JPH11186207A - Cleaning water for electronic material - Google Patents
Cleaning water for electronic materialInfo
- Publication number
- JPH11186207A JPH11186207A JP35518097A JP35518097A JPH11186207A JP H11186207 A JPH11186207 A JP H11186207A JP 35518097 A JP35518097 A JP 35518097A JP 35518097 A JP35518097 A JP 35518097A JP H11186207 A JPH11186207 A JP H11186207A
- Authority
- JP
- Japan
- Prior art keywords
- water
- cleaning water
- electronic materials
- carbonic acid
- cleaning
- 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)
- Detergent Compositions (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、電子材料用洗浄水
に関する。さらに詳しくは、本発明は、半導体用シリコ
ン基板、液晶用ガラス基板などの電子材料を扱う産業に
おいて行われるウェット洗浄に用いられる電子材料用洗
浄水に関する。[0001] The present invention relates to cleaning water for electronic materials. More specifically, the present invention relates to cleaning water for electronic materials used in wet cleaning performed in industries dealing with electronic materials such as silicon substrates for semiconductors and glass substrates for liquid crystals.
【０００２】[0002]
【従来の技術】従来より、半導体用シリコン基板、液晶
用ガラス基板などは、ＲＣＡ洗浄と呼ばれる、硫酸と過
酸化水素水の混合液、塩酸と過酸化水素水と水の混合
液、アンモニア水と過酸化水素水と水の混合液など、過
酸化水素をベースとする濃厚薬液を用いた高温洗浄によ
り清浄化されていた。この洗浄法を採用した場合の多大
な薬液コスト、リンス用の超純水コスト、廃液処理コス
ト、薬品蒸気を排気し新たに清浄空気を作る空調コスト
を低減し、さらに水の大量使用、薬物の大量廃棄、排ガ
スの放出といった環境への負荷を低減するために、近年
ウェット洗浄工程の見直しが進められている。本発明者
らは、先に特開平８−３１６１８７号公報において、高
濃度の塩酸や過酸化水素などの薬品を使用することな
く、効率よく半導体基板上の金属汚染物及び有機汚染物
の除去を可能にし、洗浄後の廃液処理を容易にする洗浄
方法として、塩素化合物を含む酸性水溶液にオゾンを吹
き込んで調製した洗浄水を用いる洗浄方法を提案した。
本発明者らは、その後さらに研究を進め、洗浄対象物及
び洗浄目的に応じて、酸化還元電位とpHを適度に調整し
た各種の電子材料用洗浄水を開発した。電子材料用洗浄
水の酸化還元電位の調整は、超純水に過酸化水素、オゾ
ン、酸素ガス、酸化性塩素などの酸化剤や、水素ガス、
次亜硫酸ナトリウムム（Ｎａ2Ｓ2Ｏ4）などの還元剤を
溶解することにより行われる。また、pHの調整は、塩
酸、硫酸、硝酸、フッ化水素酸などの酸や、アンモニ
ア、水酸化カリウムなどのアルカリを溶解することによ
り行われる。本発明者らは、また、ユースポイントにお
ける電子材料用洗浄水の使用量が変動した場合にも安定
して供給することができ、しかも超純水を無駄に廃棄す
ることのない洗浄水供給装置として、電子材料用洗浄水
を主配管を通じてユースポイントに送給し、ユースポイ
ントで使用されなかった電子材料用洗浄水を返送して再
使用する電子材料用洗浄水供給装置を開発した。ユース
ポイントで使用されなかった洗浄水は、そのまま循環し
て再使用したり、あるいは、前段の一次純水製造部に戻
して、超純水の原水として使用したりする。電子材料用
洗浄水の水質管理を簡単にするためには、ユースポイン
トで使用されなかった洗浄水は、一次純水製造部に返送
して原水とする方法が望ましい。電子材料用洗浄水は、
含有する酸化剤の濃度が同じであれば、酸の添加により
pHを低くする方が酸化還元電位が高くなり、洗浄効果を
高めることができる。このために、酸として、塩酸、硫
酸、硝酸、フッ化水素酸などを添加して、pHを調整する
場合が多い。これらの酸としては、電子工業グレードの
高純度試薬を用いるために、薬剤コストが高くなるとい
う問題があった。さらに、このような電子材料用洗浄水
を、一次純水製造部に返送して超純水の原水として使用
する場合には、あらかじめこれらの酸を除去する必要が
あり、一次純水製造部におけるイオン負荷が増大すると
いう問題があった。2. Description of the Related Art Conventionally, a silicon substrate for a semiconductor, a glass substrate for a liquid crystal, and the like have been used for cleaning a mixture of sulfuric acid and hydrogen peroxide, a mixture of hydrochloric acid, hydrogen peroxide and water, and ammonia water, which is called RCA cleaning. It has been cleaned by high-temperature cleaning using a concentrated chemical based on hydrogen peroxide, such as a mixture of aqueous hydrogen peroxide and water. If this cleaning method is adopted, the cost of chemicals, the cost of ultrapure water for rinsing, the cost of waste liquid treatment, and the cost of air conditioning that exhausts chemical vapors and creates clean air will be reduced. In order to reduce the burden on the environment such as mass disposal and emission of exhaust gas, the wet cleaning process has recently been reviewed. The present inventors have previously disclosed in Japanese Patent Application Laid-Open No. 8-316187 that efficient removal of metal contaminants and organic contaminants on a semiconductor substrate without using chemicals such as high-concentration hydrochloric acid and hydrogen peroxide. A cleaning method using washing water prepared by blowing ozone into an acidic aqueous solution containing a chlorine compound has been proposed as a cleaning method that enables the treatment of waste liquid after cleaning.
The present inventors have further researched after that, and have developed various types of electronic material cleaning water in which the oxidation-reduction potential and pH have been appropriately adjusted according to the object to be cleaned and the purpose of cleaning. Adjustment of the oxidation-reduction potential of the cleaning water for electronic materials is performed by adding an oxidizing agent such as hydrogen peroxide, ozone, oxygen gas, oxidizing chlorine, hydrogen gas,
This is performed by dissolving a reducing agent such as sodium hyposulfite (Na 2 S 2 O 4 ). The pH is adjusted by dissolving an acid such as hydrochloric acid, sulfuric acid, nitric acid or hydrofluoric acid, or an alkali such as ammonia or potassium hydroxide. The present inventors also provide a cleaning water supply apparatus that can stably supply even when the usage amount of electronic material cleaning water at a point of use fluctuates and that does not wastefully discard ultrapure water. The company has developed an electronic material cleaning water supply device that sends electronic material cleaning water to the point of use through the main pipe and returns the electronic material cleaning water that has not been used at the point of use to return to reuse. The washing water not used at the point of use is circulated and reused as it is, or returned to the first-stage primary pure water production section and used as raw water of ultrapure water. In order to simplify the quality control of the cleaning water for electronic materials, it is desirable that the cleaning water not used at the point of use be returned to the primary pure water production department to be used as raw water. Cleaning water for electronic materials
If the concentration of the oxidizing agent contained is the same,
The lower the pH, the higher the oxidation-reduction potential and the higher the cleaning effect. For this purpose, hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, or the like is often added as an acid to adjust the pH. As these acids, the use of high-purity reagents of the electronic industrial grade has the problem of increasing the cost of chemicals. Furthermore, when such electronic material washing water is returned to the primary pure water production section and used as raw water of ultrapure water, it is necessary to remove these acids in advance, and the primary pure water production section There is a problem that the ion load increases.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、薬剤を用い
ることなく電子材料用洗浄水のpHを調整して洗浄効果を
高めるとともに、ユースポイントで使用されなかった余
剰の電子材料用洗浄水を超純水の原水として利用すると
き、余剰の洗浄水の脱イオンが不要で、回収、再利用の
容易な電子材料用洗浄水を提供することを目的としてな
されたものである。SUMMARY OF THE INVENTION The present invention adjusts the pH of the electronic material cleaning water without using a chemical to enhance the cleaning effect, and removes excess electronic material cleaning water not used at the point of use. When used as raw water of ultrapure water, it is an object of the present invention to provide washing water for electronic materials that does not require deionization of excess washing water and is easy to collect and reuse.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、上記の課
題を解決すべく鋭意研究を重ねた結果、超純水に炭酸ガ
スを溶解することにより、薬剤を用いることなく超純水
のpHを調整することが可能であり、ユースポイントで使
用されなかった余剰の電子材料用洗浄水は、脱炭酸処理
により容易にＣＯ2を除去し得ることを見いだし、この
知見に基づいて本発明を完成するに至った。すなわち、
本発明は、（１）酸化剤又は還元剤と炭酸とを含有する
ことを特徴とする電子材料用洗浄水、を提供するもので
ある。さらに、本発明の好ましい態様として、（２）炭
酸が、炭酸ガスの溶解により含有させられたものである
第(１)項記載の電子材料用洗浄水、（３）炭酸ガスの溶
解が、気体透過膜モジュールを用いて行われたものであ
る第(２)項記載の電子材料用洗浄水、（４）炭酸が、あ
らかじめ調製された高濃度の炭酸水の添加により含有さ
せられたものである第(１)項記載の電子材料用洗浄水、
（５）酸化剤が、気体成分である第(１)項記載の電子材
料用洗浄水、（６）気体成分が、オゾン又は酸素ガスで
ある第(５)項記載の電子材料用洗浄水、（７）ユースポ
イントで使用されなかった、又は、ユースポイントで使
用した電子材料用洗浄水を、一次純水製造部の脱炭酸装
置の上流側に返送することを特徴とする第(１)項記載の
電子材料用洗浄水の回収、再利用方法、及び、（８）ユ
ースポイントで使用されなかった、又は、ユースポイン
トで使用した電子材料用洗浄水を、専用の脱炭酸装置で
脱炭酸したのち、一次純水製造部若しくはサブシステム
に返送することを特徴とする第(１)項記載の電子材料用
洗浄水の回収、再利用方法、を挙げることができる。Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have dissolved carbon dioxide gas in ultrapure water, so that ultrapure water can be used without using a chemical. It has been found that the pH can be adjusted and surplus electronic material washing water not used at the point of use can easily remove CO 2 by decarboxylation treatment. It was completed. That is,
The present invention provides (1) washing water for electronic materials, which comprises an oxidizing or reducing agent and carbonic acid. Further, as a preferred embodiment of the present invention, (2) the washing water for electronic materials according to (1), wherein carbonic acid is contained by dissolving carbon dioxide gas; The washing water for electronic materials according to item (2), wherein the washing is performed using a permeable membrane module, and (4) carbonic acid is contained by adding a high-concentration carbonated water prepared in advance. Cleaning water for electronic materials according to item (1),
(5) The electronic material cleaning water according to (1), wherein the oxidizing agent is a gas component; (6) the electronic material cleaning water according to (5), wherein the gas component is ozone or oxygen gas; (7) The electronic material washing water not used at the point of use or used at the point of use is returned to the upstream side of the decarbonation unit of the primary pure water production section. The method for collecting and reusing the washing water for electronic materials described in (8) The washing water for electronic materials that was not used at the point of use or used at the point of use was decarbonated with a dedicated decarbonating device. Thereafter, the method for collecting and reusing the washing water for electronic materials according to item (1), wherein the method is returned to the primary pure water producing unit or the subsystem, can be mentioned.
【０００５】[0005]
【発明の実施の形態】本発明の電子材料用洗浄水は、酸
化剤又は還元剤と炭酸を含有する。含有させる酸化剤に
は特に制限はなく、例えば、過酸化水素、オゾン、酸素
ガス、酸化性塩素などを挙げることができる。含有させ
る還元剤には特に制限はなく、例えば、水素ガス、次亜
硫酸ナトリウム（Ｎａ2Ｓ2Ｏ4）などを挙げることがで
きる。酸化剤を含有する本発明の電子材料用洗浄水は、
電子材料表面の金属汚染、有機物汚染などの洗浄に好適
に使用することができる。還元剤を含有する本発明の電
子材料用洗浄水は、電子材料表面の微粒子などの除去に
好適に使用することができる。本発明において、電子材
料用洗浄水に炭酸を含有させる方法には特に制限はな
く、例えば、超純水に炭酸ガスを直接バブリングして溶
解させることができ、気体透過膜モジュールを使用して
炭酸ガスを溶解させることもでき、あるいは、あらかじ
め炭酸ガスを高濃度に溶解した炭酸水を調製しておき、
これを超純水に添加することもできる。本発明の電子材
料用洗浄水の調製において、酸化剤又は還元剤と炭酸を
含有させる順序には特に制限はなく、酸化剤又は還元剤
を含有させたのち炭酸を含有させることができ、あるい
は逆に、炭酸を含有させたのち酸化剤又は還元剤を含有
させることもできる。本発明の電子材料用洗浄水として
は、例えば、過酸化水素と炭酸を含有する洗浄水、オゾ
ンと炭酸を含有する洗浄水、酸素ガスと炭酸を含有する
洗浄水、酸化性塩素と炭酸を含有する洗浄水、水素ガス
と炭酸を含有する洗浄水などを挙げることができる。BEST MODE FOR CARRYING OUT THE INVENTION The cleaning water for electronic materials of the present invention contains an oxidizing agent or a reducing agent and carbonic acid. The oxidizing agent to be contained is not particularly limited, and examples thereof include hydrogen peroxide, ozone, oxygen gas, and oxidizing chlorine. The reducing agent to be contained is not particularly limited, and examples thereof include hydrogen gas and sodium hyposulfite (Na 2 S 2 O 4 ). Washing water for electronic materials of the present invention containing an oxidizing agent,
The present invention can be suitably used for cleaning metal contamination and organic contamination on the surface of an electronic material. The cleaning water for electronic materials of the present invention containing a reducing agent can be suitably used for removing fine particles and the like on the surface of electronic materials. In the present invention, there is no particular limitation on the method of including carbonic acid in the cleaning water for electronic materials.For example, carbon dioxide gas can be directly bubbled and dissolved in ultrapure water, and carbonic acid can be dissolved using a gas permeable membrane module. It is also possible to dissolve the gas, or prepare a carbonated water in which carbon dioxide is dissolved in high concentration in advance,
This can be added to ultrapure water. In the preparation of the washing water for electronic materials of the present invention, the order in which the oxidizing agent or the reducing agent and the carbonic acid are contained is not particularly limited, and the oxidizing agent or the reducing agent can be added and then the carbonic acid can be contained. In addition, after containing carbonic acid, an oxidizing agent or a reducing agent may be contained. Examples of the electronic material cleaning water of the present invention include cleaning water containing hydrogen peroxide and carbonic acid, cleaning water containing ozone and carbonic acid, cleaning water containing oxygen gas and carbonic acid, containing oxidizing chlorine and carbonic acid. Washing water, washing water containing hydrogen gas and carbon dioxide, and the like.
【０００６】電子材料用洗浄水の酸化還元電位は、含有
される酸化剤又は還元剤の濃度とともに、洗浄水のpHに
よっても変化する。図１は、酸化剤を高濃度、中濃度、
低濃度に含有する電子材料用洗浄水の、pHと酸化還元電
位の関係を示す模式的説明図である。同一pHで比較する
と、酸化剤の濃度が高いほど洗浄水の酸化還元濃度は高
くなるが、酸化剤の濃度が一定であっても、洗浄水のpH
が低いほど酸化還元電位は高くなる。電子材料表面に付
着した金属汚染や有機物汚染を除去する場合は、一般に
洗浄水の酸化還元電位が高いほど洗浄効果が高まるの
で、酸化剤を含有する洗浄水に酸を添加してpHを低下さ
せることが行われる。電子材料用洗浄水のpHを下げ、酸
化還元電位を高めて有機物汚染、金属汚染などの除去効
果を高めるために、塩酸などの鉱酸を添加すると、ユー
スポイントで使用されなかった洗浄水を返送し、一次純
水製造部において再処理するとき、除去すべきイオンの
負荷が大きくなるが、塩酸などの鉱酸の代わりに、炭酸
又は炭酸ガスを用いてpHを調整することにより、一次純
水製造部において、脱炭酸装置により容易に炭酸を除去
することが可能となり、脱炭酸装置の後段に設置したイ
オン交換装置への負荷を軽減することができる。炭酸ガ
スは、水に非常に溶解しやすく、その濃度が正しくpHの
低下に反映される。例えば、中性の水に炭酸ガス１００
mg／リットルを溶解させると、pHは約４.５まで低下す
る。本発明の電子材料用洗浄水は、洗浄する対象物に応
じて、含有させる酸化剤又は還元剤と炭酸の量を調整
し、所望の酸化還元電位及びpHを有する洗浄水とするこ
とができる。[0006] The oxidation-reduction potential of the cleaning water for electronic materials varies depending on the pH of the cleaning water as well as the concentration of the oxidizing or reducing agent contained. FIG. 1 shows that the oxidizing agent has a high concentration, a medium concentration,
FIG. 4 is a schematic explanatory view showing the relationship between pH and oxidation-reduction potential of electronic material cleaning water contained at a low concentration. When compared at the same pH, the higher the concentration of the oxidizing agent, the higher the oxidation-reduction concentration of the washing water.
The lower the value, the higher the redox potential. When removing metal contamination and organic matter contamination attached to the electronic material surface, generally, the higher the oxidation-reduction potential of the cleaning water, the higher the cleaning effect, so the acid is added to the cleaning water containing the oxidizing agent to lower the pH. Is done. Mineral acid such as hydrochloric acid is added to lower the pH of the washing water for electronic materials and raise the oxidation-reduction potential to enhance the effect of removing organic matter contamination and metal contamination. Then, when reprocessing in the primary pure water production department, the load of ions to be removed increases, but by adjusting the pH using carbon dioxide or carbon dioxide gas instead of mineral acids such as hydrochloric acid, the primary pure water is removed. In the production section, carbon dioxide can be easily removed by the decarbonation device, and the load on the ion exchange device installed downstream of the decarbonation device can be reduced. Carbon dioxide is very soluble in water, and its concentration is correctly reflected in the drop in pH. For example, carbon dioxide gas 100
Dissolving mg / l lowers the pH to about 4.5. The washing water for electronic materials of the present invention can be used as the washing water having desired oxidation-reduction potential and pH by adjusting the amounts of the oxidizing agent or reducing agent and the carbonic acid to be contained in accordance with the object to be washed.
【０００７】本発明の電子材料用洗浄水は、炭酸を使用
して洗浄水のpHを調整するものであり、炭酸によりpHを
調整した洗浄水は、従来の塩酸などの鉱酸を用いてpHを
調整した洗浄水とpHが同じであれば、同等の洗浄効果を
有する。超純水自体をウェーハに高圧スプレーして洗浄
する際に、超純水に炭酸を溶解して超純水の比抵抗を下
げ、ウェーハにおける静電気の発生を抑制することは従
来も行われていたが、酸化剤又は還元剤を含有する洗浄
水に炭酸を溶解させることは行われてはいなかった。ユ
ースポイントで使用されなかった本発明の電子材料用洗
浄水は、脱炭酸処理ののち、一次純水製造部又は超純水
製造装置に戻し、再利用することができる。洗浄水中の
炭酸は、脱炭酸により容易に除去することができるの
で、塩類の増加はなく、超純水製造装置の脱塩装置の負
荷を増大させることがない。炭酸を含有する電子材料用
洗浄水の余剰分を戻すポイントは、脱炭酸装置の上流で
あれば特に制限はないが、特に前処理工程と一次純水製
造部との中間に位置する水槽が適当である。酸化剤がオ
ゾンである本発明の電子材料用洗浄水を回収する場合に
は、紫外線照射、触媒や活性炭との接触などより、オゾ
ンを分解して酸素としたのちに、一次純水製造部に戻す
ことが好ましい。本発明の電子材料用洗浄水について脱
炭酸を行う方法には特に制限はなく、例えば、炭酸を含
有する洗浄水を通常の気液接触装置に通すことによって
行うことができる。炭酸を含有する洗浄水は、通常はpH
５以下となっていて、炭酸は、炭酸イオン、重炭酸イオ
ンのようなイオン状でなく、二酸化炭素（ＣＯ2）とし
て溶解しているので、気液接触することにより、容易に
炭酸ガスとなって気相に放散される。気液接触は、例え
ば、充填材を充填した気液接触塔において、洗浄水を上
部から散水し、下部から空気などの気体を供給すること
により行うことができる。また、電子材料用洗浄水を貯
留する槽内に気体を散気し、炭酸をストリッピングする
方法によることもできる。あるいは、脱気膜装置を使用
して脱炭酸を行うことも可能である。The cleaning water for electronic materials of the present invention adjusts the pH of the cleaning water using carbonic acid. The cleaning water whose pH has been adjusted using carbonic acid is adjusted to pH using a conventional mineral acid such as hydrochloric acid. If the pH is the same as that of the adjusted washing water, an equivalent washing effect is obtained. It has been conventional to dissolve carbonic acid in ultrapure water to lower the specific resistance of ultrapure water and suppress the generation of static electricity on the wafer when cleaning the ultrapure water itself by spraying the wafer with high pressure. However, dissolving carbonic acid in washing water containing an oxidizing agent or a reducing agent has not been performed. The washing water for electronic materials of the present invention, which has not been used at the point of use, can be returned to the primary pure water producing unit or the ultrapure water producing device after the decarbonation treatment and reused. Since the carbonic acid in the washing water can be easily removed by decarbonation, the amount of salts does not increase, and the load on the desalination device of the ultrapure water production device does not increase. The point of returning the surplus of the washing water for electronic material containing carbonic acid is not particularly limited as long as it is upstream of the decarbonation apparatus, but a water tank located in the middle between the pretreatment step and the primary pure water production unit is particularly suitable. It is. When recovering the electronic material washing water of the present invention in which the oxidizing agent is ozone, the ozone is decomposed into oxygen by ultraviolet irradiation, contact with a catalyst or activated carbon, and the like. It is preferable to return. The method for decarboxylation of the electronic material cleaning water of the present invention is not particularly limited, and can be performed, for example, by passing carbonic acid-containing cleaning water through a normal gas-liquid contact device. Washing water containing carbonic acid is usually pH
It is 5 or less. Carbonic acid is not ionized like carbonate ion and bicarbonate ion, but is dissolved as carbon dioxide (CO 2 ). Is released to the gas phase. The gas-liquid contact can be performed, for example, by spraying washing water from above and supplying gas such as air from below in a gas-liquid contact tower filled with a filler. Alternatively, a method may be employed in which gas is diffused in a tank for storing the electronic material cleaning water, and carbon dioxide is stripped. Alternatively, decarboxylation can be performed using a degassing membrane device.
【０００８】ユースポイントで使用されなかった本発明
の電子材料用洗浄水は、専用の脱炭酸装置で処理すれ
ば、洗浄水の含有成分により、超純水製造装置の一次純
水製造部に戻すことができ、あるいは、二次純水製造部
（サブシステム）に戻すこともできる。脱炭酸すること
なく戻す場合には、一次純水製造部に戻すことが好まし
い。一次純水製造部には、通常、脱気装置が設けられて
いるので、使用されなかった余剰の洗浄水中の炭酸は、
一次純水製造部を通過する間に除去される。また、使用
されなかった余剰洗浄水のpHが５より高い場合には、脱
炭酸することなく一次純水製造部に戻し、一次純水製造
部で炭酸を除去することができる。図２は、酸化剤がオ
ゾンである本発明の電子材料用洗浄水の利用システムの
一態様の系統図である。超純水製造装置のサブシステム
２（二次純水製造部）から送り出された超純水は、気体
透過膜モジュール３においてオゾン発生器４から送られ
るオゾンを溶解し、次いで気体透過膜モジュール５にお
いて炭酸ガス供給器６から送られる炭酸ガスを溶解し
て、オゾンと炭酸を含有する電子材料用洗浄水となる。
電子材料用洗浄水は、ユースポイント７へ送給される
が、ユースポイントで使用されなかった電子材料用洗浄
水は、オゾン分解装置８においてオゾンを分解除去した
のち返送配管９を通じて一次純水製造部１へ返送され
る。ユースポイント７において使用された電子材料用洗
浄水であっても、含まれる不純物の少ない洗浄水は、使
用されなかった洗浄水とともに返送して再利用すること
ができる。図示の一次純水製造部１は、脱カチオン塔１
１、脱炭酸塔１２、脱アニオン塔１３及び逆浸透膜装置
１４から構成されている。返送された余剰の洗浄水は、
一次純水製造部１へ供給される原水とともに一旦水槽１
０に貯留された後、脱カチオン塔１１を経由して脱炭酸
塔１２に送られる。脱炭酸塔１２においては、空気源１
５からの空気流によって洗浄水中の炭酸が除去される。
脱炭酸塔１２において炭酸を除去した洗浄水は、脱アニ
オン塔１３に送られる。洗浄水中の炭酸はすでに脱炭酸
塔１２で除去されているので、脱アニオン塔１３のアニ
オン交換樹脂に対する負荷とはならず、脱アニオン塔１
３は再生頻度が少なく長期間使用することができる。脱
アニオン塔１３から逆浸透膜装置を経由して流出する一
次純水は、次いでサブシステム２でさらに高純度化され
て再び超純水として使用される。[0008] The cleaning water for electronic materials of the present invention, which has not been used at the point of use, is returned to the primary pure water producing section of the ultrapure water producing device by the component contained in the cleaning water, if it is treated by a dedicated decarbonation device. Alternatively, it can be returned to the secondary pure water production section (subsystem). In the case of returning without decarbonation, it is preferable to return to the primary pure water production section. Since the primary deionized water production section is usually provided with a deaerator, the carbon dioxide in the surplus washing water not used is
It is removed while passing through the primary pure water production section. When the pH of the surplus washing water that has not been used is higher than 5, it can be returned to the primary pure water producing section without decarbonation, and the carbon dioxide can be removed in the primary pure water producing section. FIG. 2 is a system diagram of an embodiment of the electronic material cleaning water utilization system of the present invention in which the oxidizing agent is ozone. The ultrapure water sent from the subsystem 2 (secondary pure water production unit) of the ultrapure water production apparatus dissolves ozone sent from the ozone generator 4 in the gas permeable membrane module 3, and then dissolves the gas permeable membrane module 5. Then, the carbon dioxide gas sent from the carbon dioxide gas supply device 6 is dissolved, and becomes the electronic material cleaning water containing ozone and carbon dioxide.
The electronic material cleaning water is supplied to the use point 7, but the electronic material cleaning water not used at the use point is decomposed and removed by the ozone decomposer 8 and then returned to the return pipe 9 to produce primary pure water. Returned to unit 1. Even for the electronic material cleaning water used at the use point 7, the cleaning water containing few impurities can be returned and reused together with the unused cleaning water. The illustrated primary pure water production section 1 includes a decation tower 1
1, a decarbonation tower 12, a deanionization tower 13, and a reverse osmosis membrane device 14. The surplus washing water returned is
Once the water tank 1 together with the raw water supplied to the primary pure water production unit 1
After being stored at 0, it is sent to the decarbonation tower 12 via the decation tower 11. In the decarbonation tower 12, the air source 1
The air flow from 5 removes carbonic acid in the wash water.
The washing water from which carbon dioxide has been removed in the decarbonation tower 12 is sent to the deanionization tower 13. Since the carbonic acid in the washing water has already been removed in the decarbonation tower 12, the load on the anion exchange resin of the deanionization tower 13 does not occur, and the deanionization tower 1
No. 3 has a low regeneration frequency and can be used for a long time. The primary purified water flowing out of the deanionization tower 13 via the reverse osmosis membrane device is then further purified in the subsystem 2 and used again as ultrapure water.
【０００９】[0009]
【実施例】以下に、実施例を挙げて本発明をさらに詳細
に説明するが、本発明はこれらの実施例によりなんら限
定されるものではない。 実施例１ 下地金属製膜を施した直径６インチのシリコンウェーハ
を、銅５μｇ／リットルを含む水に３分間浸漬したのち
乾燥することによって、表面に銅が付着した汚染ウェー
ハを１２枚作製した。洗浄処理前の銅濃度を求めるため
に、その内の３枚を抜き取り、全反射蛍光Ｘ線分析法に
より表面の銅濃度を測定した。その結果、３枚の汚染ウ
ェーハの銅濃度の平均値は１.０５×１０12原子／cm2で
あった。 超純水に、気体透過膜モジュールを用いてオゾンを溶解
して、溶存オゾン濃度を１.０mg／リットルとしたの
ち、さらに気体透過膜モジュールを用いて炭酸ガスを濃
度１００mg／リットルになるように溶解し、pHを４.５
に調整して電子材料用洗浄水を得た。３枚の汚染ウェー
ハをこの電子材料用洗浄水に５分間浸漬して洗浄し、次
いで、超純水ですすぎを行ったのち乾燥した。乾燥後の
ウェーハ表面の銅の濃度を、全反射蛍光Ｘ線分析法によ
り測定した。３枚の平均値は０.９７×１０10原子／cm2
であった。この電子材料用洗浄水を、プラスチック充填
材を充填した気液接触塔に通水させたところ、溶解して
いる炭酸ガス濃度は１mg／リットルまで低下し、実質的
にイオン負荷とはならなかった。 比較例１ 電子材料用洗浄水として、気体透過膜モジュールを用い
てオゾンを溶解して、溶存オゾン濃度を１.０mg／リッ
トルとしたのち、さらに塩酸を添加してpHを４.５に調
整した電子材料用洗浄水を用いた以外は、実施例１と同
じ操作を繰り返した。洗浄、乾燥後の３枚のウェーハ表
面の銅の濃度の平均値は０.９８×１０10原子／cm2であ
った。 実施例２ 電子材料用洗浄水として、気体透過膜モジュールを用い
てオゾンを溶解して、溶存オゾン濃度を１.０mg／リッ
トルとしたのち、さらにあらかじめ調製した飽和炭酸水
を添加してpHを４.５に調整した電子材料用洗浄水を用
いた以外は、実施例１と同じ操作を繰り返した。洗浄、
乾燥後の３枚のウェーハ表面の銅の濃度の平均値は０.
９５×１０10原子／cm2であった。 比較例２ 電子材料用洗浄水として、気体透過膜モジュールを用い
てオゾンを溶解して、溶存オゾン濃度を１.０mg／リッ
トルとしたのち、pH調整を行わないpH６.５の電子材料
用洗浄水を用いた以外は、実施例１と同じ操作を繰り返
した。洗浄、乾燥後の３枚のウェーハ表面の銅の濃度の
平均値は３.１２×１０10原子／cm2であった。実施例１
〜２及び比較例１〜２の結果を、第１表に示す。EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. Example 1 A silicon wafer having a diameter of 6 inches having a base metal film formed thereon was immersed in water containing 5 μg / liter of copper for 3 minutes, and then dried to prepare 12 contaminated wafers having copper adhered to the surface. In order to determine the copper concentration before the cleaning treatment, three of them were extracted and the surface copper concentration was measured by total reflection X-ray fluorescence analysis. As a result, the average value of the copper concentration of the three contaminated wafers was 1.05 × 10 12 atoms / cm 2 . After dissolving ozone in ultrapure water using a gas permeable membrane module to bring the dissolved ozone concentration to 1.0 mg / l, further using a gas permeable membrane module to adjust the concentration of carbon dioxide to 100 mg / l. Dissolve and adjust pH to 4.5
To obtain washing water for electronic materials. The three contaminated wafers were washed by immersing them in the electronic material cleaning water for 5 minutes, then rinsed with ultrapure water, and then dried. The concentration of copper on the wafer surface after drying was measured by total reflection X-ray fluorescence analysis. The average of the three images is 0.97 × 10 10 atoms / cm 2
Met. When the washing water for electronic materials was passed through a gas-liquid contact tower filled with a plastic filler, the dissolved carbon dioxide gas concentration was reduced to 1 mg / liter, and the ion load was not substantially reduced. . Comparative Example 1 As a washing water for electronic materials, ozone was dissolved using a gas permeable membrane module to adjust the dissolved ozone concentration to 1.0 mg / liter, and then hydrochloric acid was added to adjust the pH to 4.5. The same operation as in Example 1 was repeated except that the electronic material cleaning water was used. The average value of the copper concentration on the surfaces of the three wafers after washing and drying was 0.98 × 10 10 atoms / cm 2 . Example 2 As a washing water for electronic materials, ozone was dissolved using a gas permeable membrane module to make the dissolved ozone concentration 1.0 mg / liter, and then a saturated carbonated water prepared in advance was added to adjust the pH to 4. The same operation as in Example 1 was repeated, except that the electronic material cleaning water adjusted to 0.5 was used. Washing,
The average value of the copper concentration on the surfaces of the three wafers after drying was 0.3.
It was 95 × 10 10 atoms / cm 2 . Comparative Example 2 Washing water for electronic materials having a pH of 6.5 without dissolving ozone using a gas permeable membrane module to adjust the concentration of dissolved ozone to 1.0 mg / liter and then adjusting pH as a washing water for electronic materials. The same operation as in Example 1 was repeated, except that was used. The average value of the copper concentration on the surfaces of the three wafers after washing and drying was 3.12 × 10 10 atoms / cm 2 . Example 1
Table 1 shows the results of Comparative Examples 1 and 2 and Comparative Examples 1 and 2.
【００１０】[0010]
【表１】 [Table 1]
【００１１】第１表の結果から、超純水にオゾン１.０m
g／リットルを溶解し、さらに炭酸ガスを溶解してpHを
４.５に調整した電子材料用洗浄水を用いた実施例１
と、超純水にオゾン１.０mg／リットルを溶解し、さら
に塩酸を添加してpHを４.５に調整した電子材料用洗浄
水を用いた比較例１とで、ウェーハ表面の銅汚染は同程
度まで除去されている。すなわち、炭酸を溶解すること
によりpH調整を行った本発明の電子材料用洗浄水によっ
て、塩酸を添加することによりpH調整を行った従来の電
子材料用洗浄水と変わらぬ洗浄効果が得られることが分
かる。また、あらかじめ調製した飽和炭酸水を添加する
ことにより、炭酸を含有させた実施例２の電子材料用洗
浄水を用いても、気体透過膜モジュールを用いて炭酸ガ
スを溶解させた実施例１の電子材料用洗浄水と同じ洗浄
効果が得られている。これに対して、超純水にオゾン１.
０mg／リットルを溶解し、pH調整は行わない比較例１の
電子材料用洗浄水を用いた場合は、銅汚染の除去が不十
分である。From the results shown in Table 1, it is found that 1.0 m of ozone
g / liter and further dissolved in carbon dioxide gas to adjust the pH to 4.5 Example 1 using washing water for electronic materials
In comparison with Comparative Example 1, in which 1.0 mg / L of ozone was dissolved in ultrapure water and the pH was adjusted to 4.5 by adding hydrochloric acid, copper contamination on the wafer surface was reduced. It has been removed to the same extent. That is, the washing effect for electronic materials of the present invention, the pH of which has been adjusted by dissolving carbonic acid, can provide the same cleaning effect as the conventional washing water for electronic materials, of which pH has been adjusted by adding hydrochloric acid. I understand. In addition, even if the washing water for electronic materials of Example 2 containing carbonic acid was used by adding saturated carbonated water prepared in advance, the carbonic acid gas of Example 1 was dissolved using the gas permeable membrane module. The same cleaning effect as the cleaning water for electronic materials is obtained. In contrast, ultrapure water contains ozone 1.
When the washing water for electronic material of Comparative Example 1 in which 0 mg / liter was dissolved and the pH was not adjusted was used, the removal of copper contamination was insufficient.
【００１２】[0012]
【発明の効果】本発明の電子材料用洗浄水は、洗浄水の
pH調整に炭酸を用いるので、塩酸などの鉱酸の添加の必
要がなく、ユースポイントで使用されなかった余剰の洗
浄水は、一次純水製造部の脱炭酸装置の上流に返送する
か、専用の脱炭酸装置で処理することにより、炭酸は容
易に除去され、脱イオン装置へ負荷をかけることなく再
利用することができる。The cleaning water for electronic materials of the present invention is the cleaning water.
Since carbon dioxide is used for pH adjustment, there is no need to add a mineral acid such as hydrochloric acid, and excess washing water not used at the point of use can be returned to the upstream of the decarbonation unit in the primary pure water production department or dedicated The carbonic acid is easily removed by treating with the decarbonation apparatus of the above, and can be reused without applying a load to the deionization apparatus.
【図１】図１は、電子材料用洗浄水のpHと酸化還元電位
の関係を示す説明図である。FIG. 1 is an explanatory diagram showing the relationship between the pH of the washing water for electronic materials and the oxidation-reduction potential.
【図２】図２は、本発明の電子材料用洗浄水の利用シス
テムの一態様の系統図である。FIG. 2 is a system diagram of one embodiment of a system for using the cleaning water for electronic materials of the present invention.
１ 一次純水製造部 ２ サブシステム ３ 気体透過膜モジュール ４ オゾン発生器 ５ 気体透過膜モジュール ６ 炭酸ガス供給器 ７ ユースポイント ８ オゾン分解装置 ９ 返送配管 １０ 水槽 １１ 脱カチオン塔 １２ 脱炭酸塔 １３ 脱アニオン塔 １４ 逆浸透膜装置 １５ 空気源 DESCRIPTION OF SYMBOLS 1 Primary pure water production part 2 Subsystem 3 Gas permeable membrane module 4 Ozone generator 5 Gas permeable membrane module 6 Carbon dioxide gas supply 7 Use point 8 Ozone decomposer 9 Return piping 10 Water tank 11 Decationization tower 12 Decarbonation tower 13 Desorption Anion tower 14 Reverse osmosis membrane device 15 Air source
Claims (1)
を特徴とする電子材料用洗浄水。1. A washing water for electronic materials, comprising an oxidizing or reducing agent and carbonic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35518097A JP3914624B2 (en) | 1997-12-24 | 1997-12-24 | How to reuse cleaning water for electronic materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35518097A JP3914624B2 (en) | 1997-12-24 | 1997-12-24 | How to reuse cleaning water for electronic materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11186207A true JPH11186207A (en) | 1999-07-09 |
| JP3914624B2 JP3914624B2 (en) | 2007-05-16 |
Family
ID=18442421
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35518097A Expired - Lifetime JP3914624B2 (en) | 1997-12-24 | 1997-12-24 | How to reuse cleaning water for electronic materials |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3914624B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6310017B1 (en) * | 1999-02-01 | 2001-10-30 | Ct Associates, Inc. | Cleaner composition, method for making and using same |
| WO2003091481A1 (en) * | 2002-04-25 | 2003-11-06 | Hideo Yoshida | Method for activating surface of parent material and its activating system |
| JP2009040656A (en) * | 2007-08-10 | 2009-02-26 | Kurita Water Ind Ltd | Apparatus and method for producing carbonated water, and method of washing electronic member |
| JP2019111495A (en) * | 2017-12-25 | 2019-07-11 | 株式会社荏原製作所 | Gas solution production device |
| US11040315B2 (en) | 2018-02-23 | 2021-06-22 | Ebara Corporation | Gas-dissolved liquid producing apparatus |
-
1997
- 1997-12-24 JP JP35518097A patent/JP3914624B2/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6310017B1 (en) * | 1999-02-01 | 2001-10-30 | Ct Associates, Inc. | Cleaner composition, method for making and using same |
| WO2003091481A1 (en) * | 2002-04-25 | 2003-11-06 | Hideo Yoshida | Method for activating surface of parent material and its activating system |
| US7300527B2 (en) | 2002-04-25 | 2007-11-27 | Hideo Yoshida | Method for activating surface of base material and apparatus thereof |
| US7736442B2 (en) | 2002-04-25 | 2010-06-15 | Hideo Yoshida | Method for activating surface of base material and apparatus thereof |
| JP2009040656A (en) * | 2007-08-10 | 2009-02-26 | Kurita Water Ind Ltd | Apparatus and method for producing carbonated water, and method of washing electronic member |
| JP2019111495A (en) * | 2017-12-25 | 2019-07-11 | 株式会社荏原製作所 | Gas solution production device |
| US11040315B2 (en) | 2018-02-23 | 2021-06-22 | Ebara Corporation | Gas-dissolved liquid producing apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3914624B2 (en) | 2007-05-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5072062B2 (en) | Method, apparatus and apparatus for producing hydrogen gas-dissolved cleaning water | |
| JP3117427B2 (en) | Improved cleaning method for microelectronic circuit boards | |
| KR101514863B1 (en) | Cleaning water for electronic material, method of cleaning electronic material, and system for supplying water containing dissolved gases | |
| JP2003205299A (en) | Hydrogen dissolved water manufacturing system | |
| WO2009113682A1 (en) | Gas-dissolved water supply system | |
| WO2014069203A1 (en) | Method for manufacturing ozone-gas-dissolved water and cleaning method for electronic materials | |
| JP3296405B2 (en) | Cleaning method and cleaning device for electronic component members | |
| JP2004122020A (en) | Ultrapure water manufacturing apparatus and method for washing ultrapure water manufacturing and supplying system of the apparatus | |
| JP4273440B2 (en) | Cleaning water for electronic material and cleaning method for electronic material | |
| JP3914624B2 (en) | How to reuse cleaning water for electronic materials | |
| JPH1129794A (en) | Cleaning water for electronic material its reparation, and cleaning of electronic material | |
| JP2006278838A (en) | Sulfuric acid recycling type cleaning system | |
| JPH10225664A (en) | Wet treating device | |
| JP3928484B2 (en) | Functional water recovery method | |
| JPH10128254A (en) | Washing method for electronic members and device therefor | |
| JP3016301B2 (en) | Cleaning method | |
| JPH06285464A (en) | Method and apparatus for treating recovered water to obtain recycled water | |
| JP2000262992A (en) | Substrate washing method | |
| JP3413411B2 (en) | Method for producing reclaimed cleaning solution for metal products | |
| JP3444473B2 (en) | Electronic material cleaning method and electronic material cleaning water | |
| JP2012186348A (en) | Cleaning water for electronic material, cleaning method of electronic material and supply system of gas dissolution water | |
| KR100502589B1 (en) | Method of regenerating effluent as washing liquid for metal products | |
| JP2001062412A (en) | Cleaning method, production of cleaning liquid, cleaning liquid and producing device for cleaning liquid | |
| JPH11158494A (en) | Cleaning water for electronic material | |
| JPH11181493A (en) | Cleaning water for electronic material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20040414 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040610 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20050106 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20050309 |
|
| A911 | Transfer of reconsideration by examiner before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20050419 |
|
| A912 | Removal of reconsideration by examiner before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A912 Effective date: 20050617 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20061225 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20070205 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110209 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110209 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120209 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120209 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130209 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130209 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140209 Year of fee payment: 7 |
|
| EXPY | Cancellation because of completion of term |