JP2008084884A - Composition for cleaning semiconductor manufacturing apparatus and cleaning method employing the same - Google Patents
Composition for cleaning semiconductor manufacturing apparatus and cleaning method employing the same Download PDFInfo
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Abstract
Description
本発明は、半導体製造装置洗浄用組成物及びそれを用いた洗浄方法に関するものであり、特にプロセスチャンバー等の陽極酸化されたアルミニウム基材表面に付着した物質を除去する洗浄用組成物及びそれを用いた洗浄方法に関するものである。 The present invention relates to a semiconductor manufacturing apparatus cleaning composition and a cleaning method using the same, and in particular, a cleaning composition for removing substances adhering to an anodized aluminum substrate surface such as a process chamber and the like. It relates to the cleaning method used.
半導体製造工程では、ＣＶＤによる成膜工程やプラズマによるエッチング工程等さまざまなプロセスから成っているが、それらのうち、例えば、エッチング工程ではプロセスチャンバー内にプラズマを生成させウエハ上の不要部分をエッチングをする。このようなエッチング工程ではエッチング中に飛び散った物質が陽極酸化されたプロセスチャンバーの内壁表面に付着する。このため、多くのウエハを処理する過程で、プロセスチャンバー上に堆積した付着物の厚みは増し、これが剥がれ落ちてパーティクル発生の原因となる。 In the semiconductor manufacturing process, it consists of various processes such as a CVD film forming process and a plasma etching process. Among these processes, for example, in the etching process, plasma is generated in the process chamber to etch unnecessary portions on the wafer. To do. In such an etching process, substances scattered during etching adhere to the inner wall surface of the anodized process chamber. For this reason, in the process of processing many wafers, the thickness of the deposits deposited on the process chamber increases, which peels off and causes generation of particles.
したがって、プロセスチャンバー上に堆積した付着物を定期的に除去することが必要になるが、陽極酸化されたプロセスチャンバーは、酸、アルカリに弱く、非常に腐食しやすいため、化学的な薬液による洗浄ができなかった。 Therefore, it is necessary to periodically remove deposits deposited on the process chamber, but the anodized process chamber is sensitive to acids and alkalis, and is very corrosive. I could not.
従来は、陽極酸化されたプロセスチャンバー表面をイソプロピルアルコールや、水を濡らした布等で拭き取ったり、研磨具等でこすり落とすことにより、このような付着物を除去していた。しかしながら、これらの方法では付着物を十分に取り除くことができず、研磨具等を使用すると陽極酸化された表面にダメージを与えてしまうこともあった。 Conventionally, such deposits have been removed by wiping the anodized process chamber surface with isopropyl alcohol, a cloth wetted with water, or by rubbing it with a polishing tool or the like. However, these methods cannot sufficiently remove deposits, and when an abrasive tool or the like is used, the anodized surface may be damaged.
一方、このような物理的な除去方法に加え、加熱状態の過酸化水素により付着物を除去する方法が知られている（例えば、特許文献１参照）。この方法によれば、陽極酸化されたプロセスチャンバー表面にダメージを与えることはないが、付着物は十分に除去することができなかった。 On the other hand, in addition to such a physical removal method, a method of removing deposits with hydrogen peroxide in a heated state is known (for example, see Patent Document 1). According to this method, the surface of the anodized process chamber is not damaged, but deposits cannot be sufficiently removed.
本発明は上記の背景技術に鑑みてなされたものであり、その目的は、半導体製造装置、特に陽極酸化されたアルミニウム基材表面にダメージを与えず、それに堆積した付着物を選択的に除去することのできる洗浄用組成物及びそれを用いた洗浄方法を提供することにある。 The present invention has been made in view of the above-described background art, and an object of the present invention is to selectively remove deposits deposited thereon without damaging the surface of a semiconductor manufacturing apparatus, particularly an anodized aluminum substrate. An object of the present invention is to provide a cleaning composition capable of cleaning and a cleaning method using the same.
本発明者らは、半導体製造装置基材表面に堆積した付着物除去について鋭意検討した結果、フッ化物、及びクエン酸を含んでなる組成物が、半導体製造装置、特に陽極酸化された基材にダメージを与えることなく堆積した付着物を選択的に除去できることを見出し、本発明を完成させるに至った。 As a result of intensive studies on the removal of deposits deposited on the surface of a semiconductor manufacturing apparatus substrate, the present inventors have found that a composition comprising fluoride and citric acid is applied to a semiconductor manufacturing apparatus, particularly an anodized substrate. It has been found that the deposited deposits can be selectively removed without causing damage, and the present invention has been completed.
すなわち、本発明は、以下に示すとおりの半導体製造装置洗浄用組成物及びそれを用いた洗浄方法である。 That is, this invention is a semiconductor manufacturing apparatus cleaning composition as shown below, and a cleaning method using the same.
（１）フッ化ナトリウム、フッ化カリウム、フッ化リチウム及びフッ化アンモニウムからなる群より選ばれる一種又は二種以上のフッ化物とクエン酸を含む半導体製造装置洗浄用組成物。 (1) A composition for cleaning a semiconductor manufacturing apparatus, comprising one or more fluorides selected from the group consisting of sodium fluoride, potassium fluoride, lithium fluoride and ammonium fluoride and citric acid.
（２）フッ化物を１〜１００００ｐｐｍ、及びクエン酸を０．１〜２０重量％含むことを特徴とする上記（１）に記載の半導体製造装置洗浄用組成物。 (2) The composition for cleaning a semiconductor manufacturing apparatus according to the above (1), comprising 1 to 10,000 ppm of fluoride and 0.1 to 20% by weight of citric acid.
（３）さらにｐＨ調整剤を含むことを特徴とする上記（１）又は（２）に記載の半導体製造装置洗浄用組成物。 (3) The composition for cleaning a semiconductor production apparatus according to the above (1) or (2), further comprising a pH adjuster.
（４）ｐＨ調整剤が、アンモニア水、アルカリ金属、及び四級アンモニウム塩からなる群より選ばれる一種又は二種以上の塩基であることを特徴とする上記（３）に記載の半導体製造装置洗浄用組成物。 (4) The semiconductor manufacturing apparatus cleaning according to (3) above, wherein the pH adjuster is one or two or more bases selected from the group consisting of aqueous ammonia, alkali metals, and quaternary ammonium salts. Composition.
（５）上記（１）乃至（４）のいずれかに記載の半導体製造装置洗浄用組成物を用いて、半導体製造装置の基材表面に付着した物質を洗浄することを特徴とする半導体製造装置の洗浄方法。 (5) A semiconductor manufacturing apparatus characterized in that a material adhering to a substrate surface of a semiconductor manufacturing apparatus is cleaned using the semiconductor manufacturing apparatus cleaning composition according to any one of (1) to (4). Cleaning method.
（６）半導体製造装置の基材が陽極酸化されたアルミニウムであることを特徴とする上記（５）に記載の半導体製造装置の洗浄方法。 (6) The method for cleaning a semiconductor manufacturing apparatus according to (5), wherein the base material of the semiconductor manufacturing apparatus is anodized aluminum.
本発明の洗浄用組成物は、陽極酸化されたアルミニウム基材等半導体製造装置にダメージを与えることなく、エッチング工程等で堆積したＳｉやレジストポリマー等の付着物を除去することができる。 The cleaning composition of the present invention can remove deposits such as Si and resist polymer deposited in an etching process or the like without damaging a semiconductor manufacturing apparatus such as an anodized aluminum substrate.
以下に、本発明を詳細に説明する。 The present invention is described in detail below.
本発明の洗浄用組成物は、特定のフッ化物を含む。 The cleaning composition of the present invention contains a specific fluoride.
本発明の洗浄用組成物において、特定のフッ化物とは、フッ化ナトリウム、フッ化カリウム、フッ化リチウム、及びフッ化アンモニウムからなる群より選ばれる一種又は二種以上の化合物である。それ以外のフッ化物を併用しても差し支えないが、水への溶解度が低かったり、高価であったりするため、工業的には有利ではない。これら特定のフッ化物の中では、金属の混入がないフッ化アンモニウムが好ましい。フッ化アンモニウムとしては、電子材料用に市販されている高純度のものを使用することができるが、工業的に流通しているものを使用しても良い。 In the cleaning composition of the present invention, the specific fluoride is one or more compounds selected from the group consisting of sodium fluoride, potassium fluoride, lithium fluoride, and ammonium fluoride. Other fluorides may be used in combination, but they are not industrially advantageous because they have low solubility in water or are expensive. Among these specific fluorides, ammonium fluoride free from metal contamination is preferable. As the ammonium fluoride, a high purity commercially available for electronic materials can be used, but those commercially available may be used.
本発明において、特定のフッ化物は、付着物に含まれるＳｉ成分を除去するのに有効であるが、その他、レジストポリマー除去等を容易にする。 In the present invention, the specific fluoride is effective for removing the Si component contained in the deposit, but also facilitates removal of the resist polymer.
また、本発明の洗浄用組成物は、クエン酸を含む。本発明において、クエン酸は、付着物除去を促進する作用がある。クエン酸としては電子材料用に市販されている高純度のものを使用することができるが、工業的に流通しているものを使用しても良い。 Moreover, the cleaning composition of the present invention contains citric acid. In the present invention, citric acid has an action of promoting the removal of deposits. As citric acid, commercially available high-purity products for electronic materials can be used, but those commercially available may be used.
本発明の洗浄用組成物は、ｐＨを調整するために更にｐＨ調整剤を含有してもよい。ｐＨ調整剤としては、例えば、塩基物を使用することができる。具体的には、アンモニア水の他、水酸化カリウム、水酸化ナトリウム等のアルカリ金属、水酸化テトラメチルアンモニウム等の四級アンモニウム塩等が挙げられる。これらのうち、金属の混入がなく、安価で入手しやすいアンモニア水が好ましい。アンモニア水としては電子材料用に市販されている高純度のアンモニア水を使用することができるが、工業的に流通しているアンモニア水を使用しても良い。 The cleaning composition of the present invention may further contain a pH adjusting agent in order to adjust the pH. As the pH adjuster, for example, a base substance can be used. Specific examples include ammonia water, alkali metals such as potassium hydroxide and sodium hydroxide, and quaternary ammonium salts such as tetramethylammonium hydroxide. Of these, ammonia water which is free from metal contamination and easily available is preferable. As the ammonia water, high-purity ammonia water commercially available for electronic materials can be used, but industrially available ammonia water may be used.
本発明の洗浄用組成物において、フッ化物、及びクエン酸の含有量は特に限定するものではないが、洗浄用組成物全量に対し、通常、フッ化物は１〜１００００ｐｐｍ、クエン酸は０．１〜２０重量％の範囲であり、好ましくは、フッ化物は１０〜５０００ｐｐｍ、クエン酸は１〜１０重量％の範囲がである。フッ化物を１ｐｐｍ以上とすることにより、付着物の除去速度を工業的に実施可能な程度に向上させることができ、フッ化物を１００００ｐｐｍ以下とすることにより、陽極酸化されたアルミニウムに対するダメージを小さくすることができる。 In the cleaning composition of the present invention, the contents of fluoride and citric acid are not particularly limited, but the fluoride is usually 1 to 10,000 ppm and the citric acid is 0.1 relative to the total amount of the cleaning composition. The range is -20% by weight, preferably 10 to 5000 ppm for fluoride and 1 to 10% by weight for citric acid. By making the fluoride 1 ppm or more, the removal rate of deposits can be improved to an extent that can be industrially implemented, and by making the fluoride 10000 ppm or less, damage to the anodized aluminum is reduced. be able to.
また、クエン酸を０．１重量％以上とすることにより、付着物の除去速度を工業的な実施に可能な程度に向上させることができ、クエン酸を１０重量％以下とすることにより、陽極酸化されたアルミニウムのダメージを小さくすることができる。なお、クエン酸を１０重量％を超えて使用しても入れただけの効果は得られない。 Further, by making citric acid 0.1% by weight or more, the removal rate of deposits can be improved to an extent that can be industrially implemented, and by making citric acid 10% by weight or less, anode Damage to oxidized aluminum can be reduced. Even if citric acid is used in excess of 10% by weight, the effect of adding citric acid cannot be obtained.
ｐＨ調整剤の使用量は、洗浄用組成物中のクエン酸濃度に依存するため、一概に決められないが、一般的には、洗浄用組成物全量に対し５重量％以下が好ましい。アルミニウム材質のプロセスチャンバーは陽極酸化部分がダメージを受けやすいためｐＨ調整が特に必要である。ｐＨとしては、５〜７の範囲とすることが好ましい。 The amount of the pH adjuster used depends on the concentration of citric acid in the cleaning composition and is not generally determined, but is generally preferably 5% by weight or less based on the total amount of the cleaning composition. In the process chamber made of aluminum, pH adjustment is particularly necessary because the anodized portion is easily damaged. The pH is preferably in the range of 5-7.
本発明の洗浄用組成物には、アルミニウム等の基材に対する防食剤を添加することもできる。なお、本発明の洗浄用組成物において、残部は水である。 An anticorrosive agent for a substrate such as aluminum can also be added to the cleaning composition of the present invention. In the cleaning composition of the present invention, the balance is water.
本発明の洗浄用組成物は、半導体製造装置の基材表面に付着した物質の除去に対して、優れた性能を発揮する。それらの中でも、半導体製造装置の基材が陽極酸化されたアルミニウムである場合に特に好適に適用することができる。 The cleaning composition of the present invention exhibits excellent performance with respect to the removal of substances attached to the substrate surface of a semiconductor manufacturing apparatus. Among these, it can be particularly suitably applied when the base material of the semiconductor manufacturing apparatus is anodized aluminum.
本発明の洗浄用組成物は、０〜１００℃で使用することが好ましい。０℃以上とすることにより、付着物の除去速度を工業的な実施に可能な程度に向上させることができ、１００℃以下とすることにより、洗浄用組成物の濃度変動を工業的な実施に可能な程度に小さくすることができる。 The cleaning composition of the present invention is preferably used at 0 to 100 ° C. By setting the temperature to 0 ° C. or higher, the removal rate of deposits can be improved to the extent possible for industrial implementation. By setting the temperature to 100 ° C. or lower, the concentration fluctuation of the cleaning composition can be industrially implemented. It can be made as small as possible.
本発明の洗浄用組成物は、陽極酸化された基材にエッチングで堆積したＳｉやレジストポリマー等の付着物を除去することができる。 The cleaning composition of the present invention can remove deposits such as Si and resist polymer deposited by etching on an anodized substrate.
本発明の洗浄用組成物を使用し、付着物を除去する際、超音波等の物理的な力を加えて、除去速度を促進させても良い。 When removing the deposit using the cleaning composition of the present invention, the removal rate may be accelerated by applying a physical force such as ultrasonic waves.
以下、本発明の洗浄方法を実施例により説明するが、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。 Hereinafter, although the washing | cleaning method of this invention is demonstrated by an Example, this invention is not limited to these. In order to simplify the notation, the following abbreviations were used.
ＮＨ４Ｆ：フッ化アンモニウム
ＫＦ：フッ化カリウム
ＣＡ：クエン酸
ＮＨ４ＯＨ：アンモニア水
ＫＯＨ：水酸化カリウム
Ａｌ：アルミニウム
Ａｄ−Ａｌ：陽極酸化されたアルミニウム
実施例１〜実施例４
エッチング工程においてプロセスチャンバー内壁（基材：アルミニウム又は陽極酸化されたアルミニウム）に堆積した付着物を洗浄除去するため、当該内壁を、表１に記載の洗浄用組成物に２５℃、３０分間浸漬し、堆積物が完全に除去される時間を測定した。その結果を表１にあわせて示す。
NH 4 F: ammonium fluoride KF: potassium fluoride CA: citric acid NH 4 OH: aqueous ammonia KOH: potassium hydroxide Al: aluminum Ad-Al: anodized aluminum Examples 1 to 4
In order to clean and remove deposits deposited on the inner wall of the process chamber (substrate: aluminum or anodized aluminum) in the etching step, the inner wall is immersed in the cleaning composition described in Table 1 at 25 ° C. for 30 minutes. The time for complete removal of the deposit was measured. The results are also shown in Table 1.
比較例１
実施例３で用いた装置部品（基材：陽極酸化されたアルミニウム）と同様のものを、８０℃に過熱した３１％過酸化水素水に３０分間、浸漬した。その結果、ダメージは全くなかったが、付着物が除去できなかった。
Comparative Example 1
The same device parts (substrate: anodized aluminum) used in Example 3 were immersed in 31% hydrogen peroxide solution heated to 80 ° C. for 30 minutes. As a result, there was no damage at all, but the deposits could not be removed.
Claims (6)
6. The semiconductor manufacturing apparatus cleaning method according to claim 5, wherein the base material of the semiconductor manufacturing apparatus is anodized aluminum.
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| JP2018131377A (en) * | 2017-02-13 | 2018-08-23 | 松田産業株式会社 | Marine fertilizing material using nitrogen-containing waste solution and method of producing the same |
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| JP2005276891A (en) * | 2004-03-23 | 2005-10-06 | Ngk Insulators Ltd | Ceramic susceptor and cleaning method thereof |
| JP2006011297A (en) * | 2004-06-29 | 2006-01-12 | Kanto Chem Co Inc | Removing composition for photoresist residue and polymer residue |
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| JP2002231699A (en) * | 2001-02-02 | 2002-08-16 | Kawasaki Microelectronics Kk | Cleaning method of silicon electrode for fluorocarbon- based plasma generation, and manufacturing method of semiconductor device |
| JP2005276891A (en) * | 2004-03-23 | 2005-10-06 | Ngk Insulators Ltd | Ceramic susceptor and cleaning method thereof |
| JP2006011297A (en) * | 2004-06-29 | 2006-01-12 | Kanto Chem Co Inc | Removing composition for photoresist residue and polymer residue |
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| JP2018131377A (en) * | 2017-02-13 | 2018-08-23 | 松田産業株式会社 | Marine fertilizing material using nitrogen-containing waste solution and method of producing the same |
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