JP3198878B2 - Surface treatment composition and substrate surface treatment method using the same - Google Patents
Surface treatment composition and substrate surface treatment method using the sameInfo
- Publication number
- JP3198878B2 JP3198878B2 JP19150495A JP19150495A JP3198878B2 JP 3198878 B2 JP3198878 B2 JP 3198878B2 JP 19150495 A JP19150495 A JP 19150495A JP 19150495 A JP19150495 A JP 19150495A JP 3198878 B2 JP3198878 B2 JP 3198878B2
- Authority
- JP
- Japan
- Prior art keywords
- cleaning
- surface treatment
- substrate
- metal
- present
- 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.)
- Expired - Fee Related
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- Detergent Compositions (AREA)
- Weting (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は表面処理組成物及び
それを用いた基体の表面処理方法に関する。詳しくは表
面処理組成物から基体表面への金属不純物の汚染を防止
し、安定的に極めて清浄な基体表面を達成する事ができ
る基体の表面処理方法及びそれに用いられる表面処理組
成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface treatment composition and a method for treating a surface of a substrate using the composition. More specifically, the present invention relates to a method for treating a surface of a substrate which can prevent contamination of metal impurities from the surface treatment composition to the surface of the substrate, and stably achieve a very clean substrate surface, and a surface treatment composition used therefor.
【０００２】[0002]
【従来の技術】超ＬＳＩや、ＴＦＴ液晶等に代表される
各種デバイスの高集積化に伴い、基板表面の清浄化への
要求は益々厳しいものになっている。清浄化を妨げるも
のとして各種汚染物質があり、汚染物質の中でも、特に
金属汚染はデバイスの電気的特性を劣化させるものであ
る。かかる劣化を防止するためにはデバイスが形成され
る基板表面における金属不純物の濃度を極力低下させる
必要がある。そのため、基板表面を特定の種の洗浄剤に
より洗浄する事が一般に行われる。2. Description of the Related Art With the increasing integration of various devices typified by VLSIs and TFT liquid crystals, the demand for cleaning the substrate surface is becoming increasingly severe. There are various contaminants that hinder the cleaning, and among the contaminants, metal contamination in particular degrades the electrical characteristics of the device. In order to prevent such deterioration, it is necessary to reduce the concentration of metal impurities on the substrate surface on which the device is formed as much as possible. Therefore, the substrate surface is generally cleaned with a specific type of cleaning agent.
【０００３】従来より、この種の洗浄剤には、超純水、
酸、アルカリ、酸化剤、界面活性剤等の水溶液、電解イ
オン水、高純度有機溶媒などが一般に使用されている。
洗浄剤には優れた洗浄性能と共に、洗浄剤から基板への
金属不純物の逆汚染を防止するため、洗浄剤中の不純物
濃度が極めて低いレベルである事が要求されている。か
かる要求を満足するため、半導体用薬品の高純度化が推
進され、精製直後の薬品に含まれる金属不純物濃度は、
現在の分析技術では検出が難しいレベルにまで達してい
る。[0003] Conventionally, this type of cleaning agent includes ultrapure water,
An aqueous solution of an acid, an alkali, an oxidizing agent, a surfactant, or the like, electrolytic ionic water, a high-purity organic solvent, and the like are generally used.
In addition to excellent cleaning performance, the cleaning agent is required to have an extremely low impurity concentration in the cleaning agent in order to prevent metal contamination from the cleaning agent to the substrate. In order to satisfy such demands, purifying semiconductor chemicals has been promoted, and the concentration of metal impurities contained in the chemicals immediately after purification is as follows:
It has reached a level that is difficult to detect with current analytical techniques.
【０００４】このように、洗浄剤中の不純物が検出困難
なレベルにまで達しているにもかかわらず、いまだ高清
浄な表面の達成が難しいのは、洗浄槽において、基板か
ら除去された金属不純物が、洗浄剤を汚染する事が避け
られないためである。すなわち、表面から一旦脱離した
金属不純物が洗浄剤中に混入し洗浄剤を汚染する。そし
て、汚染された洗浄剤から金属不純物が基板に付着（逆
汚染）してしまうためである。[0004] As described above, despite the fact that the impurities in the cleaning agent have reached a level that is difficult to detect, it is still difficult to achieve a high-purity surface due to the metal impurities removed from the substrate in the cleaning tank. However, it is inevitable to contaminate the cleaning agent. That is, the metal impurities once detached from the surface are mixed into the cleaning agent and contaminate the cleaning agent. Then, metal impurities are attached to the substrate from the contaminated cleaning agent (reverse contamination).
【０００５】半導体洗浄工程においては、［アンモニア
＋過酸化水素＋水］洗浄（通称「ＳＣ−１洗浄」）（RC
A Review, p.187-206, June(1970) 等）が、広く用いら
れている。本洗浄は通常、４０〜９０℃で行われ、洗浄
剤組成として、通常、（３０重量％アンモニア水）：
（３１重量％過酸化水素水）：（水）＝０．０５〜１：
１：５程度の容量比のものが使用に供される。しかし、
本洗浄法は高いパーティクル除去能力や有機物除去能力
を持つ反面、溶液中にＦｅやＡｌ、Ｚｎ、Ｎｉ等の金属
が極微量存在すると、基板表面に付着して逆汚染してし
まうという問題がある。このため、半導体洗浄工程にお
いては、通常、［アンモニア＋過酸化水素＋水］洗浄の
後に、［塩酸＋過酸化水素＋水］洗浄（通称「ＳＣ−２
洗浄」）等の酸性洗浄剤による洗浄を行い、基板表面の
金属汚染を除去している。In the semiconductor cleaning process, [ammonia + hydrogen peroxide + water] cleaning (commonly called “SC-1 cleaning”) (RC
A Review, p.187-206, June (1970), etc.) are widely used. The main cleaning is usually performed at 40 to 90 ° C., and the cleaning composition is usually (30% by weight ammonia water):
(31% by weight aqueous hydrogen peroxide): (water) = 0.05 to 1:
Those having a capacity ratio of about 1: 5 are provided for use. But,
Although this cleaning method has high particle removal ability and organic matter removal ability, when a very small amount of metal such as Fe, Al, Zn, or Ni is present in the solution, it has a problem that it adheres to the substrate surface and causes reverse contamination. . For this reason, in the semiconductor cleaning step, usually, [ammonia + hydrogen peroxide + water] cleaning is followed by [hydrochloric acid + hydrogen peroxide + water] cleaning (so-called “SC-2”).
Cleaning with an acidic cleaning agent such as "cleaning") removes metal contamination on the substrate surface.
【０００６】このように、洗浄工程において、高清浄な
表面を効率よく、安定的に得るために、かかる逆汚染を
防止する技術が求められていた。溶液中の金属不純物が
基板表面に付着して逆汚染する問題は、洗浄工程のみな
らず、シリコン基板等のアルカリエッチングや、シリコ
ン酸化膜の希フッ酸によるエッチング工程等の、溶液を
使用した基板表面処理工程全般において大きな問題とな
っている。希フッ酸エッチング工程では、液中にＣｕや
Ａｕ等の貴金属不純物があると、シリコン表面に付着し
て、キャリアライフタイム等のデバイスの電気的特性を
著しく劣化させる。また、アルカリエッチング工程で
は、液中にＦｅやＡｌ等の微量金属不純物があると、基
板表面に容易に付着してしまう。そこでかかる汚染を防
止するための技術が強く求められていた。As described above, in order to efficiently and stably obtain a highly clean surface in the cleaning step, a technique for preventing such reverse contamination has been required. The problem of metal impurities in the solution adhering to the substrate surface and contaminating the substrate surface is not only a cleaning process, but also a substrate using a solution such as an alkali etching process for a silicon substrate or an etching process for a silicon oxide film using diluted hydrofluoric acid. This is a major problem in the entire surface treatment process. In the diluted hydrofluoric acid etching step, if there is a noble metal impurity such as Cu or Au in the liquid, it adheres to the silicon surface and significantly degrades the electrical characteristics of the device such as carrier lifetime. In addition, in the alkaline etching step, if there is a trace amount of metal impurities such as Fe and Al in the liquid, the impurities easily adhere to the substrate surface. Therefore, a technique for preventing such contamination has been strongly demanded.
【０００７】この問題を解決するために、表面処理剤に
キレート剤等の錯化剤を添加し、液中の金属不純物を安
定な水溶性錯体として捕捉し、基板表面への付着を防止
する方法が提案されている。特開昭５０−１５８２８１
号公報では、テトラアルキル水酸化アンモニウム水溶液
に、シアン化アンモニウムやエチレンジアミン４酢酸
（ＥＤＴＡ）等の錯化剤を添加し、半導体基板表面への
金属不純物の付着を防止する事が提案されている。特開
平３−２１９０００号公報では、カテコール、チロン等
のキレート剤を、特開平５−２７５４０５号公報ではホ
スホン酸系キレート剤または縮合リン酸等の錯化剤を、
特開平６−１６３４９５号公報ではヒドラゾン誘導体等
の錯化剤を、［アンモニア＋過酸化水素＋水］等のアル
カリ性洗浄液に添加して基板への金属不純物付着を防止
し、これによって、パーティクル、有機物汚染と共に、
金属汚染のない基板表面を達成する技術が提案されてい
る。In order to solve this problem, a method of adding a complexing agent such as a chelating agent to a surface treating agent to trap metal impurities in the liquid as a stable water-soluble complex and prevent the metal impurities from adhering to the substrate surface. Has been proposed. JP-A-50-158281
In Japanese Patent Application Laid-Open Publication No. H11-163, it is proposed that a complexing agent such as ammonium cyanide or ethylenediaminetetraacetic acid (EDTA) is added to an aqueous solution of tetraalkylammonium hydroxide to prevent metal impurities from adhering to the surface of the semiconductor substrate. In JP-A-3-219000, a chelating agent such as catechol and thyrone is used. In JP-A-5-275405, a complexing agent such as a phosphonic acid chelating agent or condensed phosphoric acid is used.
In JP-A-6-163495, a complexing agent such as a hydrazone derivative is added to an alkaline cleaning solution such as [ammonia + hydrogen peroxide + water] to prevent metal impurities from adhering to the substrate, thereby allowing particles and organic substances to be removed. Along with pollution
Techniques for achieving a substrate surface free of metal contamination have been proposed.
【０００８】しかしながら、これらの錯化剤を添加した
場合、特定の金属（例えば、Ｆｅ）に関しては付着防
止、あるいは除去効果が見られたものの、処理液や基板
を汚染しやすいＦｅ以外の金属（例えば、Ａｌ）につい
ては上記錯化剤の効果が極めて小さく、大量の錯化剤を
添加しても十分な効果が得られないという問題があっ
た。However, when these complexing agents are added, a specific metal (for example, Fe) has an effect of preventing adhesion or removing, but a metal other than Fe (which tends to contaminate the processing solution and the substrate). For example, Al) has a problem that the effect of the complexing agent is extremely small, and a sufficient effect cannot be obtained even if a large amount of complexing agent is added.
【０００９】特開平６−２１６０９８号公報には、この
問題を解決するために、ホスホン酸系キレート剤等のキ
レート剤を添加した［アンモニア＋過酸化水素＋水］洗
浄液で基板を洗浄し、次いで１ppm 以上のフッ酸水溶液
でリンスする事が記載されている。これは、ホスホン酸
系キレート剤を添加しても、基板表面のＡｌ汚染は十分
に低減できないため、後工程で１ppm 以上のフッ酸水溶
液を用いて、Ａｌをエッチングによって除去しようとす
るものである。この様に、従来の金属付着防止方法は効
果が十分とは言えず、基板の清浄化が必要な場合には、
後工程で金属汚染を除去せざるを得ず、これにより、工
程数が増えて、生産コスト増大の原因となっていた。Japanese Patent Application Laid-Open No. 6-216098 discloses that in order to solve this problem, the substrate is washed with a [ammonia + hydrogen peroxide + water] cleaning solution to which a chelating agent such as a phosphonic acid chelating agent is added, It describes that rinsing is performed with a hydrofluoric acid aqueous solution of 1 ppm or more. This is because the addition of a phosphonic acid-based chelating agent does not sufficiently reduce Al contamination on the substrate surface, and is intended to remove Al by etching using a hydrofluoric acid aqueous solution of 1 ppm or more in a later step. . As described above, the conventional metal adhesion preventing method is not sufficiently effective, and when the substrate needs to be cleaned,
Metal contamination must be removed in a later step, which increases the number of steps and causes an increase in production cost.
【００１０】[0010]
【発明が解決しようとする課題】以上のように、表面処
理組成物から基体表面への金属不純物汚染が深刻な問題
となっているが、それを防止する技術は、いまだ不十分
である。そのため、様々な錯化剤の添加によって付着防
止が試みられているが、いまだ十分な改善がなされてい
ない現状にある。As described above, contamination of metal impurities from the surface treatment composition to the surface of the substrate is a serious problem, but the technique for preventing it is still insufficient. For this reason, various kinds of complexing agents have been added to prevent adhesion, but at present there is no sufficient improvement.
【００１１】本発明は上記問題を解決するためになされ
たものであり、表面処理組成物から基体表面への金属不
純物の汚染を防止し、安定的に極めて清浄な基体表面を
達成する事ができる基体の表面処理方法及びそのために
用いられる表面処理組成物を提供する事を目的とするも
のである。The present invention has been made to solve the above-mentioned problems, and can prevent contamination of metal impurities from the surface treatment composition to the substrate surface, and can stably achieve a very clean substrate surface. An object of the present invention is to provide a surface treatment method for a substrate and a surface treatment composition used for the method.
【００１２】[0012]
【課題を解決するための手段】本発明者らは、上記課題
を解決するために鋭意検討を重ねた結果、表面処理組成
物中に金属付着防止剤として特定の錯化剤を添加含有せ
しめると、処理液から基体への金属不純物の付着防止効
果が著しく向上する事を見いだし、本発明に到達した。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, it has been found that a specific complexing agent is added and contained as a metal adhesion inhibitor in a surface treatment composition. The present inventors have found that the effect of preventing metal impurities from adhering to the substrate from the processing solution is remarkably improved, and arrived at the present invention.
【００１３】すなわち本発明の要旨は、金属付着防止剤
として、エチレンジアミンジオルトヒドロキシフェニル
酢酸［通称：ＥＤＤＨＡ］からなる錯化剤を含有する半
導体基板の表面処理用液状組成物、及びそれを用いた半
導体基板の表面処理方法に存する。That is, the gist of the present invention is to provide a liquid composition for surface treatment of a semiconductor substrate containing a complexing agent composed of ethylenediaminediorthohydroxyphenylacetic acid [commonly known as EDDHA] as a metal adhesion inhibitor, and to use the same. A method for treating a surface of a semiconductor substrate.
【００１４】[0014]
【発明の実施の形態】以下、本発明を詳細に説明する。
本発明において、表面処理用液状組成物とは、基体の洗
浄、エッチング、研磨、成膜等を目的として用いられる
表面処理液の総称である。本発明において、金属付着防
止剤として使用される錯化剤は、エチレンジアミンジオ
ルトヒドロキシフェニル酢酸である。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In the present invention, the surface treatment liquid composition is a general term for a surface treatment liquid used for the purpose of cleaning, etching, polishing, forming a film, and the like of a substrate. In the present invention, the complexing agent used as the metal adhesion inhibitor is ethylenediaminediorthohydroxyphenylacetic acid.
【００１５】含有量一定の際の金属付着防止効果の点で
は、エチレンジアミンジオルトヒドロキシフェニル酢酸
が優れており、好ましく用いられる。In terms of the effect of preventing metal adhesion when the content is constant, ethylenediamine diorthohydroxyphenylacetic acid is excellent and is preferably used.
【００１６】金属付着防止剤として加えられる錯化剤の
添加量は、付着防止対象である液中の金属不純物の種類
と量、基体表面に要求される清浄度レベルによって異な
るので一概には決められないが、表面処理組成物中の総
添加量として、通常１０-7〜５重量％、好ましくは１０
-6〜０．１重量％である。上記添加量より少なすぎると
金属付着防止効果が十分ではなく、一方、多すぎてもそ
れ以上の効果は得られず、また、基体表面に金属付着防
止剤である錯化剤が付着する危険性が高くなので好まし
くない。The amount of the complexing agent added as a metal adhesion inhibitor varies depending on the type and amount of metal impurities in the liquid to be prevented from adhesion and the level of cleanliness required on the surface of the substrate. However, as a total addition amount in the surface treatment composition, it is usually 10 -7 to 5% by weight, preferably 10
-6 to 0.1% by weight. If the amount is too small, the effect of preventing metal adhesion is not sufficient, while if it is too large, no further effect is obtained, and there is a risk that the complexing agent, which is a metal adhesion inhibitor, adheres to the substrate surface. Is not preferable because it is expensive.
【００１７】主成分となる成分としては、通常、水や
酸、アルカリ、酸化剤、還元剤、界面活性剤等の水溶
液、電解イオン水、有機溶媒、あるいはこれらの混合溶
液が用いられる。特に、半導体基板の洗浄やエッチング
に用いられるアルカリ性水溶液や希フッ酸溶液において
は、溶液中の金属不純物が基体表面に極めて付着し易い
ため、本発明が好ましく用いられる。As the main component, an aqueous solution of water, an acid, an alkali, an oxidizing agent, a reducing agent, a surfactant, or the like, electrolytic ionic water, an organic solvent, or a mixed solution thereof is usually used. In particular, the present invention is preferably used in an alkaline aqueous solution or a diluted hydrofluoric acid solution used for cleaning or etching a semiconductor substrate, since metal impurities in the solution are extremely easily attached to the substrate surface.
【００１８】本発明において、アルカリ性水溶液とはそ
のｐＨが７よりも大きい水溶液の総称である。アルカリ
性成分としては、代表的なものとしてアンモニアが挙げ
られる。また、水酸化ナトリウム、水酸化カリウム、水
酸化カルシウム等のアルカリ金属またはアルカリ土類金
属の水酸化物、炭酸水素ナトリウム、炭酸水素アンモニ
ウム等のアルカリ性塩類、あるいはテトラメチルアンモ
ニウムヒドロキシド、トリメチル−２−ヒドロキシエチ
ルアンモニウムヒドロキシド（コリン）等の第４級アン
モニウムヒドロキシドなども用いられる。これらのアル
カリは、２種以上添加しても何等差し支えなく、通常、
表面処理組成物全溶液中の全濃度が０．０１〜３０重量
％になるように用いられる。In the present invention, an alkaline aqueous solution is a general term for aqueous solutions whose pH is higher than 7. Representative examples of the alkaline component include ammonia. Further, hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide, potassium hydroxide and calcium hydroxide; alkaline salts such as sodium hydrogen carbonate and ammonium hydrogen carbonate; or tetramethylammonium hydroxide, trimethyl-2- A quaternary ammonium hydroxide such as hydroxyethylammonium hydroxide (choline) is also used. These alkalis may be added at least two times without any problem.
The surface treatment composition is used so that the total concentration in the whole solution is 0.01 to 30% by weight.
【００１９】さらに、このようなアルカリ性水溶液中に
は過酸化水素等の酸化剤が適宜配合されていても良い。
半導体ウェハ洗浄工程においては、ベア（酸化膜のな
い）シリコンを洗浄する際に、酸化剤を配合することに
より、ウェハのエッチングや表面荒れを抑える事ができ
る。本発明のアルカリ性水溶液に過酸化水素を配合する
場合には、通常、表面処理組成物全溶液中の過酸化水素
濃度が０．０１〜３０重量％の濃度範囲になるように用
いられる。Further, an oxidizing agent such as hydrogen peroxide may be appropriately blended in such an alkaline aqueous solution.
In the semiconductor wafer cleaning step, when cleaning bare (silicon-free) silicon, an oxidizing agent is added, whereby etching and surface roughness of the wafer can be suppressed. When hydrogen peroxide is added to the alkaline aqueous solution of the present invention, it is usually used so that the concentration of hydrogen peroxide in the entire solution of the surface treatment composition is in the range of 0.01 to 30% by weight.
【００２０】また、本発明は、水を電気分解することに
より得られると言われている、いわゆるアルカリ電解イ
オン水を主成分とする表面処理組成物にも好ましく用い
られる。本発明において、錯化剤を表面処理組成物に配
合する方法は特に限定されない。表面処理組成物を主と
して構成している成分（例えば、前記ＳＣ−１洗浄に用
いる洗浄用組成物であればアンモニア水、過酸化水素
水、水）のうち、いずれか一成分、あるいは複数成分に
あらかじめ錯化剤を配合し、後に残余の成分を混合して
使用しても良いし、主として構成している成分を混合し
た後に錯化剤を配合して使用しても良い。The present invention is also preferably used for a surface treatment composition containing so-called alkaline electrolytic ionic water as a main component, which is said to be obtained by electrolyzing water. In the present invention, the method of adding the complexing agent to the surface treatment composition is not particularly limited. Among the components that mainly constitute the surface treatment composition (for example, ammonia water, hydrogen peroxide water, and water in the case of the cleaning composition used for the SC-1 cleaning), any one component or a plurality of components is used. A complexing agent may be blended in advance and the remaining components may be mixed and used later, or the complexing agent may be blended and used after mixing mainly constituent components.
【００２１】本発明の表面処理用液状組成物は基体の金
属不純物汚染が問題となる半導体等の基体の、洗浄、エ
ッチング、研磨、成膜等の表面処理に用いられる。特
に、高清浄な基体表面が要求される半導体基板の洗浄、
エッチングに本発明が好適に使用される。半導体基板の
洗浄の中でも特に［アンモニア＋過酸化水素＋水］洗浄
等のアルカリ洗浄に本発明を適用すると、該洗浄法の問
題点であった基板への金属不純物付着の問題が改善さ
れ、これにより該洗浄によって、パーティクル、有機物
汚染と共に、金属汚染のない高清浄な基体表面が達成さ
れるため、極めて好適である。The liquid composition for surface treatment of the present invention is used for surface treatment such as cleaning, etching, polishing, film formation and the like of a substrate such as a semiconductor in which metal impurity contamination of the substrate becomes a problem. In particular, cleaning of semiconductor substrates that require a highly clean substrate surface,
The present invention is suitably used for etching. When the present invention is applied to alkali cleaning such as [ammonia + hydrogen peroxide + water] cleaning among semiconductor substrate cleaning, the problem of metal impurity adhesion to the substrate, which was a problem of the cleaning method, is improved. By this cleaning, a highly clean substrate surface free of metal contamination as well as particles and organic contamination is achieved, which is extremely preferable.
【００２２】本発明を基体の洗浄に用いる場合、液を直
接、基体に接触させる方法が用いられる。このような洗
浄方法としては、洗浄槽に洗浄液を満たして基体を浸漬
させるディップ式クリーニング、基体に液を噴霧して洗
浄するスプレー式クリーニング、基体上に洗浄液を滴下
して高速回転させるスピン式クリーニング等が挙げられ
る。本発明は、上記洗浄方法のいずれにも用いられる
が、好ましくはディップ式クリーニングが用いられる。
洗浄時間については、適当な時間洗浄されるが、好まし
くは１０秒〜３０分、より好ましくは３０秒〜１５分で
ある。時間が短すぎると洗浄効果が十分でなく、長すぎ
るとスループットが悪くなるだけで、洗浄効果は上がら
ず意味がない。洗浄は常温で行っても良いが、洗浄効果
を向上させる目的で、加温して行う事もできる。また、
洗浄の際には、物理力による洗浄方法と併用させても良
い。このような物理力による洗浄方法としては、たとえ
ば、超音波洗浄、洗浄ブラシを用いた機械的洗浄などが
挙げられる。When the present invention is used for cleaning a substrate, a method of directly contacting a liquid with the substrate is used. Such cleaning methods include dip-type cleaning in which a cleaning tank is filled with a cleaning liquid and immersing the substrate, spray-type cleaning in which the liquid is sprayed on the substrate and cleaning, and spin-type cleaning in which the cleaning liquid is dropped on the substrate and rotated at high speed. And the like. The present invention can be used in any of the above cleaning methods, but preferably uses dip-type cleaning.
Regarding the washing time, the washing is performed for an appropriate time, but is preferably 10 seconds to 30 minutes, more preferably 30 seconds to 15 minutes. If the time is too short, the cleaning effect will not be sufficient, and if it is too long, the throughput will only be deteriorated, and the cleaning effect will not increase and is meaningless. The washing may be performed at room temperature, but may be performed with heating for the purpose of improving the washing effect. Also,
At the time of cleaning, a cleaning method using physical force may be used in combination. Examples of such a cleaning method using physical force include ultrasonic cleaning and mechanical cleaning using a cleaning brush.
【００２３】[0023]
【実施例】次に実施例を用いて、本発明の具体的態様を
説明するが、本発明はその要旨を越えない限り以下の実
施例により何ら限定されるものではない。 実施例−１〜２及び比較例−１〜１１ アンモニア水（３０重量％）、過酸化水素水（３１重量
％）及び水を０．２５：１：５の容量比で混合し、得ら
れた水性溶媒に金属付着防止剤として表−１に示す錯化
剤を所定量添加せしめ、表面処理用組成物を調製した。
なお、錯化剤の添加量は該水性溶媒に対する重量％で示
し、名称は前記の通称名で示した。（実施例１〜２およ
び比較例４〜１１）また、比較例１〜３として、該水性
溶媒に、特開平５−２７５４０５号公報に記載された錯
化剤であるエチレンジアミンテトラキス（メチルホスホ
ン酸）〔通称：ＥＤＴＰＯ〕を添加したもの、特開平６
−１６３４９５号公報に記載の錯化剤であるオキサリッ
クビス（サリシリデンヒドラジド）を添加したもの、及
び錯化剤を一切添加しないものも調製した。EXAMPLES Next, specific embodiments of the present invention will be described with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. Examples-1 to 2 and Comparative Examples-1 to 11 Ammonia water (30% by weight), hydrogen peroxide solution (31% by weight) and water were mixed in a volume ratio of 0.25: 1: 5, and the mixture was obtained. A predetermined amount of the complexing agent shown in Table 1 was added to the aqueous solvent as a metal adhesion inhibitor to prepare a composition for surface treatment.
The amount of the complexing agent added was shown in% by weight based on the aqueous solvent, and the name was shown by the above-mentioned common name. (Examples 1 and 2 and Comparative Examples 4 to 11) As Comparative Examples 1 to 3, ethylenediaminetetrakis (methylphosphonic acid), a complexing agent described in JP-A-5-275405, was added to the aqueous solvent. Commonly known as EDTPO]
A composition to which oxalic bis (salicylidenehydrazide) as a complexing agent described in JP-B-163495 was added and a composition to which no complexing agent was added were also prepared.
【００２４】こうして調製した表面処理液に、Ａｌ、Ｆ
ｅを１０ｐｐｂずつ、各々塩化物として添加した後、清
浄なシリコンウェハ（ｐ型、ＣＺ、面方位（１００））
を１０分間浸漬した。浸漬の間、表面処理液の液温は、
加温して４０〜５０℃に保持した。浸漬後のシリコンウ
ェハは、超純水で１０分間オーバーフローリンスした
後、窒素ブローにより乾燥し、ウェハ表面に付着したＡ
ｌ、Ｆｅを定量した。シリコンウェハ上に付着したＡ
ｌ、Ｆｅはフッ酸０．１重量％と過酸化水素１重量％の
混合液で回収し、フレームレス原子吸光法により該金属
量を測定し、基板表面濃度（atoms/cm2 ）に換算した。
結果を表−１に示す。Al, F were added to the surface treatment solution thus prepared.
e was added as chlorides by 10 ppb each, and then a clean silicon wafer (p-type, CZ, plane orientation (100))
For 10 minutes. During the immersion, the temperature of the surface treatment liquid is
Warmed and maintained at 40-50 ° C. The silicon wafer after the immersion was overflow-rinsed with ultrapure water for 10 minutes, then dried by nitrogen blowing, and A
l, Fe was quantified. A adhered on silicon wafer
1 and Fe were recovered with a mixed solution of hydrofluoric acid 0.1% by weight and hydrogen peroxide 1% by weight, the amount of the metal was measured by a flameless atomic absorption method, and converted to a substrate surface concentration (atoms / cm 2 ). .
The results are shown in Table 1.
【００２５】[0025]
【表１】 [Table 1]
【００２６】[0026]
【発明の効果】本発明の表面処理組成物は、金属付着防
止剤として特定の錯化剤を含有する事により、表面処理
組成物から基体表面へのＡｌ、Ｆｅ等の金属不純物汚染
を防止し、安定的に極めて清浄な基体表面を達成する事
ができる。特に、［アンモニア＋過酸化水素＋水］洗浄
等に代表される半導体基板のアルカリ洗浄に本発明を適
用すると、該洗浄法の問題点であった基板への金属不純
物付着の問題が改善され、これにより該洗浄によって、
パーティクル、有機物汚染と共に、金属汚染のない高清
浄な基板表面が達成される。このため、従来、該洗浄の
後に用いられてきた、［塩酸＋過酸化水素＋水］洗浄等
の酸洗浄が省略でき、洗浄コスト、及び排気設備等のク
リーンルームのコストの大幅な低減が可能となるため、
半導体集積回路の工業生産上利するところ大である。ま
た、金属基体あるいは、表面を金属で成膜した基体のエ
ッチングや洗浄の際には、処理される金属よりイオン化
傾向の低い金属が不純物として液中に存在すると基体表
面に電気化学的に付着するが、本発明を用いれば金属不
純物は安定な水溶性金属錯体となるので、これを防止す
る事が出来る。また、本発明を、基体を研磨する研磨剤
スラリーに適用すれば、研磨剤スラリー中に多量存在
し、基体の研磨と共にスラリー中に濃縮されていく金属
不純物の基体への付着を防止することができる。The surface treatment composition of the present invention contains a specific complexing agent as a metal adhesion inhibitor, thereby preventing contamination of metal impurities such as Al and Fe from the surface treatment composition onto the substrate surface. An extremely clean substrate surface can be stably achieved. In particular, when the present invention is applied to alkali cleaning of a semiconductor substrate typified by [ammonia + hydrogen peroxide + water] cleaning and the like, the problem of metal impurity attachment to the substrate, which was a problem of the cleaning method, is improved. Thereby, by the washing,
A highly clean substrate surface free of metal contamination as well as particles and organic contamination is achieved. For this reason, acid cleaning such as [hydrochloric acid + hydrogen peroxide + water] cleaning, which has been conventionally used after the cleaning, can be omitted, and the cleaning cost and the cost of a clean room such as exhaust equipment can be significantly reduced. To become
This is a great advantage for industrial production of semiconductor integrated circuits. In addition, when etching or cleaning a metal substrate or a substrate whose surface is formed with a metal, if a metal having a lower ionization tendency than the metal to be treated is present as an impurity in the liquid, the metal adheres electrochemically to the substrate surface. However, when the present invention is used, the metal impurities become a stable water-soluble metal complex, which can be prevented. Further, if the present invention is applied to an abrasive slurry for polishing a substrate, it is possible to prevent metal impurities present in a large amount in the abrasive slurry and being concentrated in the slurry as the substrate is polished from adhering to the substrate. it can.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C11D 7/06 C11D 3/60 H01L 21/304 H01L 21/308 ＣＡ（ＳＴＮ) ＣＡＯＬＤ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)──────────────────────────────────────────────────続 き Continued on the front page (58) Fields surveyed (Int. Cl. 7 , DB name) C11D 7/06 C11D 3/60 H01L 21/304 H01L 21/308 CA (STN) CAOLD (STN) REGISTRY (STN )
Claims (5)
ンジオルトヒドロキシフェニル酢酸からなる錯化剤を含
有する事を特徴とする半導体基板の表面処理用液状組成
物。1. A liquid composition for treating a surface of a semiconductor substrate, comprising a complexing agent comprising ethylenediaminediorthohydroxyphenylacetic acid as a metal adhesion inhibitor.
面のエッチング、研磨または洗浄である請求項１に記載
の表面処理用液状組成物。 2. The method according to claim 1 , wherein the surface treatment of the semiconductor substrate is performed on a semiconductor substrate.
2. The method according to claim 1, wherein the surface is etched, polished or cleaned.
Liquid composition for surface treatment.
１または２に記載の表面処理用液状組成物。3. A surface treatment liquid composition according to claim 1 or 2 as a main component an aqueous alkaline solution.
化水素を含有する水溶液である請求項３に記載の表面処
理用液状組成物。4. The liquid composition for surface treatment according to claim 3 , wherein the alkaline aqueous solution is an aqueous solution containing ammonia and hydrogen peroxide.
面処理用液状組成物を用いて半導体基板の表面を処理す
る方法。5. A method for treating a surface of a semiconductor substrate with claim 1 for surface treatment liquid composition according to any one of the four.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19150495A JP3198878B2 (en) | 1995-07-27 | 1995-07-27 | Surface treatment composition and substrate surface treatment method using the same |
| DE69636618T DE69636618T2 (en) | 1995-07-27 | 1996-07-25 | METHOD FOR THE TREATMENT OF A SUBSTRATE SURFACE AND TREATMENT THEREFOR |
| EP96925074A EP0789071B1 (en) | 1995-07-27 | 1996-07-25 | Method for treating surface of substrate and surface treatment composition therefor |
| US08/809,147 US5885362A (en) | 1995-07-27 | 1996-07-25 | Method for treating surface of substrate |
| PCT/JP1996/002077 WO1997005228A1 (en) | 1995-07-27 | 1996-07-25 | Method for treating surface of substrate and surface treatment composition therefor |
| KR1019970702024A KR100429440B1 (en) | 1995-07-27 | 1996-07-25 | Method of surface treatment of gas and surface treatment composition used therefor |
| US09/218,000 US6228823B1 (en) | 1995-07-27 | 1998-12-22 | Method for treating surface of substrate and surface treatment composition used for the same |
| US09/749,545 US6498132B2 (en) | 1995-07-27 | 2000-12-28 | Method for treating surface of substrate and surface treatment composition used for the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19150495A JP3198878B2 (en) | 1995-07-27 | 1995-07-27 | Surface treatment composition and substrate surface treatment method using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0940997A JPH0940997A (en) | 1997-02-10 |
| JP3198878B2 true JP3198878B2 (en) | 2001-08-13 |
Family
ID=16275758
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19150495A Expired - Fee Related JP3198878B2 (en) | 1995-07-27 | 1995-07-27 | Surface treatment composition and substrate surface treatment method using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3198878B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2567676A (en) * | 2016-10-20 | 2019-04-24 | Marneros Loukas | A method for securing a covering in place on bedding and a bifurcated securement device therefor |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8338087B2 (en) * | 2004-03-03 | 2012-12-25 | Advanced Technology Materials, Inc | Composition and process for post-etch removal of photoresist and/or sacrificial anti-reflective material deposited on a substrate |
| JP2015088712A (en) * | 2013-11-01 | 2015-05-07 | 日本酢ビ・ポバール株式会社 | Texture etchant, liquid additive agent for texture etchant, texture-formed substrate, method for manufacturing texture-formed substrate, and solar battery |
-
1995
- 1995-07-27 JP JP19150495A patent/JP3198878B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2567676A (en) * | 2016-10-20 | 2019-04-24 | Marneros Loukas | A method for securing a covering in place on bedding and a bifurcated securement device therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0940997A (en) | 1997-02-10 |
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