JPH1129794A - Cleaning water for electronic material, method for producing the same, and method for cleaning electronic material - Google Patents
Cleaning water for electronic material, method for producing the same, and method for cleaning electronic materialInfo
- Publication number
- JPH1129794A JPH1129794A JP19778297A JP19778297A JPH1129794A JP H1129794 A JPH1129794 A JP H1129794A JP 19778297 A JP19778297 A JP 19778297A JP 19778297 A JP19778297 A JP 19778297A JP H1129794 A JPH1129794 A JP H1129794A
- Authority
- JP
- Japan
- Prior art keywords
- cleaning
- water
- electronic material
- fine particles
- electronic
- 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)
- Separation Using Semi-Permeable Membranes (AREA)
- Degasification And Air Bubble Elimination (AREA)
- Detergent Compositions (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
(57)【要約】
【課題】微粒子により汚染された半導体用シリコーン基
板、液晶用ガラス基板などの電子材料を、使用する薬剤
の量が少なく、しかも効率よく高い汚染物除去率で洗浄
することができる電子材料用洗浄水を提供する。
【解決手段】(１)溶存水素濃度が０.７mg／リットル以
上飽和濃度以下であり、pHが６〜１２である超純水から
なることを特徴とする電子材料用洗浄水、(２)超純水を
脱気し、ガス透過膜を介して水素ガスを供給するととも
に、アルカリを添加することを特徴とする該電子材料用
洗浄水の製造方法、及び、(３)微粒子で汚染された電子
材料を、該電子材料用洗浄水と超音波を照射しながら接
触させることを特徴とする電子材料の洗浄方法。
[PROBLEMS] To efficiently clean an electronic material such as a silicon substrate for a semiconductor and a glass substrate for a liquid crystal contaminated by fine particles with a small amount of a chemical used and at a high contaminant removal rate. Provide cleaning water for electronic materials that can be used. (1) Ultra-pure water having a dissolved hydrogen concentration of 0.7 mg / liter or more and a saturation concentration or less and a pH of 6 to 12; Degassing pure water, supplying hydrogen gas through a gas permeable membrane, and adding alkali, the method for producing the washing water for electronic materials, and (3) electrons contaminated with fine particles. A method for cleaning an electronic material, comprising: bringing a material into contact with the electronic material cleaning water while irradiating an ultrasonic wave.
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、微粒子により汚
染された半導体用シリコーン基板、液晶用ガラス基板な
どの電子材料を、使用する薬剤の量が少なく、超音波を
用いて、しかも効率よく高い汚染物除去率で洗浄するこ
とができ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 an electronic material, such as a silicon substrate for semiconductors and a glass substrate for liquid crystal, which is contaminated by fine particles, which uses a small amount of chemicals, uses ultrasonic waves, and efficiently achieves a high contaminant removal rate. The present invention relates to a washing water for electronic materials that can be washed with water.
【０００２】[0002]
【従来の技術】従来、ＬＳＩ製造工程における半導体表
面などの洗浄は、主として、濃アンモニア水又は濃塩酸
と、過酸化水素水と超純水とを混合して調製した溶液に
半導体を浸漬した後に超純水ですすぐ、いわゆるＲＣＡ
洗浄法によって行われてきた。ＲＣＡ洗浄法は、半導体
表面の金属分を除去するために有効な方法であるが、同
時に半導体表面に付着した微粒子も除去される。しか
し、このような方法では、高濃度の酸、アルカリや過酸
化水素を多量に使用するために、廃液中にこれらの薬品
が排出され、廃水処理において中和や沈殿処理などに多
大な負担がかかるとともに、多量の汚泥が発生する。す
なわち、半導体基板表面の清浄度を確保するために、薬
品及び廃液処理に多大な費用を必要としていた。このた
め、洗浄効率を落とすことなく、薬品使用量を低減する
ことができる洗浄方法が求められていた。2. Description of the Related Art Conventionally, cleaning of a semiconductor surface or the like in an LSI manufacturing process is mainly performed by immersing a semiconductor in a solution prepared by mixing concentrated ammonia water or concentrated hydrochloric acid, hydrogen peroxide solution and ultrapure water. Rinse with ultrapure water, so-called RCA
It has been done by a washing method. The RCA cleaning method is an effective method for removing metal components on the semiconductor surface, but also removes fine particles attached to the semiconductor surface. However, in such a method, since a large amount of high-concentration acid, alkali or hydrogen peroxide is used, these chemicals are discharged into a waste liquid, and a large burden is imposed on neutralization and precipitation treatment in wastewater treatment. At the same time, a large amount of sludge is generated. That is, in order to ensure the cleanliness of the surface of the semiconductor substrate, a large amount of cost is required for treating the chemical and the waste liquid. Therefore, there has been a demand for a cleaning method capable of reducing the amount of chemicals used without lowering the cleaning efficiency.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、微粒子によ
り汚染された半導体用シリコーン基板、液晶用ガラス基
板などの電子材料を、使用する薬剤の量が少なく、しか
も効率よく高い汚染物除去率で洗浄することができる電
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。DISCLOSURE OF THE INVENTION The present invention is intended to reduce the amount of chemicals used in electronic materials such as silicone substrates for semiconductors and glass substrates for liquid crystals contaminated by fine particles, and to achieve an efficient and high contaminant removal rate. An object of the present invention is to provide a washing water for electronic materials that can be washed.
【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、水素ガスを溶解
したアルカリ性の超純水が、微粒子で汚染された電子材
料の洗浄に極めて有効であることを見いだし、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）溶存水素濃度が０.７mg／リットル以上飽
和濃度以下であり、pHが６〜１２である超純水からなる
ことを特徴とする電子材料用洗浄水、（２）超純水を脱
気し、ガス透過膜を介して水素ガスを供給するととも
に、アルカリを添加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製造方法、及び、（３）微粒子で
汚染された電子材料を、第(１)項記載の電子材料用洗浄
水と超音波を照射しながら接触させることを特徴とする
電子材料の洗浄方法、を提供するものである。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, alkaline ultrapure water in which hydrogen gas has been dissolved has been used for cleaning electronic materials contaminated with fine particles. Was found to be extremely effective, and the present invention was completed based on this finding. That is, the present invention provides (1) ultrapure water having a dissolved hydrogen concentration of 0.7 mg / liter or more and a saturation concentration or less and a pH of 6 to 12, (1) The method for producing cleaning water for electronic materials according to (1), wherein ultrapure water is degassed, hydrogen gas is supplied through a gas permeable membrane, and alkali is added. 3) A method of cleaning an electronic material, wherein the method comprises contacting the electronic material contaminated with fine particles with the electronic material cleaning water described in (1) while applying ultrasonic waves.
【０００５】[0005]
【発明の実施の形態】本発明の電子材料用洗浄水は、溶
存水素濃度が０.７mg／リットル以上飽和濃度以下であ
り、pHが６〜１２である超純水からなる洗浄水である。
本発明の電子材料用洗浄水により洗浄することができる
電子材料としては、例えば、半導体用シリコン基板、液
晶用ガラス基板、精密電子部品、これらの製造装置の部
品などを挙げることができる。本発明に用いる超純水の
製造方法には特に制限はなく、例えば、脱イオン水、蒸
留水などの１次純水を、逆浸透膜、限外ろ過膜、精密ろ
過膜などを用いて処理することによって得ることができ
る。本発明に用いる超純水は、２５℃における電気抵抗
率が１８ＭΩ・cm以上であり、有機体炭素が１０μｇ／
リットル以下であり、微粒子が１０,０００個／／リッ
トル以下であることが好ましい。図１は、本発明の電子
材料用洗浄水の製造工程の一態様の工程系統図である。
超純水は、流量計１を経由して脱気膜装置２に送られ
る。脱気膜装置は、ガス透過膜を介して超純水と接する
気相側が真空ポンプ３により減圧状態に保たれ、超純水
中に溶存しているガス分が除去される。脱気された超純
水は、次いで溶解膜装置４に送られる。溶解膜装置にお
いては、水素供給器５から供給された水素ガスが気相側
に送られ、ガス透過膜を介して超純水に供給される。溶
存水素濃度が所定の値に達した超純水には、薬液貯槽６
から薬注ポンプ７によりアンモニア水などの薬液が供給
され、所定のpH値に調整される。水素を溶解し、アルカ
リ性となった超純水は、最後に精密ろ過装置８に送ら
れ、ＭＦフィルターなどにより微粒子を除去して本発明
の電子材料用洗浄水が得られる。BEST MODE FOR CARRYING OUT THE INVENTION The washing water for electronic materials of the present invention is a washing water comprising ultrapure water having a dissolved hydrogen concentration of 0.7 mg / liter or more and a saturation concentration or less and a pH of 6 to 12.
Examples of the electronic material that can be washed with the electronic material washing water of the present invention include a silicon substrate for a semiconductor, a glass substrate for a liquid crystal, a precision electronic component, and a component of these manufacturing apparatuses. The method for producing ultrapure water used in the present invention is not particularly limited. For example, primary pure water such as deionized water or distilled water is treated using a reverse osmosis membrane, an ultrafiltration membrane, a microfiltration membrane, or the like. Can be obtained. The ultrapure water used in the present invention has an electric resistivity at 25 ° C. of 18 MΩ · cm or more, and organic carbon of 10 μg / cm.
Liters or less, and the number of fine particles is preferably 10,000 particles / liter or less. FIG. 1 is a process flow chart of one embodiment of the process for producing electronic material cleaning water of the present invention.
The ultrapure water is sent to the degassing membrane device 2 via the flow meter 1. In the degassing membrane device, the gas phase in contact with the ultrapure water through the gas permeable membrane is kept in a reduced pressure state by the vacuum pump 3 to remove the gas dissolved in the ultrapure water. The degassed ultrapure water is then sent to the dissolved film device 4. In the dissolved membrane device, the hydrogen gas supplied from the hydrogen supplier 5 is sent to the gas phase and supplied to ultrapure water via the gas permeable membrane. The ultrapure water whose dissolved hydrogen concentration has reached a predetermined value
A chemical solution such as aqueous ammonia is supplied from the chemical injection pump 7 to adjust the pH value to a predetermined value. The ultrapure water that has dissolved the hydrogen and has become alkaline is finally sent to the microfiltration device 8 to remove fine particles with an MF filter or the like, thereby obtaining the electronic material cleaning water of the present invention.
【０００６】本発明において、超純水の脱気及び水素ガ
スの供給に用いるガス透過膜には特に制限はなく、例え
ば、ポリプロピレン、ポリジメチルシロキサン、ポリカ
ーボネート−ポリジメチルシロキサンブロック共重合
体、ポリビニルフェノール−ポリジメチルシロキサン−
ポリスルホンブロック共重合体、ポリ(４−メチルペン
テン−１)、ポリ(２,６−ジメチルフェニレンオキシ
ド)、ポリテトラフルオロエチレンなどの高分子膜など
を挙げることができる。水素ガスの供給方法には特に制
限はなく、例えば、重質油のガス化反応により得られる
合成ガスからの分離、メタノールの接触分解や水蒸気改
質、水の電気分解などを挙げることができる。もちろ
ん、高純度水素ガスボンベを使用してもよい。ガス透過
膜の液体側に脱気した超純水を通過させ、気体側に水素
ガスを供給することにより、水素ガスはガス透過膜を経
由して超純水中に移行する。本発明の電子材料用洗浄水
は、溶存水素濃度が０.７mg／リットル以上飽和濃度以
下である。水素ガスの水への飽和溶解度は、水素ガスと
水蒸気の分圧の合計が７６０mmHgのとき、１０℃におい
ては１.７mg／リットル、２０℃においては１.６mg／リ
ットル、３０℃においては１.５mg／リットル、４０℃
においては１.４mg／リットルである。電子材料用洗浄
水中の溶存水素濃度が０.７mg／リットル未満である
と、微粒子で汚染された電子材料からの微粒子の除去が
不十分となるおそれがある。In the present invention, the gas permeable membrane used for deaeration of ultrapure water and supply of hydrogen gas is not particularly limited. For example, polypropylene, polydimethylsiloxane, polycarbonate-polydimethylsiloxane block copolymer, polyvinylphenol -Polydimethylsiloxane-
Polymer membranes such as polysulfone block copolymer, poly (4-methylpentene-1), poly (2,6-dimethylphenylene oxide), and polytetrafluoroethylene can be given. The method for supplying hydrogen gas is not particularly limited, and examples thereof include separation of heavy oil from a synthesis gas obtained by a gasification reaction, catalytic cracking of methanol, steam reforming, and electrolysis of water. Of course, a high-purity hydrogen gas cylinder may be used. By passing degassed ultrapure water to the liquid side of the gas permeable membrane and supplying hydrogen gas to the gas side, the hydrogen gas moves into the ultrapure water via the gas permeable membrane. The cleaning water for electronic materials of the present invention has a dissolved hydrogen concentration of 0.7 mg / liter or more and a saturation concentration or less. The saturated solubility of hydrogen gas in water is 1.7 mg / liter at 10 ° C., 1.6 mg / liter at 20 ° C., and 1.0 mg at 30 ° C. when the total partial pressure of hydrogen gas and water vapor is 760 mmHg. 5mg / liter, 40 ℃
Is 1.4 mg / liter. If the dissolved hydrogen concentration in the electronic material washing water is less than 0.7 mg / liter, there is a possibility that the removal of the fine particles from the electronic material contaminated with the fine particles may be insufficient.
【０００７】本発明の電子材料用洗浄水は、pHが６〜１
２であり、より好ましくはpHが８〜１１である。電子材
料用洗浄水のpH調整のために添加するアルカリには特に
制限はないが、アンモニア水を特に好適に使用すること
ができる。電子材料用洗浄水のpHが６未満であると、微
粒子で汚染された電子材料からの微粒子の除去が不十分
となるおそれがある。電子材料用洗浄水のpHが１２を超
えると、洗浄後のすすぎ工程に多量の超純水と長時間を
要する上に、廃液の中和に必要な酸の量が多くなる。本
発明の電子材料用洗浄水を、微粒子で汚染された電子材
料と接触させる方法には特に制限はなく、微粒子の種
類、粒度、付着量などに応じて適宜選択することができ
る。例えば、微粒子で汚染された電子材料を電子材料用
洗浄水に浸漬してバッチ洗浄することができ、あるい
は、１枚ずつ処理する枚葉式洗浄を行うこともできる。
枚葉式洗浄の方法としては、微粒子で汚染された電子材
料を回転させつつ電子材料用洗浄水を流しかけるスピン
洗浄などが挙げられる。本発明においては、微粒子で汚
染された電子材料の洗浄に際して、電子材料用洗浄水に
超音波を照射する。電子材料用洗浄水に超音波を照射す
る方法には特に制限はなく、例えば、バッチ洗浄におい
ては、電子材料用洗浄水を貯留した槽に超音波の振動を
伝達することができ、スピン洗浄においては、流しかけ
る電子材料用洗浄水のノズル部において、超音波の振動
を伝達することができる。照射する超音波の周波数は、
２０kHz以上であることが好ましく、４００kHz以上であ
ることがより好ましい。超音波の周波数が２０kHz未満
であると、微粒子で汚染された電子材料からの微粒子の
除去が不十分となるおそれがある。被洗浄物表面に損傷
を与えない精密洗浄を行うには、４００kHz以上の、特
に高周波の超音波が望ましい。The washing water for electronic materials of the present invention has a pH of 6-1.
2, and more preferably the pH is 8-11. The alkali added for adjusting the pH of the washing water for electronic materials is not particularly limited, but ammonia water can be particularly preferably used. If the pH of the electronic material cleaning water is less than 6, the removal of the fine particles from the electronic material contaminated with the fine particles may be insufficient. If the pH of the washing water for electronic materials exceeds 12, a large amount of ultrapure water and a long time are required for the rinsing step after washing, and the amount of acid necessary for neutralizing the waste liquid increases. The method for bringing the electronic material cleaning water of the present invention into contact with the electronic material contaminated with the fine particles is not particularly limited, and can be appropriately selected according to the type, the particle size, the attached amount and the like of the fine particles. For example, the electronic material contaminated with the fine particles can be immersed in the electronic material cleaning water to perform batch cleaning, or can perform single-wafer cleaning in which one by one is processed.
As a method of single-wafer cleaning, spin cleaning in which a cleaning water for electronic materials is flown while rotating electronic materials contaminated with fine particles is exemplified. In the present invention, when cleaning an electronic material contaminated with fine particles, ultrasonic waves are applied to the electronic material cleaning water. There is no particular limitation on the method of irradiating ultrasonic waves to the electronic material cleaning water.For example, in batch cleaning, ultrasonic vibration can be transmitted to a tank storing electronic material cleaning water, and in spin cleaning, Can transmit ultrasonic vibrations in the nozzle portion of the washing water for electronic material to be poured. The frequency of the ultrasonic wave to be irradiated is
It is preferably at least 20 kHz, more preferably at least 400 kHz. If the frequency of the ultrasonic wave is less than 20 kHz, the removal of the fine particles from the electronic material contaminated with the fine particles may be insufficient. In order to perform precision cleaning that does not damage the surface of the object to be cleaned, ultrasonic waves of 400 kHz or more, particularly high frequency, are desirable.
【０００８】本発明によれば、微粒子で汚染された電子
材料の洗浄に使用する薬品の量を大幅に減少し、かつ高
い洗浄効果を得ることができ、さらに、電子材料の洗浄
後の廃液処理が容易になる。すなわち、従来の洗浄廃液
は、アンモニアや過酸化水素を大量に含んだ高濃度の状
態で排出されるため、中和処理や分解処理が必要であ
り、廃液処理においても洗浄液の調製に使用したのと同
程度の量の薬品が必要となる。本発明においては、排出
されるのはアルカリを含んだpH６〜１２の液であり、例
えば、少量の酸を加えて中和することにより放流し得る
水質となる。もちろん、超純水の原水として再利用する
こともできる水質である。廃液中に含まれる水素ガスは
微量であり、通常は安全上の問題を生ずることはない
が、使用環境によっては、必要に応じて廃液中に溶存す
る水素ガスを分解することができる。例えば、溶存水素
を含有した水に空気吹き込みなどによって酸素を溶解
し、パラジウム触媒などの存在下において、水素と酸素
の反応により水を生成して、溶存水素を除去することが
できる。According to the present invention, the amount of chemicals used for cleaning electronic materials contaminated with fine particles can be greatly reduced, and a high cleaning effect can be obtained. Becomes easier. That is, since the conventional cleaning waste liquid is discharged in a high concentration state containing a large amount of ammonia and hydrogen peroxide, a neutralization treatment and a decomposition treatment are required. The same amount of chemicals is required. In the present invention, what is discharged is a solution having a pH of 6 to 12 containing an alkali. For example, by adding a small amount of acid to neutralize the solution, the water quality can be released. Of course, the water quality can be reused as raw water of ultrapure water. The amount of hydrogen gas contained in the waste liquid is very small and does not usually cause a safety problem. However, depending on the use environment, the hydrogen gas dissolved in the waste liquid can be decomposed as needed. For example, dissolved oxygen can be removed by dissolving oxygen into water containing dissolved hydrogen by blowing air into the water and reacting hydrogen with oxygen to generate water in the presence of a palladium catalyst or the like.
【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（電子材料用洗浄水の製造） 図１に示す装置を用いて、電子材料用洗浄水を製造し
た。脱気膜装置、溶解膜装置ともに、ポリプロピレン製
のガス透過膜を備えたものであり、脱気膜装置の気相側
は真空ポンプにより５０Torr以下の減圧とし、溶解膜装
置の気相側には水素ガスを１kg／cm2（ゲージ圧）の圧
力で供給した。この装置に、超純水を７００ml／分で供
給し、薬注ポンプから希釈したアンモニア水を３.５ml
／分で供給した。精密ろ過装置から流出する電子材料用
洗浄水は、溶存水素濃度が１.４２mg／リットルであ
り、pHは１０.６であった。 比較例１ 図１に示す装置の配管を変更し、超純水を脱気膜装置で
脱気することなく、直接溶解膜装置へ送りこんだ以外
は、実施例１と同じ操作を繰り返した。精密ろ過装置か
ら流出する電子材料用洗浄水は、溶存水素濃度が０.６
３mg／リットルであり、pHは１０.６であった。実施例
１と比較例１の結果から、超純水を脱気したのち、ガス
透過膜を介して水素ガスを供給することにより、溶存水
素濃度を０.７mg／リットル以上とし得ることが分か
る。 比較例２ ５０Ａ、４.５Ｖで、流速が３.５リットル／分の条件で
調製した電解カソード水中の溶存水素濃度を測定したと
ころ、０.５５mg／リットルであった。この結果から、
電気分解によっては、溶存水素濃度を０.７mg／リット
ル以上とすることは困難であることが分かる。 実施例２（シリコンウェーハの洗浄） オゾンを含有する超純水で表面を酸化した直径６インチ
のシリコンウェーハを、アルミナ微粉末で汚染すること
により、表面にアルミナの微粒子が付着した汚染ウェー
ハを作製した。この汚染ウェーハについて、レーザー散
乱光検出方式にもとづくウェーハ・ゴミ検出装置［東京
光学機械(株)］により付着微粒子数を測定したところ、
ウェーハ１枚当たり、直径０.２〜０.５μｍの微粒子が
１２,６００個、直径０.５〜１.０μｍの微粒子が３１,
２００個、直径１.０μｍ以上の微粒子が２００個、合
計４４,０００個であった。この汚染ウェーハを５００r
pmで回転させ、実施例１の精密ろ過装置より流出する溶
存水素濃度１.４２mg／リットル、pH１０.６の電子材料
用洗浄水に、超音波照射ノズル［プレテック社、Ｆｉｎ
ｅ Ｊｅｔ］を用いて周波数１.６MHzの超音波を出力１
３.５Ｗ／cm2で照射しつつ、７００ml／分で流しかけ、
６０秒間スピン洗浄を行った。次いで、超純水を用いて
すすぎを行ったのち乾燥した。乾燥後のウェーハ表面の
付着微粒子数を、同様にして測定したところ、ウェーハ
１枚当たり、直径０.２〜０.５μｍの微粒子が４００
個、直径０.５〜１.０μｍの微粒子が３００個、直径
１.０μｍ以上の微粒子が１０個、合計７１０個であ
り、ウェーハ表面の微粒子の除去率は９８.４％であっ
た。 比較例３ 実施例１で得られる電子材料用洗浄水の代わりに、比較
例２で得られる電解カソード水にアンモニア水を添加し
てpHを１０.６に調整した液を洗浄水として用いた以外
は、実施例２と同じ操作を繰り返した。洗浄、乾燥後の
ウェーハ表面の付着微粒子数は、ウェーハ１枚当たり、
直径０.２〜０.５μｍの微粒子が２,１００個、直径０.
５〜１.０μｍの微粒子が１,４００個、直径１.０μｍ
以上の微粒子が１０個、合計３,５１０個であり、ウェ
ーハ表面の微粒子の除去率は９２.０％であった。 比較例４ 実施例１で得られる電子材料用洗浄水の代わりに、超純
水にアンモニア水を添加してpHを１０.６に調整した液
を洗浄水として用い、洗浄時間を３分間とした以外は、
実施例２と同じ操作を繰り返した。洗浄、乾燥後のウェ
ーハ表面の付着微粒子数は、ウェーハ１枚当たり７,９
００個であり、ウェーハ表面の微粒子の除去率は８２.
０％であった。 比較例５ 実施例１で得られる電子材料用洗浄水の代わりに、超純
水をそのまま洗浄水として用い、洗浄時間を３分間とし
た以外は、実施例２と同じ操作を繰り返した。洗浄、乾
燥後のウェーハ表面の付着微粒子数は、ウェーハ１枚当
たり３５,４００個であり、ウェーハ表面の微粒子の除
去率は１９.５％であった。実施例２及び比較例３〜５
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 (Production of cleaning water for electronic material) Using the apparatus shown in FIG. 1, cleaning water for electronic material was produced. Both the degassing membrane device and the dissolving membrane device are equipped with a gas permeable membrane made of polypropylene.The gas phase side of the degassing membrane device is evacuated to 50 Torr or less by a vacuum pump. Hydrogen gas was supplied at a pressure of 1 kg / cm 2 (gauge pressure). Ultrapure water is supplied to this apparatus at a rate of 700 ml / min, and 3.5 ml of diluted ammonia water is supplied from a chemical injection pump.
/ Min. The washing water for electronic materials flowing out of the microfiltration device had a dissolved hydrogen concentration of 1.42 mg / liter and a pH of 10.6. Comparative Example 1 The same operation as in Example 1 was repeated except that the piping of the apparatus shown in FIG. 1 was changed, and ultrapure water was directly sent to the dissolving membrane apparatus without being degassed by the degassing membrane apparatus. The washing water for electronic materials flowing out of the microfiltration device has a dissolved hydrogen concentration of 0.6.
It was 3 mg / l and the pH was 10.6. From the results of Example 1 and Comparative Example 1, it can be seen that the concentration of dissolved hydrogen can be increased to 0.7 mg / liter or more by degassing ultrapure water and then supplying hydrogen gas through a gas permeable membrane. Comparative Example 2 The concentration of dissolved hydrogen in the electrolytic cathode water prepared at 50 A, 4.5 V and a flow rate of 3.5 L / min was 0.55 mg / L. from this result,
It can be seen that it is difficult to increase the dissolved hydrogen concentration to 0.7 mg / liter or more by electrolysis. Example 2 (Washing of Silicon Wafer) A 6-inch diameter silicon wafer whose surface was oxidized with ultrapure water containing ozone was contaminated with alumina fine powder to prepare a contaminated wafer having fine alumina particles adhered to the surface. did. For this contaminated wafer, the number of attached fine particles was measured by a wafer / dust detector [Tokyo Optical Machinery Co., Ltd.] based on the laser scattered light detection method.
12,600 fine particles having a diameter of 0.2 to 0.5 μm and 31, fine particles having a diameter of 0.5 to 1.0 μm per wafer.
There were 200 particles and 200 particles having a diameter of 1.0 μm or more, for a total of 44,000 particles. 500 r of this contaminated wafer
pm, and an ultrasonic irradiation nozzle [Pretec, Fintech Co., Ltd.]
e Jet] to output an ultrasonic wave with a frequency of 1.6 MHz1
While irradiating at 3.5 W / cm 2 , pour at 700 ml / min.
Spin cleaning was performed for 60 seconds. Next, the substrate was rinsed with ultrapure water and dried. The number of fine particles adhering to the surface of the wafer after drying was measured in the same manner. As a result, 400 fine particles having a diameter of 0.2 to
The number of particles was 300, the number of fine particles having a diameter of 0.5 to 1.0 μm was 300, and the number of fine particles having a diameter of 1.0 μm or more was 10, 710 in total. The removal rate of fine particles on the wafer surface was 98.4%. Comparative Example 3 Instead of using the cleaning water for electronic materials obtained in Example 1, a solution adjusted to pH 10.6 by adding ammonia water to the electrolytic cathode water obtained in Comparative Example 2 was used as the cleaning water. The same operation as in Example 2 was repeated. The number of fine particles adhering to the wafer surface after cleaning and drying is as follows:
2,100 fine particles having a diameter of 0.2 to 0.5 μm, and a diameter of 0.5
1,400 microparticles of 5-1.0 μm, 1.0 μm in diameter
The number of the above fine particles was 10, that is, 3,510 in total, and the removal rate of the fine particles on the wafer surface was 92.0%. Comparative Example 4 Instead of the washing water for electronic materials obtained in Example 1, a solution adjusted to pH 10.6 by adding ammonia water to ultrapure water was used as washing water, and the washing time was set to 3 minutes. except,
The same operation as in Example 2 was repeated. The number of fine particles adhering to the wafer surface after cleaning and drying was 7.9 per wafer
00, and the removal rate of fine particles on the wafer surface was 82.
It was 0%. Comparative Example 5 The same operation as in Example 2 was repeated except that ultrapure water was used as the cleaning water instead of the electronic material cleaning water obtained in Example 1 and the cleaning time was 3 minutes. The number of attached fine particles on the wafer surface after cleaning and drying was 35,400 per wafer, and the removal rate of fine particles on the wafer surface was 19.5%. Example 2 and Comparative Examples 3 to 5
Table 1 shows the results.
【００１０】[0010]
【表１】 [Table 1]
【００１１】第１表の結果から、本発明の電子材料用洗
浄水を用いて洗浄した汚染ウェーハからは、アルミナの
微粒子が高い除去率で洗浄、除去されているが、電解カ
ソード水にアンモニア水を加えてアルカリ性にした洗浄
水及び超純水にアンモニア水を加えてアルカリ性にした
洗浄水を用いた場合は、微粒子の除去率が低く、単に超
純水をそのまま洗浄水として用いた場合は、除去率が極
端に低くなることが分かる。 実施例３（シリコンウェーハの洗浄） スピン洗浄時間を３０秒間及び３分間とした以外は、実
施例２と同じ操作を繰り返した。洗浄、乾燥後のウェー
ハ表面の付着微粒子数及び微粒子の除去率は、洗浄時間
３０秒間のとき、それぞれ１,４００個、９６.８％であ
り、洗浄時間３分のとき、それぞれ２００個、９９.５
％であった。 比較例６ スピン洗浄時間を３０秒間及び３分間とした以外は、比
較例３と同じ操作を繰り返した。洗浄、乾燥後のウェー
ハ表面の付着微粒子数及び微粒子の除去率は、洗浄時間
３０秒間のとき、それぞれ７,９００個、８２.０％であ
り、洗浄時間３分のとき、それぞれ３,１００個、９３.
０％であった。実施例３及び比較例６の結果に実施例２
及び比較例３の結果を合わせて、洗浄時間と付着微粒子
数及び微粒子の除去率の関係を第２表に示す。From the results in Table 1, it can be seen that alumina particles were washed and removed at a high removal rate from the contaminated wafer washed with the electronic material washing water of the present invention. In the case where washing water made alkaline by adding ammonia and washing water made alkaline by adding ammonia water to ultrapure water is used, the removal rate of fine particles is low, and when ultrapure water is used as washing water as it is, It can be seen that the removal rate becomes extremely low. Example 3 (Cleaning of silicon wafer) The same operation as in Example 2 was repeated except that the spin cleaning time was 30 seconds and 3 minutes. The number of fine particles adhered to the wafer surface after cleaning and drying and the removal rate of fine particles were 1,400 and 96.8%, respectively, when the cleaning time was 30 seconds, and 200, 99, respectively when the cleaning time was 3 minutes. .5
%Met. Comparative Example 6 The same operation as in Comparative Example 3 was repeated except that the spin cleaning times were 30 seconds and 3 minutes. The number of fine particles adhered to the wafer surface after cleaning and drying and the removal rate of fine particles were 7,900 and 82.0%, respectively, for a cleaning time of 30 seconds, and 3,100 for a cleaning time of 3 minutes. , 93.
It was 0%. The results of Example 3 and Comparative Example 6 were compared to Example 2
Table 2 shows the relationship between the washing time, the number of attached fine particles, and the removal rate of the fine particles, together with the results of Comparative Example 3.
【００１２】[0012]
【表２】 [Table 2]
【００１３】第２表の結果から、本発明の電子材料用洗
浄水を用いて洗浄した汚染ウェーハからは、３分間の洗
浄により、アルミナの微粒子はほぼ完全に除去されてい
るが、電解カソード水にアンモニア水を加えてアルカリ
性にした洗浄水を用いた場合は、微粒子の除去率が低
く、しかも除去率が頭打ちになる傾向があり、洗浄時間
を延長しても微粒子の完全な除去は困難であろうと推定
される。From the results shown in Table 2, from the contaminated wafer cleaned using the cleaning water for electronic materials of the present invention, alumina particles were almost completely removed by cleaning for 3 minutes. In the case of using washing water made alkaline by adding aqueous ammonia, the removal rate of fine particles tends to be low, and the removal rate tends to plateau, and it is difficult to completely remove the fine particles even if the cleaning time is extended. It is estimated that there will be.
【００１４】[0014]
【発明の効果】本発明の電子材料用洗浄水は、使用する
薬剤の量が少なく、容易に製造することができ、微粒子
で汚染された電子材料の表面を高い洗浄効率で洗浄して
微粒子を除去することができ、さらに発生する廃液を容
易に処理することができる。The cleaning water for electronic materials of the present invention uses a small amount of chemicals, can be easily produced, and cleans the surface of electronic materials contaminated with fine particles with high cleaning efficiency to remove fine particles. It can be removed, and the generated waste liquid can be easily treated.
【図面の簡単な説明】[Brief description of the drawings]
【図１】図１は、本発明の電子材料用洗浄水の製造工程
の一態様の工程系統図である。FIG. 1 is a process flow diagram of one embodiment of a process for producing electronic material cleaning water of the present invention.
１ 流量計 ２ 脱気膜装置 ３ 真空ポンプ ４ 溶解膜装置 ５ 水素供給器 ６ 薬液貯槽 ７ 薬注ポンプ ８ 精密ろ過装置 DESCRIPTION OF SYMBOLS 1 Flow meter 2 Deaeration membrane device 3 Vacuum pump 4 Dissolution membrane device 5 Hydrogen supply 6 Chemical storage tank 7 Chemical injection pump 8 Microfiltration device
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｈ０１Ｌ 21/304 ３４１ Ｈ０１Ｌ 21/304 ３４１Ｍ ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI H01L 21/304 341 H01L 21/304 341M
Claims (3)
和濃度以下であり、pHが６〜１２である超純水からなる
ことを特徴とする電子材料用洗浄水。1. A cleaning water for electronic materials, comprising ultrapure water having a dissolved hydrogen concentration of 0.7 mg / liter or more and a saturation concentration or less and a pH of 6 to 12.
ガスを供給するとともに、アルカリを添加することを特
徴とする請求項１記載の電子材料用洗浄水の製造方法。2. The method according to claim 1, wherein ultrapure water is degassed, hydrogen gas is supplied through a gas permeable membrane, and alkali is added.
記載の電子材料用洗浄水と超音波を照射しながら接触さ
せることを特徴とする電子材料の洗浄方法。3. An electronic material contaminated with fine particles, wherein
A method for cleaning an electronic material, comprising bringing the electronic material into contact with the electronic material cleaning water while irradiating the ultrasonic wave.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19778297A JP3940967B2 (en) | 1997-07-08 | 1997-07-08 | Method for producing cleaning water for electronic material and method for cleaning electronic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19778297A JP3940967B2 (en) | 1997-07-08 | 1997-07-08 | Method for producing cleaning water for electronic material and method for cleaning electronic material |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JPH1129794A true JPH1129794A (en) | 1999-02-02 |
| JPH1129794A5 JPH1129794A5 (en) | 2005-04-07 |
| JP3940967B2 JP3940967B2 (en) | 2007-07-04 |
Family
ID=16380269
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19778297A Expired - Fee Related JP3940967B2 (en) | 1997-07-08 | 1997-07-08 | Method for producing cleaning water for electronic material and method for cleaning electronic material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3940967B2 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000306868A (en) * | 1999-02-17 | 2000-11-02 | Kurita Water Ind Ltd | Method for planarizing electronic material surface oxide film |
| JP2002045806A (en) * | 2000-08-01 | 2002-02-12 | Kurita Water Ind Ltd | Cleaning equipment |
| US6497240B1 (en) | 1999-04-21 | 2002-12-24 | Sharp Kabushiki Kaisha | Ultrasound cleaning device and resist-stripping device |
| US6903015B2 (en) | 2002-03-12 | 2005-06-07 | Kabushiki Kaisha Toshiba | Method of manufacturing a semiconductor device using a wet process |
| US7077915B2 (en) | 1999-05-20 | 2006-07-18 | Renesas Technology Corp. | Method of and apparatus for washing photomask and washing solution for photomask |
| JP2010241787A (en) * | 2009-03-13 | 2010-10-28 | Mizu Kk | Method and apparatus for producing hydrogen-containing biological fluid |
| JP2011147917A (en) * | 2010-01-25 | 2011-08-04 | Shin Etsu Handotai Co Ltd | Ultrasonic washing method, ultrasonic washing apparatus and method for producing propagation water used for ultrasonic washing |
| JP2011177242A (en) * | 2010-02-26 | 2011-09-15 | Mizu Kk | Method and device for manufacturing hydrogen-containing biocompatible solution |
| US20170015956A1 (en) * | 2015-07-17 | 2017-01-19 | Nomura Micro Science Co., Ltd. | Washing hydrogen water producing method and producing apparatus |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101255895B1 (en) * | 2009-12-10 | 2013-04-17 | 가부시키가이샤 코아테크노로지 | Method for manufacturing nano-bubble water containing saturated gas |
-
1997
- 1997-07-08 JP JP19778297A patent/JP3940967B2/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000306868A (en) * | 1999-02-17 | 2000-11-02 | Kurita Water Ind Ltd | Method for planarizing electronic material surface oxide film |
| US6497240B1 (en) | 1999-04-21 | 2002-12-24 | Sharp Kabushiki Kaisha | Ultrasound cleaning device and resist-stripping device |
| KR100483975B1 (en) * | 1999-04-21 | 2005-04-19 | 샤프 가부시키가이샤 | Ultrasonic Cleaning Device And Resist-Stripping Device |
| US7077915B2 (en) | 1999-05-20 | 2006-07-18 | Renesas Technology Corp. | Method of and apparatus for washing photomask and washing solution for photomask |
| JP2002045806A (en) * | 2000-08-01 | 2002-02-12 | Kurita Water Ind Ltd | Cleaning equipment |
| US6903015B2 (en) | 2002-03-12 | 2005-06-07 | Kabushiki Kaisha Toshiba | Method of manufacturing a semiconductor device using a wet process |
| US7727891B2 (en) | 2002-03-12 | 2010-06-01 | Kabushiki Kaisha Toshiba | Method of manufacturing a semiconductor device using a wet process |
| JP2010241787A (en) * | 2009-03-13 | 2010-10-28 | Mizu Kk | Method and apparatus for producing hydrogen-containing biological fluid |
| JP2011147917A (en) * | 2010-01-25 | 2011-08-04 | Shin Etsu Handotai Co Ltd | Ultrasonic washing method, ultrasonic washing apparatus and method for producing propagation water used for ultrasonic washing |
| JP2011177242A (en) * | 2010-02-26 | 2011-09-15 | Mizu Kk | Method and device for manufacturing hydrogen-containing biocompatible solution |
| US20170015956A1 (en) * | 2015-07-17 | 2017-01-19 | Nomura Micro Science Co., Ltd. | Washing hydrogen water producing method and producing apparatus |
| US10059911B2 (en) * | 2015-07-17 | 2018-08-28 | Nomura Micro Science Co., Ltd. | Washing hydrogen water producing method and producing apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3940967B2 (en) | 2007-07-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3409849B2 (en) | Manufacturing equipment for cleaning liquid for cleaning electronic components | |
| WO1996021242A1 (en) | Cleaning method | |
| JPH09153473A (en) | Wet processing method | |
| WO2009128327A1 (en) | Cleaning water for electronic material, method of cleaning electronic material, and system for supplying water containing dissolved gases | |
| JP3296405B2 (en) | Cleaning method and cleaning device for electronic component members | |
| CN110168705B (en) | Semiconductor substrate cleaning device and semiconductor substrate cleaning method | |
| US20150303053A1 (en) | Method for producing ozone gas-dissolved water and method for cleaning electronic material | |
| KR101431615B1 (en) | Silicon surface preparation | |
| JP2012143708A (en) | Washing method | |
| JP3940967B2 (en) | Method for producing cleaning water for electronic material and method for cleaning electronic material | |
| JPH1022246A (en) | Cleaning method | |
| JP4273440B2 (en) | Cleaning water for electronic material and cleaning method for electronic material | |
| JP4482844B2 (en) | Wafer cleaning method | |
| JP3639102B2 (en) | Wet processing equipment | |
| JP3332323B2 (en) | Cleaning method and cleaning device for electronic component members | |
| JP3296407B2 (en) | Cleaning method and cleaning device for electronic component members | |
| JP2004296463A (en) | Cleaning method and cleaning device | |
| JP2000288495A (en) | Cleaning method | |
| JP2002001243A (en) | How to clean electronic materials | |
| JPH1129795A (en) | Cleaning water for electronic material, method for producing the same, and method for cleaning electronic material | |
| JP3797775B2 (en) | Wet cleaning device for electronic material and processing method for cleaning liquid for electronic material | |
| JP3375052B2 (en) | Cleaning water for electronic materials | |
| JP3507590B2 (en) | Wet processing method and processing apparatus | |
| JPH11186207A (en) | Cleaning water for electronic materials | |
| JP6020626B2 (en) | Device Ge substrate cleaning method, cleaning water supply device and cleaning device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040520 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20040520 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20050815 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20050830 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20051021 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20051208 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20070309 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20070322 |
|
| 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: 20100413 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110413 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120413 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130413 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140413 Year of fee payment: 7 |
|
| LAPS | Cancellation because of no payment of annual fees |