JP2007311411A - Method of cleaning inside of cleaning apparatus - Google Patents
Method of cleaning inside of cleaning apparatus Download PDFInfo
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- JP2007311411A JP2007311411A JP2006136617A JP2006136617A JP2007311411A JP 2007311411 A JP2007311411 A JP 2007311411A JP 2006136617 A JP2006136617 A JP 2006136617A JP 2006136617 A JP2006136617 A JP 2006136617A JP 2007311411 A JP2007311411 A JP 2007311411A
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本発明は、高圧流体洗浄用装置内部の洗浄方法に関するものである。 The present invention relates to a method for cleaning the inside of a high-pressure fluid cleaning apparatus.
半導体回路の微細化に伴い、超臨界流体を始めとした高圧流体を用いて半導体集積回路上のフォトレジストを除去する方法が提案されている。これは流体の粘度が低く、微細パターン内部の洗浄が可能であるためである。超臨界流体のような高圧流体としては温和な条件で超臨界状態となるため、二酸化炭素が広く用いられている。 Along with miniaturization of semiconductor circuits, a method for removing photoresist on a semiconductor integrated circuit using a high-pressure fluid such as a supercritical fluid has been proposed. This is because the fluid has a low viscosity and the inside of the fine pattern can be cleaned. Carbon dioxide is widely used as a high-pressure fluid such as a supercritical fluid because it becomes supercritical under mild conditions.
ところが、超臨界二酸化炭素（以下「ｓｃＣＯ２」と略記する）は、ヘキサンなどの無極性溶媒と同程度の極性のため、レジストやその残渣を十分に除去できなかった。そこでアルキルアミン類、有機溶剤、フッ化物などをｓｃＣＯ２と併用する方法が提案されている。（例えば、特許文献１参照） However, supercritical carbon dioxide (hereinafter abbreviated as “scCO 2 ”) has the same degree of polarity as a non-polar solvent such as hexane, and thus the resist and its residue could not be removed sufficiently. Therefore, a method of using alkylamines, organic solvents, fluorides and the like in combination with scCO 2 has been proposed. (For example, see Patent Document 1)
一方、これら剥離用の組成物とｓｃＣＯ２を併用すると、薬液成分が装置内部隅々までいきわたるため、薬液成分が装置内部に残存しやすく、除去するのが困難であった。特に装置内部の金属に付着したアミン類、フッ化物は除去困難であり、流水などによる通常の方法では薬液がいきわたらず、洗浄が不十分であった。また、ｓｃＣＯ２による装置内部の洗浄も提案されているが（例えば、特許文献２参照）、ｓｃＣＯ２による洗浄のみではアミン類、フッ化物の除去が十分ではなかった。 On the other hand, when these stripping compositions and scCO 2 are used in combination, the chemical component spreads throughout the device, so that the chemical component tends to remain inside the device and is difficult to remove. In particular, amines and fluorides adhering to the metal inside the apparatus are difficult to remove, and the usual method using running water or the like did not allow chemicals to flow, and cleaning was insufficient. Further, although cleaning of the inside of the apparatus with scCO 2 has been proposed (see, for example, Patent Document 2), removal of amines and fluorides has not been sufficient only by cleaning with scCO 2 .
そこで、装置内部を汚染する薬液成分、特にアミン類、フッ化物を洗浄除去するための洗浄方法が求められていた。 Therefore, there has been a demand for a cleaning method for cleaning and removing chemical components that contaminate the inside of the apparatus, particularly amines and fluorides.
本発明の目的は、上記課題に鑑み、高圧流体洗浄用装置内部を洗浄する方法を提供することにある。 In view of the above problems, an object of the present invention is to provide a method for cleaning the inside of a high-pressure fluid cleaning apparatus.
本発明者らは、上記課題について鋭意検討した結果、硫酸及び有機溶媒を含んでなる洗浄液をｓｃＣＯ２と併せ用いた場合、装置内部の至る所に残存する薬液成分の洗浄に極めて優れていることを見出し、本発明を完成させるに至った。 As a result of intensive studies on the above problems, the present inventors have found that when a cleaning liquid containing sulfuric acid and an organic solvent is used together with scCO 2 , it is extremely excellent in cleaning chemical components remaining throughout the apparatus. As a result, the present invention has been completed.
すなわち本発明は、高圧流体洗浄用装置内部に付着したアミン類及びフッ化物の洗浄方法において、硫酸、有機溶媒及び超臨界二酸化炭素からなる洗浄液を用いて洗浄することを特徴とする洗浄装置内部の洗浄方法に関するものである。 That is, the present invention provides a method for cleaning amines and fluorides adhering to the inside of a high-pressure fluid cleaning apparatus, wherein cleaning is performed using a cleaning liquid comprising sulfuric acid, an organic solvent, and supercritical carbon dioxide. The present invention relates to a cleaning method.
以下に、本発明をさらに詳細に説明する。 The present invention is described in further detail below.
本発明の洗浄方法に用いる洗浄液は、硫酸、有機溶媒及び超臨界二酸化炭素からなるものである。 The cleaning liquid used in the cleaning method of the present invention is composed of sulfuric acid, an organic solvent, and supercritical carbon dioxide.
本発明の洗浄液に使用する有機溶媒は、ｓｃＣＯ２との相溶性及び洗浄性の観点から、アセトニトリル、プロピオニトリル、スクシノニトリル、ブチロニトリル、ベンゾニトリル、アジポニトリル、メタノール、エタノール、プロパノール、ブタノール、ペンタノール、ヘキサノール、シクロヘキサノール、ベンジルアルコール、エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、トリプロピレングリコール、メトキシエタノール、エトキシエタノール、プロポキシエタノール、ブトキシエタノール、ブトキシエトキシエタノール、メトキシプロパノール、エトキシプロパノール、プロポキシプロパノール、ブトキシプロパノール、ギ酸メチル、ギ酸エチル、酢酸メチル、酢酸エチル、プロピオン酸メチル、プロピオン酸エチル、炭酸エチレン、炭酸プロピレン、炭酸ジメチル、炭酸ジエチル、アセトン、メチルエチルケトン、２−ペンタノン、３−ペンタノン、２−ヘキサノン、メチルイソブチルケトン、２−ヘプタノン、４−ヘプタノン、ジイソブチルケトン、アセトニルアセトン、イソホロン、シクロヘキサノンなどが挙げられる。これらのうち、アセトニトリル、メタノール、エタノールが好ましい。これらは単独で使用しても良いが、２種以上を混合して使用しても良い。これらの有機溶媒は洗浄を促進する。 The organic solvent used in the cleaning liquid of the present invention includes acetonitrile, propionitrile, succinonitrile, butyronitrile, benzonitrile, adiponitrile, methanol, ethanol, propanol, butanol, pen from the viewpoint of compatibility with scCO 2 and cleaning properties. Tanol, hexanol, cyclohexanol, benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, methoxyethanol, ethoxyethanol, propoxyethanol, butoxyethanol, butoxyethoxyethanol, methoxypropanol, ethoxy Propanol, propoxypropanol, butoxypropanol, methyl formate, ethyl formate, methyl acetate , Ethyl acetate, methyl propionate, ethyl propionate, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone, 2-heptanone, 4 -Heptanone, diisobutyl ketone, acetonyl acetone, isophorone, cyclohexanone and the like. Of these, acetonitrile, methanol, and ethanol are preferred. These may be used alone or in combination of two or more. These organic solvents facilitate cleaning.
また、本発明の洗浄液には水を添加しても良い。水は洗浄を促進する効果がある。水は、特にアミン類の洗浄に有効である。水の添加量には特に制限はないが、洗浄液全体に対し、３０重量％以下が好ましい。３０重量％を超える水を添加すると超臨界二酸化炭素と洗浄液の相溶性が悪くなり、洗浄効果が小さくなる。 Further, water may be added to the cleaning liquid of the present invention. Water has the effect of promoting cleaning. Water is particularly effective for cleaning amines. Although there is no restriction | limiting in particular in the addition amount of water, 30 weight% or less is preferable with respect to the whole washing | cleaning liquid. When water exceeding 30% by weight is added, the compatibility between the supercritical carbon dioxide and the cleaning liquid is deteriorated, and the cleaning effect is reduced.
本発明の洗浄液には硫酸を用いる。硫酸は装置内壁や配管の金属に付着した薬液成分を分解すると共に、フッ化物の除去を促進する効果がある。本発明の洗浄液に使用する硫酸には特に制限はなく、濃硫酸、希硫酸、発煙硫酸など問題なく使用することができ、一般に工業的に流通している硫酸を使用することができる。 Sulfuric acid is used in the cleaning liquid of the present invention. Sulfuric acid has an effect of decomposing chemical components adhering to the inner wall of the apparatus and piping and promoting the removal of fluoride. There is no restriction | limiting in particular in the sulfuric acid used for the washing | cleaning liquid of this invention, Concentrated sulfuric acid, dilute sulfuric acid, fuming sulfuric acid, etc. can be used without problems, and generally the sulfuric acid currently distribute | circulated industrially can be used.
本発明の洗浄液において、硫酸濃度は１０重量％以下が好ましく、５重量％以下が特に好ましい。硫酸が１０重量％を越えると有機溶媒と反応する危険性が高い。 In the cleaning liquid of the present invention, the sulfuric acid concentration is preferably 10% by weight or less, particularly preferably 5% by weight or less. When sulfuric acid exceeds 10% by weight, there is a high risk of reacting with an organic solvent.
洗浄時のｓｃＣＯ２の圧力は５〜２０ＭＰａ、特に１０〜２０ＭＰａであることが好ましい。 The pressure of scCO 2 at the time of washing is preferably 5 to 20 MPa, particularly 10 to 20 MPa.
また、本発明の方法における洗浄温度は、３１℃以上が好ましい。一方、温度を高くすればするほど圧力が高くなり、洗浄装置が高価になるため、２００℃以下とするのが好ましい。いずれの場合においても、洗浄液の圧力が１〜２０ＭＰａ、特に好ましくは１０〜２０ＭＰａとなる温度を選択することが好ましい。 The washing temperature in the method of the present invention is preferably 31 ° C. or higher. On the other hand, the higher the temperature, the higher the pressure and the more expensive the cleaning device. In any case, it is preferable to select a temperature at which the pressure of the cleaning liquid is 1 to 20 MPa, particularly preferably 10 to 20 MPa.
本発明の洗浄液は、高圧流体洗浄用装置内に付着した汚染物を洗浄するのに使用する。洗浄対象の汚染物としては、アミン類などの有機物、フッ化物などの酸、塩が挙げられる。洗浄されるアミン類、フッ化物に特に制限はなく、一般の薬液に含まれるものであれば、本発明の洗浄方法により除去することが可能である。 The cleaning liquid of the present invention is used for cleaning contaminants adhering to the high-pressure fluid cleaning apparatus. Examples of contaminants to be cleaned include organic substances such as amines, acids and salts such as fluorides, and the like. The amines and fluorides to be washed are not particularly limited, and can be removed by the washing method of the present invention as long as they are contained in a general chemical solution.
本発明の洗浄方法によれば、薬液成分によって汚染された装置内部を速やかに残渣なく洗浄除去することができる。 According to the cleaning method of the present invention, the inside of the apparatus contaminated with chemical liquid components can be quickly cleaned and removed without residue.
本発明を以下の実施例によりさらに詳細に説明するが、本発明はこれらに限定されるものではない。なお、表記を簡潔にするため、以下の略記号を使用した。
ＡｃＣＮ：アセトニトリル
ＥｔＯＨ：エタノール
ＭｅＯＨ：メタノール
Ｈ２Ｏ：水
実施例１〜５、比較例１〜３
薬液中にステンレス片（ＳＵＳ３１６Ｌ）を７０℃で１時間浸漬し、ステンレス上に薬液を付着させた。このステンレス片を耐圧容器に入れ、表１に示す洗浄液及び二酸化炭素（炭酸ガス）を容器に導入した（除去用洗浄液濃度は二酸化炭素の３０重量％とした）。７０℃に加熱し、圧力を１５ＭＰａとして二酸化炭素を超臨界状態にした。所定時間維持した後、冷却しステンレス片を取り出し、乾燥した。表面をＸＰＳ（Ｘ線光電子分光法）で観察し、ステンレス表面の薬液成分の洗浄状況を調べた。なお、ＸＰＳは島津製作所製ＥＳＣＡ−３４００を用いた。 薬液の洗浄状態は、以下の様に評価した。
○：除去性良好
×：大部分残存
各洗浄液のｓｃＣＯ２への溶解性は、以下の様に評価した。
○：溶解
×：不溶
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. In order to simplify the notation, the following abbreviations were used.
AcCN: acetonitrile EtOH: ethanol MeOH: methanol H 2 O: water Examples 1-5, Comparative Examples 1-3
A piece of stainless steel (SUS316L) was immersed in the chemical solution at 70 ° C. for 1 hour, and the chemical solution was adhered onto the stainless steel. This stainless steel piece was put into a pressure vessel, and the cleaning liquid and carbon dioxide (carbon dioxide gas) shown in Table 1 were introduced into the container (the concentration of the cleaning liquid for removal was 30% by weight of carbon dioxide). It heated to 70 degreeC, the pressure was set to 15 Mpa, and the carbon dioxide was made into the supercritical state. After maintaining for a predetermined time, it was cooled and the stainless steel piece was taken out and dried. The surface was observed by XPS (X-ray photoelectron spectroscopy), and the cleaning condition of the chemical component on the stainless steel surface was examined. As XPS, ESCA-3400 manufactured by Shimadzu Corporation was used. The cleaning state of the chemical solution was evaluated as follows.
○: Good removability x: Most of remaining The solubility of each cleaning solution in scCO 2 was evaluated as follows.
○: dissolved ×: insoluble
本発明の除去用洗浄液は、汚染物の除去性、ｓｃＣＯ２溶解性に優れていたが、比較例の洗浄液は汚染物の除去性が不十分であった。 The cleaning solution for removal of the present invention was excellent in contaminant removal and scCO 2 solubility, but the cleaning solution of the comparative example was insufficient in contaminant removal.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006136617A JP2007311411A (en) | 2006-05-16 | 2006-05-16 | Method of cleaning inside of cleaning apparatus |
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| Application Number | Priority Date | Filing Date | Title |
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| JP2006136617A JP2007311411A (en) | 2006-05-16 | 2006-05-16 | Method of cleaning inside of cleaning apparatus |
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| JP2007311411A true JP2007311411A (en) | 2007-11-29 |
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| JP2006136617A Withdrawn JP2007311411A (en) | 2006-05-16 | 2006-05-16 | Method of cleaning inside of cleaning apparatus |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021044457A (en) * | 2019-09-12 | 2021-03-18 | 東京エレクトロン株式会社 | Cleaning method of substrate processing apparatus and substrate processing system |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021044457A (en) * | 2019-09-12 | 2021-03-18 | 東京エレクトロン株式会社 | Cleaning method of substrate processing apparatus and substrate processing system |
| JP7394563B2 (en) | 2019-09-12 | 2023-12-08 | 東京エレクトロン株式会社 | Cleaning method for substrate processing equipment and substrate processing system |
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| A300 | Withdrawal of application because of no request for examination |
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