evaluated by jetting high-pressure water at a pressure of 1500 psi for 30 seconds by a one-point concentrated cleaning method using a high-pressure water cleaning device, observing pattern defects in the cleaning region with an optical microscope, and counting. The number of 5 μm square dot patterns in the cleaning region was about 2000.
以上の条件での実施結果を第３表に示す。Table 3 shows the results of implementation under the above conditions.
第３表の試験結果で明らかなように、洗浄液が硝酸のみ
の場合、洗浄サイクルが20回でパターン欠陥数の増加が
認められたが、１％NaNO3あるいは１％KNO3を加える事
によって洗浄効果を低下させることなく、パターン欠陥
発生数の増加を阻止する事ができた。 As is clear from the test results in Table 3, when the cleaning solution was only nitric acid, an increase in the number of pattern defects was observed after 20 cleaning cycles, but cleaning was performed by adding 1% NaNO 3 or 1% KNO 3. It was possible to prevent an increase in the number of pattern defects generated without lowering the effect.
［発明の効果］ 本発明による酸洗浄液を用いることにより、ガラスの表
面からのアルカリ金属イオンの溶出を防止または低減さ
せることが可能になる。[Advantages of the Invention] By using the acid cleaning liquid of the present invention, it becomes possible to prevent or reduce the elution of alkali metal ions from the surface of glass.
フォトマスク用ガラス基板の場合に本発明の酸洗浄液を
用いて洗浄を行なうと、満足すべき表面の清浄度が得ら
れると同様に、該基板の表面にスパッタ法等により形成
したクロム系膜は該基板への付着力が大きくかつ機械的
な洗浄に対する耐久性が優れている。When a glass substrate for a photomask is washed with the acid cleaning solution of the present invention, a satisfactory surface cleanliness is obtained. Similarly, a chromium-based film formed on the surface of the substrate by a sputtering method or the like is not formed. It has a large adhesive force to the substrate and excellent durability against mechanical cleaning.
またアルカリ金属イオンを含有するガラスからなり、表
面層が所要のイオン交換処理されたガラスた化学強化ガ
ラス等の酸洗浄に本発明を適用すれば、清浄なガラス表
面が得られると同時に、該酸洗浄後に前記したガラスの
表面に形成し該ガラスと一体化した機能性材料の膜等
が、前記ガラスに含有されるアルカリ金属イオンの溶出
に起因する性能の低下（ガラス表面への付着力の低下や
機械的な洗浄に対する耐久性の低下）を蒙ることを防止
できる。Further, when the present invention is applied to acid cleaning of chemically strengthened glass or the like, which is made of glass containing alkali metal ions and has a surface layer subjected to the required ion exchange treatment, a clean glass surface can be obtained and the acid A film of a functional material formed on the surface of the above-mentioned glass after cleaning and integrated with the glass has a decrease in performance due to elution of alkali metal ions contained in the glass (decrease in adhesion to the glass surface. And deterioration of durability against mechanical cleaning) can be prevented.
更に、処理されるガラスが含有するアルカリ金属イオン
に対してそれとは異種のアルカリ金属イオンを選び、酸
洗浄液に該異種アルカリ金属イオンを予め含有させて前
記処理されるガラスの酸洗浄を行なうことにより、前記
処理されるガラスの表面に若干のイオン交換層が形成さ
れる効果も期待できる。Furthermore, by selecting an alkali metal ion different from that of the alkali metal ion contained in the glass to be treated, and preliminarily containing the different alkali metal ion in the acid cleaning liquid, the acid cleaning of the glass to be treated is performed. The effect of forming a slight ion exchange layer on the surface of the glass to be treated can also be expected.
更にまた本発明は、ガラスが平板状の場合に限定され
ず、ガラスの形状に制限なく適用でき、前記の効果を有
する特色をもっている。Furthermore, the present invention is not limited to the case where the glass has a flat plate shape, and can be applied to the shape of the glass without restriction, and has a feature that has the above-mentioned effects.
Claims (5)
水溶液で洗浄する方法において、該硝酸水溶液に硝酸リ
チウム、硝酸ナトリウム、および硝酸カリウムのうち少
なくとも１つを予め含有させることを特徴とするガラス
基板の洗浄方法。1. A method of cleaning a glass substrate containing an alkali metal with an aqueous nitric acid solution, wherein the aqueous nitric acid solution contains at least one of lithium nitrate, sodium nitrate and potassium nitrate in advance. Cleaning method.
属がリチウムであるとき、硝酸水溶液中に硝酸リチウム
を予め含有させることを特徴とする特許請求の範囲第１
項記載のガラス基板の洗浄方法。2. When the main alkali metal contained in the glass substrate is lithium, lithium nitrate is contained in the nitric acid aqueous solution in advance.
The method for cleaning a glass substrate according to the item.
属がナトリウムであるとき、硝酸水溶液中に硝酸ナトリ
ウムを予め含有させることを特徴とする特許請求の範囲
第１項記載のガラス基板の洗浄方法。3. The method for cleaning a glass substrate according to claim 1, wherein when the main alkali metal contained in the glass substrate is sodium, sodium nitrate is contained in the nitric acid aqueous solution in advance.
属がカリウムであるとき、硝酸水溶液中に硝酸カリウム
を予め含有させることを特徴とする特許請求の範囲第１
項記載のガラス基板の洗浄方法。4. When the main alkali metal contained in the glass substrate is potassium, potassium nitrate is preliminarily contained in the aqueous nitric acid solution.
The method for cleaning a glass substrate according to the item.
板であることを特徴とする特許請求の範囲第１項乃至第
４項のいずれか１項記載のガラス基板の洗浄方法。5. The method of cleaning a glass substrate according to claim 1, wherein the glass substrate is a photomask glass substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61076476A JPH0712956B2 (en) | 1986-04-04 | 1986-04-04 | Glass substrate cleaning method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61076476A JPH0712956B2 (en) | 1986-04-04 | 1986-04-04 | Glass substrate cleaning method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62235236A JPS62235236A (en) | 1987-10-15 |
| JPH0712956B2 true JPH0712956B2 (en) | 1995-02-15 |
Family
ID=13606239
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61076476A Expired - Lifetime JPH0712956B2 (en) | 1986-04-04 | 1986-04-04 | Glass substrate cleaning method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0712956B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5448619B2 (en) | 2009-07-21 | 2014-03-19 | 東京応化工業株式会社 | Cleaning the support plate |
| JP5375725B2 (en) * | 2010-04-12 | 2013-12-25 | コニカミノルタ株式会社 | Metal pattern manufacturing method and metal pattern |
| CN113620569B (en) * | 2021-08-29 | 2023-07-11 | 咸宁南玻光电玻璃有限公司 | Method for improving adhesion of float process glass printing ink |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52144020A (en) * | 1976-05-26 | 1977-12-01 | Seiko Instr & Electronics | Method of etching glass surface |
| JPS5992945A (en) * | 1982-10-13 | 1984-05-29 | エリツヒ・ゼルツレ | Glass product polishing method |
-
1986
- 1986-04-04 JP JP61076476A patent/JPH0712956B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62235236A (en) | 1987-10-15 |
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