JP4560966B2 - Cleaning method for electronic materials - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、電子材料の洗浄方法に関する。さらに詳しくは、本発明は、低濃度のオゾン含有水を用いて高い洗浄効果を得ることができる電子材料の洗浄方法に関する。
【０００２】
【従来の技術】
半導体用シリコン基板、液晶用ガラス基板、フォトマスク用石英基板などに付着した有機物は、従来はＳＰＭと呼ばれる硫酸と過酸化水素水の濃厚な混合薬液や、５０mg／Ｌ以上の高濃度のオゾン含有水を用いる洗浄により清浄化されていた。ＳＰＭ洗浄は、半導体表面のレジストなどの強固に付着した有機物や金属を除去するためには有効な方法であるが、高濃度の酸と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剤が排出され、廃液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、半導体基板などの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きた。また、近年、濃厚な薬液を使用しない、オゾン含有水による洗浄も普及し始めたが、強固に付着した有機物を除去するためには、５０〜１００mg／Ｌという高濃度のオゾン含有水を必要とする。高濃度のオゾン含有水を調製するためには、高濃度のオゾン含有ガスを大量に製造する必要がある。そのためには、高価なオゾン発生器が必要であり、製造費が嵩み、洗浄機、配管などの材質を傷めることになるので、頻繁にメンテナンスする必要があり、高濃度のオゾン含有ガスは人体に有害で、取り扱いに注意しなければならないなどの問題点がある。以上の点から、近年様々な新しい洗浄方法が試みられようとしている。
【０００３】
【発明が解決しようとする課題】
本発明は、低濃度のオゾン含有水を用いて高い洗浄効果を得ることができる電子材料の洗浄方法を提供することを目的としてなされたものである。
【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、電子材料の洗浄に用いる低濃度のオゾン含有水を常温以上に僅かに加温することにより、その洗浄効果を飛躍的に高め、低濃度のオゾン含有水を用いて高濃度のオゾン水に匹敵する有機物除去効果が得られることを見いだし、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）オゾン濃度１５〜５０ｍｇ／Ｌの温度２０℃以上のオゾン含有水を用いて電子材料の表面に付着した有機物を洗浄によって除去する方法であって、オゾン含有水のオゾン濃度ｃｍｇ／Ｌ、温度ｔ℃としたとき、１００≧ｃ＋ｔ＞４５を満たす条件で洗浄することにより、下記の指紋除去率測定試験における指紋除去率に換算して８０％以上の指紋除去率に相当する付着有機物の除去を行うことを特徴とする電子材料の洗浄方法、
指紋除去率測定試験：
１．直径６インチのシリコンウェーハに指を押しつけることにより、表面を指紋の有機物で汚染したシリコンウェーハを調製した。
２．別に、エジェクターに純水２Ｌ／分を送り込み、無声放電によるオゾン発生器で発生させたオゾン濃度２００ｇ／Ｎｍ 3 のオゾン含有ガス１ＮＬ／分を吸い込ませ、オゾン含有水を調製した。得られたオゾン含有水を純水で希釈して、オゾン濃度ｃｍｇ／Ｌの洗浄水を調製した。
３．表面を指紋の有機物で汚染したシリコンウェーハの指紋の付着面積を顕微鏡観察により測定したのち、温度ｔ℃の洗浄水に１０分間浸漬して洗浄を行い、洗浄後の指紋の付着面積を測定し、洗浄前後の指紋の付着面積から、指紋の除去率を算出した。
（２）オゾン含有水が、純水にオゾンを溶解したのち加温して調製したものである第１項記載の電子材料の洗浄方法、
（３）薬剤を添加して酸化性を向上させたオゾン含有水を用いる第１項又は第２項記載の電子材料の洗浄方法、及び、
（４）周波数２０ｋＨｚ〜３ＭＨｚの超音波を照射しつつ洗浄する第１〜３項のいずれかに記載の電子材料の洗浄方法、
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、
（５）薬剤が、酸又は過酸化水素である第３項記載の電子材料の洗浄方法、
（６）電子材料が、半導体用シリコン基板、液晶用ガラス基板又はフォトマスク用石英基板である第１項記載の電子材料の洗浄方法、
（７）オゾン含有水が、純水を加温して調製したのちオゾンを溶解したものである第１項記載の電子材料の洗浄方法、及び、
（８）オゾン含有水が、純水に高温のオゾン含有ガスを溶解したものである第１項記載の電子材料の洗浄方法、
を挙げることができる。
【０００５】
【発明の実施の形態】
本発明の電子材料の洗浄方法は、オゾン濃度５〜５０mg／Ｌのオゾン含有水を用いて電子材料を洗浄する方法であって、オゾン含有水のオゾン濃度ｃmg／Ｌ、温度ｔ℃としたとき、ｃ＋ｔ≧４５を満たす条件で洗浄する。本発明方法においては、オゾン含有水が、純水にオゾンを溶解したのち加温して調製したものであることが好ましい。本発明方法により、半導体用シリコン基板、液晶用ガラス基板、フォトマスク用石英基板などの表面に付着した有機物を効果的に除去することができる。
本発明方法に用いるオゾン含有水のオゾン濃度は、５〜５０mg／Ｌであり、より好ましくは１５〜４０mg／Ｌである。オゾン含有水のオゾン濃度が５mg／Ｌ未満であると、オゾン含有水の温度を高めても十分な洗浄効果が得られないおそれがある。オゾン含有水のオゾン濃度は５０mg／Ｌ以下で十分な洗浄効果が得られ、５０mg／Ｌを超えるオゾン濃度のオゾン含有水を用いると、経済性が損なわれるおそれがある。
本発明方法においては、オゾン含有水のオゾン濃度ｃmg／Ｌ、温度ｔ℃としたとき、ｃ＋ｔ≧４５、より好ましくはｃ＋ｔ≧５０、さらに好ましくはｃ＋ｔ≧５５を満たす条件で洗浄する。すなわち、オゾン含有水のオゾン濃度が５mg／Ｌのときは、温度４０℃以上、より好ましくは４５℃以上、さらに好ましくは５０℃以上で洗浄し、オゾン含有水のオゾン濃度が４０mg／Ｌのときは、温度５℃以上、より好ましくは１０℃以上、さらに好ましくは１５℃以上で洗浄する。ｃ＋ｔ＜４５であると、洗浄効果が不十分となるおそれがある。
【０００６】
本発明方法において、オゾン含有ガスの製造方法に特に制限はなく、例えば、無声放電によるオゾン製造、水の電気分解によるオゾン製造などを挙げることができる。オゾン含有水の製造方法にも特に制限はなく、例えば、エジェクター、吸引型のガス溶解ポンプ、バブリング装置、気体透過膜装置などを用いてオゾン含有ガスを純水に溶解することにより製造することができる。これらの中で、エジェクターと吸引型のガス溶解ポンプは、オゾン含有ガスを加圧して供給する必要がないので好適に用いることができ、エジェクターは、耐オゾン性に優れた部材による簡単な装置構成が可能なので、特に好適に用いることができる。
本発明方法において、オゾン含有水の製造装置や供給配管などの部材は、酸化性の強いオゾン含有ガスやオゾン含有水と接触するので、十分な耐オゾン性を有する材料で構成することが好ましい。このような材料としては、例えば、ポリテトラフルオロエチレン、テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体などのフッ素樹脂、表面を不動態化した金属、石英などの不活性材料で表面をコートした材料などを挙げることができる。
本発明方法においては、周波数２０kHz〜３MHz、より好ましくは周波数４００kHz〜３MHzの超音波を照射しつつ洗浄することができる。超音波を照射する方法に特に制限はなく、例えば、バッチ洗浄においては、オゾン含有水を貯留した槽に超音波の振動を伝達することができ、また、枚葉式スピン洗浄においては、電子材料に注ぎかけるオゾン含有水に、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。オゾン含有水に超音波を照射することにより、電子材料の表面に損傷を与えることなく、洗浄効果を高めることができる。超音波の周波数が２０kHz未満であると、洗浄効果の向上が不十分となるおそれがある。超音波の周波数が３MHzを超えると、周波数の増大に見合う洗浄効果の向上は期待できない。
【０００７】
本発明方法においては、オゾン含有水に薬剤を添加して酸化性を向上させることができる。添加する薬剤としては、例えば、塩酸、硫酸、硝酸、炭酸などの酸や、過酸化水素などを挙げることができる。オゾン含有水に薬剤を添加して酸化性を向上させることにより、オゾン含有水の有機物除去効果をさらに高めることができる。
本発明方法において、加温されたオゾン含有水を調製する方法に特に制限はなく、例えば、純水にオゾン含有ガスを溶解してオゾン含有水としたのち加温することができ、純水を加温したのちオゾン含有ガスを溶解することもでき、あるいは、純水に加温されたオゾン含有ガスを溶解することもできる。図１は、加温されたオゾン含有水を調製する三態様の説明図である。図１(ａ)に示す態様においては、オゾン発生器１において発生したオゾン含有ガスが、オゾン溶解部２において純水に溶解されたのち、加温部３において加温され、加温されたオゾン含有水の温度は温度計４により管理される。図１(ｂ)に示す態様においては、純水が加温部３において加温されたのち、オゾン発生器１において発生したオゾン含有ガスがオゾン溶解部２において溶解され、加温されたオゾン含有水の温度は温度計４により管理される。図１(ｃ)に示す態様においては、オゾン発生器１において発生したオゾン含有ガスが加温部３において加温されたのち、オゾン溶解部２において純水に溶解されて加温されたオゾン含有水となり、その温度は温度計４により管理される。加温部の構造に特に制限はなく、例えば、熱交換器、ヒーターなどを用いることができる。
【０００８】
これらの中で、図１(ａ)に示す態様は、オゾン溶解部から洗浄装置までの距離が長い場合であっても、洗浄装置の近傍に加温部を設置することができ、配管全体を保温処理する必要がないので、好適に用いることができる。また、加温されたオゾン含有水で有機物を除去する洗浄工程と、加温されていないオゾン含有水を使用する酸化工程などがあっても、オゾン溶解部１台で複数の工程にオゾン含有水を供給することができる。さらに、洗浄装置に近い位置で加温することにより、図１(ｂ)及び図１(ｃ)に示す態様に比べ、低い温度の加温で洗浄装置に同じ温度のオゾン含有水を供給することができる。
本発明方法においては、加温されたオゾン含有水による洗浄効果を高めるために、必要に応じて、オゾン含有水に高純度の試薬を添加することができる。添加する高純度の試薬としては、例えば、塩酸や界面活性剤などを挙げることができる。オゾン含有水に高純度の試薬を添加する位置に特に制限はなく、オゾン含有ガスの溶解前又は溶解後のいずれでもよく、また、水の加温前又は加温後のいずれでもよい。
本発明の電子材料の洗浄方法によれば、簡単な加温装置を設けて、オゾン含有水の温度を僅かに上げることにより、オゾン含有水の洗浄効果を顕著に高めることができる。これにより、使用するオゾン含有水のオゾン濃度を低減することができ、高濃度のオゾン含有ガスを発生させるための高価なオゾン発生器の使用効率を高め、また、発生する廃液を容易に処理することができる。
【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及び比較例１
直径６インチのシリコンウェーハに指を押しつけることにより、表面を指紋の有機物で汚染したシリコンウェーハを調製し、バッチ洗浄試験を行った。
エジェクターに純水２Ｌ／分を送り込み、無声放電によるオゾン発生器で発生させたオゾン濃度２００ｇ／Ｎｍ3のオゾン含有ガス１ＮＬ／分を吸い込ませ、オゾン含有水を調製した。得られたオゾン含有水を純水で希釈して、オゾン濃度１、５、１５、２０、４０、５０mg／Ｌとしたオゾン含有水を調製し、純水とともに洗浄水として用いた。
汚染シリコンウェーハの指紋の付着面積を顕微鏡観察により測定したのち、温度２０、２５、３０、３５、４０、５０℃の洗浄水に１０分間浸漬して洗浄を行い、洗浄後の指紋の付着面積を測定し、洗浄前後の指紋の付着面積から、指紋の除去率を算出した。結果を、第１表に示す。
【００１０】
【表１】
【表２】
第１表に見られるように、洗浄水のオゾン濃度が１mg／Ｌの場合は、ｃ＋ｔが４５以上であっても、指紋除去率は５０％に達しない。洗浄水のオゾン濃度が５〜５０mg／Ｌの場合は、ｃ＋ｔが４５以上であると、指紋除去率は８０％以上となり、良好な洗浄効果が発現する。
実施例２及び比較例２
実施例１と同様にして、指紋の有機物で汚染したシリコンウェーハを作製し、枚葉式スピン洗浄試験を行った。
オゾン濃度１５mg／Ｌのオゾン含有水を洗浄水とし、温度２５、３０、３５、４０℃で、枚葉式スピン洗浄装置を用いて洗浄した。メガソニックノズル［本多電子(株)、パルスジェット］より周波数１MHzの超音波を照射しつつ、ウェーハを５００rpmで回転させながら、洗浄液ノズルをウェーハ中央からエッジの間１往復１０秒でスイングさせ、洗浄水を２５mL／秒の流量で注ぎかけ、６０秒間洗浄を行った。
実施例１と同様にして、洗浄前後の指紋の付着面積を測定し、指紋の除去率を算出した。結果を、第２表に示す。
【００１３】
【表３】
第２表に見られるように、オゾン濃度１５mg／Ｌのオゾン含有水を用いて枚葉式スピン洗浄を行ったとき、ｃ＋ｔが４５未満であると、指紋除去率は８０％に達しないが、ｃ＋ｔが４５以上であると、指紋除去率は８０％以上となり、良好な洗浄効果が発現する。
実施例３
シリコンウェーハの代わりにガラス製レンズを用い、実施例１と同様にして、指を押しつけることにより表面を指紋の有機物で汚染し、オゾン濃度１５mg／Ｌのオゾン含有水に２５、４０℃で、オゾン濃度２０mg／Ｌのオゾン含有水に２０、３０℃で、それぞれ１０分間浸漬して洗浄し、洗浄前後の指紋の付着面積から、指紋の除去率を算出した。結果を、第３表に示す。
【００１５】
【表４】
第３表に見られるように、シリコンウェーハ以外の材料に対しても、オゾン含有水を室温でそのまま洗浄水として用いた場合より、水温を僅かに高めた方が低いオゾン濃度で同等の洗浄効果を示すことが分かる。
【００１７】
【発明の効果】
本発明の電子材料の洗浄方法によれば、簡単な加温装置を設けて、オゾン含有水の温度を僅かに上げることにより、オゾン含有水の洗浄効果を顕著に高めることができる。これにより、使用するオゾン含有水のオゾン濃度を低減することができ、高濃度のオゾン含有ガスを発生させるための高価なオゾン発生器の使用効率を高め、また、発生する廃液を容易に処理することができる。
【図面の簡単な説明】
【図１】図１は、加温されたオゾン含有水を調製する三態様の説明図である。
【符号の説明】
１ オゾン発生器
２ オゾン溶解部
３ 加温部
４ 温度計[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for cleaning an electronic material. More specifically, the present invention relates to an electronic material cleaning method capable of obtaining a high cleaning effect using low concentration ozone-containing water.
[0002]
[Prior art]
Organic substances adhering to silicon substrates for semiconductors, glass substrates for liquid crystals, quartz substrates for photomasks, etc., conventionally contain a rich mixed chemical solution of sulfuric acid and hydrogen peroxide, which is called SPM, and high concentrations of ozone of 50 mg / L or more. It was cleaned by washing with water. SPM cleaning is an effective method for removing strongly adhering organic substances and metals such as resist on the semiconductor surface. However, in order to use a large amount of high-concentration acid and hydrogen peroxide, The chemicals are discharged, and a large burden is imposed on neutralization and precipitation in waste liquid treatment, and a large amount of sludge is generated. That is, in order to ensure the cleanliness of the surface of a semiconductor substrate or the like, a great deal of cost has been required for chemicals and waste liquid treatment. In recent years, washing with ozone-containing water that does not use a concentrated chemical solution has begun to spread. However, in order to remove organic substances that adhere firmly, ozone-containing water with a high concentration of 50 to 100 mg / L is required. To do. In order to prepare high-concentration ozone-containing water, it is necessary to produce a large amount of high-concentration ozone-containing gas. For that purpose, an expensive ozone generator is required, which increases the manufacturing cost and damages the materials of the washing machine, piping, etc., so it needs frequent maintenance, and high-concentration ozone-containing gas is There are problems such as being harmful and needing care in handling. In view of the above, various new cleaning methods are being tried in recent years.
[0003]
[Problems to be solved by the invention]
The present invention has been made for the purpose of providing a method for cleaning an electronic material capable of obtaining a high cleaning effect using low-concentration ozone-containing water.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventors have drastically improved the cleaning effect by slightly warming the low-concentration ozone-containing water used for cleaning electronic materials to room temperature or higher. It was found that an organic substance removal effect comparable to that of high-concentration ozone water was obtained using low-concentration ozone-containing water, and the present invention was completed based on this finding.
That is, the present invention
(1) A method of removing organic substances adhering to the surface of an electronic material by washing using ozone-containing water having an ozone concentration of 15 to 50 mg / L and a temperature of 20 ° C. or more, wherein the ozone concentration of the ozone-containing water is cmg / L, When the temperature is set to t ° C., cleaning is performed under conditions satisfying 100 ≧ c + t> 45, thereby removing attached organic matter corresponding to a fingerprint removal rate of 80% or more in terms of the fingerprint removal rate in the following fingerprint removal rate measurement test. A method for cleaning electronic materials,
Fingerprint removal rate measurement test:
1. By pressing a finger against a 6-inch diameter silicon wafer, a silicon wafer having a surface contaminated with organic fingerprints was prepared.
2. Separately, 2 L / min of pure water was sent to the ejector, and ozone-containing gas 1 NL / min with an ozone concentration of 200 g / Nm 3 generated by an ozone generator by silent discharge was sucked in to prepare ozone-containing water. The obtained ozone-containing water was diluted with pure water to prepare washing water having an ozone concentration of cmg / L.
3. After measuring the adhesion area of the fingerprint of the silicon wafer whose surface is contaminated with organic fingerprints by microscopic observation, immersing it in cleaning water at a temperature of t ° C. for 10 minutes and measuring the adhesion area of the fingerprint after cleaning, The fingerprint removal rate was calculated from the fingerprint adhesion area before and after washing.
(2) The method for cleaning an electronic material according to item 1, wherein the ozone-containing water is prepared by dissolving ozone in pure water and then heating.
(3) The method for cleaning an electronic material according to
(4) The electronic material cleaning method according to any one of Items 1 to 3, wherein the cleaning is performed while irradiating ultrasonic waves having a frequency of 20 kHz to 3 MHz.
Is to provide.
Furthermore, as a preferred embodiment of the present invention,
(5) The electronic material cleaning method according to
(6) The electronic material cleaning method according to item 1, wherein the electronic material is a semiconductor silicon substrate, a liquid crystal glass substrate or a photomask quartz substrate;
(7) The method for cleaning an electronic material according to Item 1, wherein the ozone-containing water is prepared by heating pure water and then dissolving ozone; and
(8) The method for cleaning an electronic material according to Item 1, wherein the ozone-containing water is obtained by dissolving a high-temperature ozone-containing gas in pure water.
Can be mentioned.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The electronic material cleaning method of the present invention is a method of cleaning an electronic material using ozone-containing water having an ozone concentration of 5 to 50 mg / L, when the ozone concentration of the ozone-containing water is cmg / L and the temperature is t ° C. , And cleaning is performed under conditions that satisfy c + t ≧ 45. In the method of the present invention, the ozone-containing water is preferably prepared by dissolving ozone in pure water and then heating. By the method of the present invention, organic substances adhering to the surface of a semiconductor silicon substrate, a liquid crystal glass substrate, a photomask quartz substrate, and the like can be effectively removed.
The ozone concentration of the ozone-containing water used in the method of the present invention is 5 to 50 mg / L, more preferably 15 to 40 mg / L. If the ozone concentration of the ozone-containing water is less than 5 mg / L, a sufficient cleaning effect may not be obtained even if the temperature of the ozone-containing water is increased. A sufficient cleaning effect is obtained when the ozone concentration of the ozone-containing water is 50 mg / L or less. If ozone-containing water having an ozone concentration exceeding 50 mg / L is used, the economy may be impaired.
In the method of the present invention, when the ozone concentration of the ozone-containing water is cmg / L and the temperature is t ° C., the cleaning is performed under the condition of satisfying c + t ≧ 45, more preferably c + t ≧ 50, and further preferably c + t ≧ 55. That is, when the ozone concentration of ozone-containing water is 5 mg / L, washing is performed at a temperature of 40 ° C. or more, more preferably 45 ° C. or more, and even more preferably 50 ° C. or more. When the ozone concentration of ozone-containing water is 40 mg / L Is washed at a temperature of 5 ° C. or higher, more preferably 10 ° C. or higher, and even more preferably 15 ° C. or higher. If c + t <45, the cleaning effect may be insufficient.
[0006]
In the method of the present invention, the production method of the ozone-containing gas is not particularly limited, and examples thereof include ozone production by silent discharge and ozone production by water electrolysis. There is no particular limitation on the method for producing ozone-containing water, and for example, it can be produced by dissolving ozone-containing gas in pure water using an ejector, a suction-type gas dissolution pump, a bubbling device, a gas permeable membrane device, or the like. it can. Among these, the ejector and the suction-type gas dissolution pump do not need to pressurize and supply the ozone-containing gas, and thus can be suitably used. The ejector has a simple device configuration with a member excellent in ozone resistance. Can be used particularly preferably.
In the method of the present invention, members such as the ozone-containing water production apparatus and the supply pipe are in contact with highly oxidative ozone-containing gas and ozone-containing water, and are therefore preferably made of a material having sufficient ozone resistance. Such materials include, for example, fluorine resins such as polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, surface passivated metal, quartz Examples thereof include a material whose surface is coated with an inert material.
In the method of the present invention, cleaning can be performed while irradiating ultrasonic waves having a frequency of 20 kHz to 3 MHz, more preferably a frequency of 400 kHz to 3 MHz. There is no particular limitation on the method of irradiating ultrasonic waves. For example, in batch cleaning, ultrasonic vibration can be transmitted to a tank in which ozone-containing water is stored, and in single-wafer spin cleaning, an electronic material is used. The ultrasonic vibration can be transmitted to the ozone-containing water poured into the nozzle portion at the nozzle portion. By irradiating the ozone-containing water with ultrasonic waves, the cleaning effect can be enhanced without damaging the surface of the electronic material. If the ultrasonic frequency is less than 20 kHz, the cleaning effect may not be sufficiently improved. When the frequency of the ultrasonic wave exceeds 3 MHz, an improvement in cleaning effect commensurate with the increase in frequency cannot be expected.
[0007]
In the method of the present invention, an oxidizing agent can be improved by adding a chemical to ozone-containing water. Examples of the agent to be added include acids such as hydrochloric acid, sulfuric acid, nitric acid, and carbonic acid, and hydrogen peroxide. By adding a chemical | medical agent to ozone-containing water and improving oxidation property, the organic substance removal effect of ozone-containing water can further be improved.
In the method of the present invention, there is no particular limitation on the method for preparing the heated ozone-containing water. For example, the ozone-containing gas can be dissolved in pure water to obtain ozone-containing water and heated. The ozone-containing gas can be dissolved after heating, or the ozone-containing gas heated in pure water can be dissolved. Drawing 1 is an explanatory view of three modes which prepare warmed ozone content water. In the embodiment shown in FIG. 1 (a), ozone-containing gas generated in the ozone generator 1 is dissolved in pure water in the
[0008]
Among these, the embodiment shown in FIG. 1 (a) can install a heating unit in the vicinity of the cleaning device even when the distance from the ozone dissolving unit to the cleaning device is long. Since there is no need for heat treatment, it can be suitably used. Moreover, even if there is a washing process that removes organic substances with warmed ozone-containing water and an oxidation process that uses unheated ozone-containing water, ozone-containing water can be added to multiple processes with one ozone dissolution unit. Can be supplied. Furthermore, by heating at a position close to the cleaning device, ozone-containing water having the same temperature is supplied to the cleaning device at a lower temperature than in the embodiment shown in FIGS. 1 (b) and 1 (c). Can do.
In the method of the present invention, a high-purity reagent can be added to the ozone-containing water as necessary in order to enhance the cleaning effect of the heated ozone-containing water. Examples of the high-purity reagent to be added include hydrochloric acid and a surfactant. There is no restriction | limiting in particular in the position which adds a highly purified reagent to ozone-containing water, either before melt | dissolution of ozone-containing gas or after melt | dissolution, and any before or after warming water may be sufficient.
According to the electronic material cleaning method of the present invention, the cleaning effect of ozone-containing water can be remarkably enhanced by providing a simple heating device and slightly raising the temperature of the ozone-containing water. Thereby, the ozone concentration of the ozone-containing water to be used can be reduced, the use efficiency of an expensive ozone generator for generating a high-concentration ozone-containing gas is increased, and the generated waste liquid is easily treated. be able to.
[0009]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Example 1 and Comparative Example 1
By pressing a finger against a 6-inch diameter silicon wafer, a silicon wafer having a surface contaminated with organic fingerprints was prepared, and a batch cleaning test was performed.
Pure water 2 L / min was fed into the ejector, and ozone-containing gas 1 NL / min with an ozone concentration of 200 g / Nm 3 generated by an ozone generator by silent discharge was sucked in to prepare ozone-containing water. The obtained ozone-containing water was diluted with pure water to prepare ozone-containing water having an ozone concentration of 1, 5, 15, 20, 40, 50 mg / L, and used as washing water together with pure water.
After measuring the adhesion area of the fingerprint on the contaminated silicon wafer by microscopic observation, the wafer is immersed in cleaning water at a temperature of 20, 25, 30, 35, 40, and 50 ° C. for 10 minutes for cleaning. Measurement was performed, and the fingerprint removal rate was calculated from the fingerprint adhesion area before and after cleaning. The results are shown in Table 1.
[0010]
[Table 1]
[Table 2]
As seen in Table 1, when the ozone concentration of the cleaning water is 1 mg / L, the fingerprint removal rate does not reach 50% even if c + t is 45 or more. When the ozone concentration of the cleaning water is 5 to 50 mg / L, if c + t is 45 or more, the fingerprint removal rate is 80% or more, and a good cleaning effect is exhibited.
Example 2 and Comparative Example 2
In the same manner as in Example 1, a silicon wafer contaminated with fingerprint organic substances was produced, and a single wafer spin cleaning test was performed.
Washing was performed using ozone-containing water having an ozone concentration of 15 mg / L at a temperature of 25, 30, 35, and 40 ° C. using a single wafer spin cleaning apparatus. While irradiating ultrasonic waves with a frequency of 1 MHz from a megasonic nozzle [Honda Electronics Co., Ltd., Pulse Jet], while rotating the wafer at 500 rpm, the cleaning liquid nozzle is swung from the wafer center to the edge in one round and 10 seconds, Washing water was poured at a flow rate of 25 mL / second, and washing was performed for 60 seconds.
In the same manner as in Example 1, the adhesion area of the fingerprint before and after cleaning was measured, and the fingerprint removal rate was calculated. The results are shown in Table 2.
[0013]
[Table 3]
As seen in Table 2, when single-wafer spin cleaning is performed using ozone-containing water having an ozone concentration of 15 mg / L, if c + t is less than 45, the fingerprint removal rate does not reach 80%. When c + t is 45 or more, the fingerprint removal rate is 80% or more, and a good cleaning effect is exhibited.
Example 3
A glass lens is used instead of a silicon wafer, and the surface is contaminated with fingerprint organic matter by pressing a finger in the same manner as in Example 1, and ozone is contained in ozone-containing water having an ozone concentration of 15 mg / L at 25 and 40 ° C. It was immersed in ozone-containing water with a concentration of 20 mg / L at 20 and 30 ° C. for 10 minutes for cleaning, and the fingerprint removal rate was calculated from the fingerprint adhesion area before and after cleaning. The results are shown in Table 3.
[0015]
[Table 4]
As can be seen in Table 3, even for materials other than silicon wafers, the same cleaning effect can be obtained at a lower ozone concentration when the water temperature is slightly increased than when ozone-containing water is used as cleaning water at room temperature. It can be seen that
[0017]
【The invention's effect】
According to the electronic material cleaning method of the present invention, the cleaning effect of ozone-containing water can be remarkably enhanced by providing a simple heating device and slightly raising the temperature of the ozone-containing water. Thereby, the ozone concentration of the ozone-containing water to be used can be reduced, the use efficiency of an expensive ozone generator for generating a high-concentration ozone-containing gas is increased, and the generated waste liquid is easily treated. be able to.
[Brief description of the drawings]
FIG. 1 is an explanatory view of three modes for preparing warm ozone-containing water.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1
Claims (4)
指紋除去率測定試験：
１．直径６インチのシリコンウェーハに指を押しつけることにより、表面を指紋の有機物で汚染したシリコンウェーハを調製した。
２．別に、エジェクターに純水２Ｌ／分を送り込み、無声放電によるオゾン発生器で発生させたオゾン濃度２００ｇ／Ｎｍ 3 のオゾン含有ガス１ＮＬ／分を吸い込ませ、オゾン含有水を調製した。得られたオゾン含有水を純水で希釈して、オゾン濃度ｃｍｇ／Ｌの洗浄水を調製した。
３．表面を指紋の有機物で汚染したシリコンウェーハの指紋の付着面積を顕微鏡観察により測定したのち、温度ｔ℃の洗浄水に１０分間浸漬して洗浄を行い、洗浄後の指紋の付着面積を測定し、洗浄前後の指紋の付着面積から、指紋の除去率を算出した。 A method of removing organic substances adhering to the surface of an electronic material by using ozone-containing water having an ozone concentration of 15 to 50 mg / L and a temperature of 20 ° C. or more, wherein the ozone concentration of the ozone-containing water is cmg / L and the temperature is t ° C. In this case, by cleaning under the condition satisfying 100 ≧ c + t> 45 , organic substances corresponding to a fingerprint removal rate of 80% or more in terms of fingerprint removal rate in the following fingerprint removal rate measurement test are removed. A method for cleaning an electronic material.
Fingerprint removal rate measurement test:
1. By pressing a finger against a 6-inch diameter silicon wafer, a silicon wafer having a surface contaminated with organic fingerprints was prepared.
2. Separately, 2 L / min of pure water was sent to the ejector, and ozone-containing gas 1 NL / min with an ozone concentration of 200 g / Nm 3 generated by an ozone generator by silent discharge was sucked in to prepare ozone-containing water. The obtained ozone-containing water was diluted with pure water to prepare washing water having an ozone concentration of cmg / L.
3. After measuring the adhesion area of the fingerprint of the silicon wafer whose surface is contaminated with organic fingerprints by microscopic observation, immersing it in cleaning water at a temperature of t ° C. for 10 minutes to measure the adhesion area of the fingerprint after cleaning, The fingerprint removal rate was calculated from the fingerprint adhesion area before and after washing.
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| JP4919388B2 (en) * | 2006-03-09 | 2012-04-18 | 国立大学法人広島大学 | Cleaning apparatus and method for cleaning an object to be cleaned in a food production facility |
| TW200802575A (en) * | 2006-03-20 | 2008-01-01 | Eiji Matsumura | Substrate cleaning method and substrate cleaning apparatus |
| TWI448551B (en) | 2008-02-15 | 2014-08-11 | Lion Corp | Detergent composition and washing method of substrate for electronic device |
| JP6062712B2 (en) * | 2012-10-30 | 2017-01-18 | 三菱電機株式会社 | Solar cell manufacturing method and solar cell manufacturing apparatus used therefor |
| CN116313748A (en) * | 2023-03-28 | 2023-06-23 | 通威太阳能(眉山)有限公司 | Polysilicon removing method, cleaning liquid and polysilicon removing system |
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| JP2000290693A (en) * | 1999-04-12 | 2000-10-17 | Japan Organo Co Ltd | Cleaning of electronic parts and members |
| JP2000331979A (en) * | 1999-05-21 | 2000-11-30 | Dainippon Screen Mfg Co Ltd | Device and method for treating substrate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2000290693A (en) * | 1999-04-12 | 2000-10-17 | Japan Organo Co Ltd | Cleaning of electronic parts and members |
| JP2000331979A (en) * | 1999-05-21 | 2000-11-30 | Dainippon Screen Mfg Co Ltd | Device and method for treating substrate |
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