JP3219020B2 - Cleaning agent - Google Patents
Cleaning agentInfo
- Publication number
- JP3219020B2 JP3219020B2 JP15283497A JP15283497A JP3219020B2 JP 3219020 B2 JP3219020 B2 JP 3219020B2 JP 15283497 A JP15283497 A JP 15283497A JP 15283497 A JP15283497 A JP 15283497A JP 3219020 B2 JP3219020 B2 JP 3219020B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- cleaning
- cleaning agent
- agent according
- group
- 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 - Lifetime
Links
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- Cleaning By Liquid Or Steam (AREA)
- Detergent Compositions (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Description
【発明の属する技術分野】本発明は半導体やＬＣＤの製
造工程等に於て使用される半導体基板表面の洗浄処理剤
及び処理方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning agent and a cleaning method for a semiconductor substrate surface used in a semiconductor or LCD manufacturing process.
【０００２】[0002]
【従来の技術】現在、ＬＳＩの高集積化に伴い、それに
導入される技術も多種多様となっている。ＬＳＩの半導
体デバイスに主に用いられるシリコンウェーハは、単結
晶のシリコンインゴットから切り取られ、ラッピングや
ポリッシング（研磨）工程を経て作製される為、シリコ
ンウェーハの表面は多量の金属不純物により汚染をうけ
る。その後、デバイスを作成するにあたっても、不純物
拡散工程や金属電極形成等を経て製造される為、シリコ
ンウェーハの表面は金属により汚染をうける危険性が高
い。2. Description of the Related Art At present, with the increasing integration of LSIs, the technologies introduced therein have become diversified. A silicon wafer mainly used for an LSI semiconductor device is cut from a single-crystal silicon ingot and manufactured through a lapping or polishing (polishing) process, so that the surface of the silicon wafer is contaminated by a large amount of metal impurities. After that, when a device is manufactured, the device is manufactured through an impurity diffusion process, a metal electrode formation, and the like, so that the surface of the silicon wafer is highly likely to be contaminated with metal.
【０００３】近年、半導体基板表面の多層配線化に伴う
平坦化の要望から、デバイスを作製する際も化学的物理
的研磨（ＣＭＰ）技術を導入することが提案されてい
る。ＣＭＰは、シリカやアルミナのスラリーを用いて半
導体基板表面を平坦化する方法であり、研磨の対象はシ
リコン酸化膜や配線、プラグなどである。この際も使用
したシリカやアルミナスラリー自身やスラリー中に含ま
れる不純物金属、さらには研磨された配線やプラグの金
属により半導体基板表面が汚染される。この場合、金属
不純物による汚染はウェーハ表面の全面に多量に分布し
ている。[0003] In recent years, in response to a demand for flattening due to the formation of multilayer wiring on the surface of a semiconductor substrate, it has been proposed to introduce a chemical-physical polishing (CMP) technique when manufacturing a device. CMP is a method of planarizing the surface of a semiconductor substrate using a slurry of silica or alumina, and the object to be polished is a silicon oxide film, wiring, plug, and the like. Also at this time, the surface of the semiconductor substrate is contaminated with the silica or alumina slurry used itself, the impurity metal contained in the slurry, and the metal of the polished wiring or plug. In this case, a large amount of contamination by metal impurities is distributed over the entire surface of the wafer.
【０００４】半導体基板表面が金属不純物による汚染を
受けると半導体の電気特性に影響を与え、デバイスの信
頼性が低下する。更に、金属汚染が著しい場合、デバイ
スが破壊されてしまうため、ＣＭＰ工程後に洗浄工程を
導入し、半導体基板表面から金属不純物を除去する必要
がある。When the surface of a semiconductor substrate is contaminated with metal impurities, the electrical characteristics of the semiconductor are affected, and the reliability of the device is reduced. Furthermore, if metal contamination is significant, the device will be destroyed. Therefore, it is necessary to remove the metal impurities from the surface of the semiconductor substrate by introducing a cleaning step after the CMP step.
【０００５】今日、洗浄工程は化学的洗浄、物理的洗浄
又はそれらの併用によって行われており、化学的洗浄と
しては1970年代に開発されたＲＣＡ洗浄が広く用いられ
ている。ＲＣＡ洗浄は酸系洗浄液とアルカリ系洗浄液か
ら構成され、金属除去にはＨＰＭ（塩酸−過酸化水素水
系）やＤＨＦ（希フッ酸系）等の酸系洗浄液が用いられ
ている。一方、ＡＰＭ（アンモニア−過酸化水素水）に
代表されるアルカリ洗浄液はパーティクルの除去能力に
は優れているが、金属の除去能力は不充分である。[0005] Today, the cleaning step is performed by chemical cleaning, physical cleaning, or a combination thereof, and RCA cleaning developed in the 1970s is widely used as chemical cleaning. The RCA cleaning includes an acid-based cleaning solution and an alkali-based cleaning solution, and an acid-based cleaning solution such as HPM (hydrochloric acid-hydrogen peroxide) or DHF (dilute hydrofluoric acid) is used for metal removal. On the other hand, an alkaline cleaning liquid represented by APM (ammonia-hydrogen peroxide solution) is excellent in the ability to remove particles, but insufficient in the ability to remove metals.
【０００６】そこで、金属汚染の除去には酸系洗浄液の
ＨＰＭまたはＤＨＦに頼らざるを得ないのが現状である
が、これらの洗浄液は金属の溶解力が強く、半導体基板
表面に施された金属配線を腐食してしまうので問題が残
る。そこで、半導体基板表面に施された金属配線の腐食
を回避するために物理的洗浄が用いられている。物理的
洗浄としては高速回転のブラシで表面を洗浄するブラシ
スクラブ洗浄や微小な氷を表面にぶつけるアイススクラ
ブ洗浄、超純水をノズルから噴射する高圧ジェット洗
浄、高周波を用いるメガソニック洗浄などがあるが、こ
れらは何れも金属配線の腐食を回避する点では有効であ
るが金属の除去能力が期待できず、酸系洗浄液と併用す
ることが提案されている。Therefore, at present, it is necessary to rely on HPM or DHF of an acid-based cleaning liquid to remove metal contamination. However, these cleaning liquids have a strong metal dissolving power, and the metal applied to the surface of the semiconductor substrate is hardly removed. The problem remains because the wiring is corroded. Therefore, physical cleaning is used to avoid corrosion of metal wiring provided on the surface of the semiconductor substrate. Examples of physical cleaning include brush scrub cleaning in which the surface is cleaned with a high-speed rotating brush, ice scrub cleaning in which minute ice is hit on the surface, high-pressure jet cleaning in which ultrapure water is sprayed from a nozzle, and megasonic cleaning using high frequency. However, any of these is effective in avoiding corrosion of metal wiring, but cannot remove metal, and it is proposed to use it together with an acid-based cleaning solution.
【０００７】しかし、ＲＣＡ洗浄用の無機酸系洗浄剤を
併用した場合、金属の除去効果は期待できるが、やはり
金属配線にダメージを与えてしまったり、絶縁膜のシリ
コン酸化物表面をエッチングしてしまったりする為、酸
濃度を極力薄くしたり、洗浄時間を極力短くしたりなど
の工夫が必要となる。これでは、充分な洗浄効果は期待
できなくなる。However, when an inorganic acid-based cleaning agent for RCA cleaning is used together, an effect of removing metal can be expected, but it also damages metal wiring and etches the silicon oxide surface of the insulating film. Therefore, it is necessary to take measures such as reducing the acid concentration as much as possible and shortening the cleaning time as much as possible. In this case, a sufficient cleaning effect cannot be expected.
【０００８】また、例えば、モノカルボン酸と界面活性
剤との水溶液を用い、半導体基板表面を洗浄する方法も
あるが、これは界面活性剤が液と半導体基板表面との濡
れ性を改善しているにすぎず、金属汚染の除去に長時間
を必要とし、尚且つ充分な洗浄効果が得られない。ま
た、クエン酸水溶液とブラシスクラブ洗浄とを組合せ、
金属除去を行った例もあるが、クエン酸水溶液のみでは
金属汚染の除去効果が弱く、充分な洗浄効果が得られな
い。In addition, for example, there is a method of cleaning the surface of a semiconductor substrate using an aqueous solution of a monocarboxylic acid and a surfactant. However, this method improves the wettability between the liquid and the surface of the semiconductor substrate. However, it takes a long time to remove metal contamination, and a sufficient cleaning effect cannot be obtained. In addition, a combination of citric acid aqueous solution and brush scrub cleaning,
Although there is an example in which metal is removed, the effect of removing metal contamination is weak with only citric acid aqueous solution, and a sufficient cleaning effect cannot be obtained.
【０００９】以上のように半導体材料上に施された金属
配線の腐食を起こすことなく、また、半導体基板表面の
平坦度を損なうことなしに、パーティクルや金属汚染の
除去が行える有効な手段は未だ見出されていない。As described above, there is still no effective means for removing particles and metal contamination without causing corrosion of the metal wiring provided on the semiconductor material and without impairing the flatness of the surface of the semiconductor substrate. Not found.
【００１０】[0010]
【発明が解決しようとする課題】上記した如き状況に鑑
み本発明が解決しようとする課題は、半導体基板表面に
施された金属配線の腐食の問題や半導体基板表面のマイ
クロラフネスの増加の問題を起こすことなく洗浄が可能
な、半導体基板表面の洗浄処理剤及びこれを用いた処理
方法を提供することにある。SUMMARY OF THE INVENTION In view of the above circumstances, the present invention has been made to solve the problems of corrosion of metal wiring provided on the surface of a semiconductor substrate and of micro-roughness on the surface of the semiconductor substrate. An object of the present invention is to provide a cleaning agent for a semiconductor substrate surface, which can be cleaned without causing the cleaning, and a processing method using the same.
【００１１】[0011]
【発明を解決するための手段】本発明は上記課題を解決
する目的でなされたものであり、本発明は、カルボキシ
ル基を少なくとも１個有する有機酸と、錯化剤とを含ん
で成る半導体基板表面の洗浄処理剤に関する。また、本
発明は更に、カルボキシル基を少なくとも１個有する有
機酸と、錯化剤とを含んで成る洗浄処理剤で、半導体基
板表面を処理することから成る半導体基板表面の洗浄処
理方法に関する。SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and the present invention provides a semiconductor substrate comprising an organic acid having at least one carboxyl group and a complexing agent. It relates to a surface treatment agent. Further, the present invention further relates to a method for cleaning the surface of a semiconductor substrate, comprising treating the surface of the semiconductor substrate with a cleaning agent comprising an organic acid having at least one carboxyl group and a complexing agent.
【００１２】本発明者らは上記目的を達成すべく鋭意研
究を重ねた結果、カルボキシル基を少なくとも１個有す
る有機酸に、金属汚染物質と錯化合物を形成する錯化剤
を添加して半導体基板表面を洗浄することにより、強酸
や強アルカリ性溶液を使用する際に生じる、半導体基板
表面に施された金属配線の腐食を起こすことなく、ま
た、半導体基板表面の平坦度を損なうことなく、容易に
半導体基板表面に吸着又は付着した金属汚染の除去を行
うことができることを見出し、本発明を完成させるに至
った。The present inventors have conducted intensive studies to achieve the above object, and as a result, added a complexing agent which forms a complex compound with a metal contaminant to an organic acid having at least one carboxyl group to form a semiconductor substrate. By cleaning the surface, it is easy to prevent corrosion of metal wiring applied to the surface of the semiconductor substrate, which occurs when using a strong acid or strong alkaline solution, and without impairing the flatness of the surface of the semiconductor substrate. The inventors have found that metal contamination adsorbed or attached to the surface of a semiconductor substrate can be removed, and have completed the present invention.
【００１３】本発明の方法により上記目的を達成し得る
理由は定かではないが、例えば有機酸がわずかではある
がFeやAlの金属酸化物や金属水酸化物を溶解し、溶解し
た金属イオンが錯化剤と金属錯体を形成すれば金属が溶
解する方向に平衡が移動して有機酸の金属溶解力が向上
し、半導体基板表面に吸着又は付着した金属の除去が可
能となるのではないかと考えられる。The reason why the above-mentioned object can be achieved by the method of the present invention is not clear, but, for example, although the amount of the organic acid is small, the metal oxide or metal hydroxide of Fe or Al is dissolved and the dissolved metal ion is dissolved. Forming a metal complex with a complexing agent shifts the equilibrium in the direction in which the metal dissolves, improving the metal dissolving power of the organic acid, and removing the metal adsorbed or attached to the semiconductor substrate surface. Conceivable.
【００１４】本発明に係る有機酸は、カルボキシル基を
少なくとも１個、好ましくは１〜３個、より好ましくは
２〜３個有する有機酸であり、さらに、１〜３個の水酸
基及び／または１〜３個のアミノ基を有していても良
い。これら本発明に係る有機酸の具体例としては、例え
ば、ぎ酸、酢酸、プロピオン酸等のモノカルボン酸類；
シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン
酸、ピメリン酸、マレイン酸、フマル酸、フタル酸等の
ジカルボン酸類；トリメリト酸、トリカルバリリル酸等
のトリカルボン酸類；以下のようなオキシカルボン酸
類、例えば、ヒドロキシ酪酸、乳酸、サリチル酸等のオ
キシモノカルボン酸類、リンゴ酸、酒石酸等のオキシジ
カルボン酸類、クエン酸等のオキシトリカルボン酸類；
アスパラギン酸、グルタミン酸等のアミノカルボン酸類
等が挙げられる。上記有機酸の中でも、ジカルボン酸類
またはオキシカルボン酸類が好ましい。本発明に係る有
機酸は、単独で使用しても、また、２種以上適宜組合せ
て用いてもよい。The organic acid according to the present invention is an organic acid having at least one, preferably one to three, more preferably two to three carboxyl groups, and further has one to three hydroxyl groups and / or one to three carboxyl groups. It may have up to 3 amino groups. Specific examples of these organic acids according to the present invention include, for example, monocarboxylic acids such as formic acid, acetic acid, and propionic acid;
Dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, fumaric acid, and phthalic acid; tricarboxylic acids such as trimellitic acid and tricarbarylyl acid; and the following oxycarboxylic acids For example, oxymonocarboxylic acids such as hydroxybutyric acid, lactic acid, and salicylic acid; oxydicarboxylic acids such as malic acid and tartaric acid; and oxytricarboxylic acids such as citric acid;
Examples include aminocarboxylic acids such as aspartic acid and glutamic acid. Among the organic acids, dicarboxylic acids and oxycarboxylic acids are preferred. The organic acids according to the present invention may be used alone or in an appropriate combination of two or more.
【００１５】また、本発明に係る、FeやAlなどの金属汚
染物質と錯化合物を形成する錯化剤（以下、本発明に係
る錯化剤と略記する。）としては、例えば、エチレンジ
アミン四酢酸〔ＥＤＴＡ〕、トランス−1,2-ジアミノシ
クロヘキサン四酢酸〔ＣｙＤＴＡ〕等のアミノポリカル
ボン酸類、エチレンジアミンテトラ（メチレンホスホン
酸）〔ＥＤＴＰＯ〕、エチレンジアミンジ（メチレンホ
スホン酸）〔ＥＤＤＰＯ〕、ニトリロトリス（メチレン
ホスホン酸）〔ＮＴＰＯ〕、1-ヒドロキシエチリデン-
1,1'-ジホスホン酸〔ＨＥＤＰＯ〕等のホスホン酸類、
トリポリリン酸、ヘキサメタリン酸等の縮合リン酸類、
アセチルアセトン、ヘキサフルオロアセチルアセトン等
のジケトン類、エチレンジアミン、トリエタノールアミ
ン等のアミン類、またはハロゲン化物イオン（Ｆ-、C
l-、Br-、Ｉ-）、シアン化物イオン、チオシアン酸イオ
ン、チオ硫酸イオン、アンモニウムイオン等の無機イオ
ン等が挙げられる。上記錯化剤の中でもホスホン酸類が
好ましい。本発明に係る錯化剤は、単独で使用しても、
また、２種以上適宜組合せて用いてもよい。Examples of the complexing agent according to the present invention which forms a complex compound with a metal contaminant such as Fe or Al (hereinafter, abbreviated as the complexing agent according to the present invention) include, for example, ethylenediaminetetraacetic acid. [EDTA], aminopolycarboxylic acids such as trans-1,2-diaminocyclohexanetetraacetic acid [CyDTA], ethylenediaminetetra (methylenephosphonic acid) [EDTPO], ethylenediaminedi (methylenephosphonic acid) [EDDPO], nitrilotris (methylene Phosphonic acid) [NTPO], 1-hydroxyethylidene-
Phosphonic acids such as 1,1'-diphosphonic acid [HEDPO],
Condensed phosphoric acids such as tripolyphosphoric acid and hexametaphosphoric acid,
Diketones such as acetylacetone and hexafluoroacetylacetone, amines such as ethylenediamine and triethanolamine, or halide ions (F − , C
l -, Br -, I - ), cyanide ions, thiocyanate ions, thiosulfate ions, inorganic ions, etc. and an ammonium ion. Among the above complexing agents, phosphonic acids are preferred. The complexing agent according to the present invention, even when used alone,
Also, two or more kinds may be used in appropriate combination.
【００１６】本発明の半導体基板表面の洗浄処理剤（以
下、「本発明の処理剤」と略記する。）は、通常溶液、
好ましくは水溶液として使用されるものであり、本発明
に係る有機酸及び本発明に係る錯化剤を水に溶解して作
製する。The cleaning agent for cleaning the surface of a semiconductor substrate of the present invention (hereinafter abbreviated as “the processing agent of the present invention”) is usually a solution,
It is preferably used as an aqueous solution, and is prepared by dissolving the organic acid according to the present invention and the complexing agent according to the present invention in water.
【００１７】本発明に係る有機酸及び本発明に係る錯化
剤それぞれの使用濃度が低すぎると、洗浄効果が充分で
なく、半導体基板表面に予想以上の汚染があった場合な
どには効果が薄れてしまう。一方、本発明に係る有機酸
の使用濃度が高すぎる場合は洗浄効果には特に不都合は
ないが、コストの面から好ましくない。また、本発明に
係る錯化剤の使用濃度が高すぎる場合は洗浄効果には特
に不都合はないが、錯化剤を多量に使用することは半導
体基板表面に有害な炭素汚染は生ぜしめ電気的特性に問
題が起こるし、また、コストの面から好ましくない。If the concentration of each of the organic acid according to the present invention and the complexing agent according to the present invention is too low, the cleaning effect is not sufficient, and the effect is unsatisfactory when the surface of the semiconductor substrate is contaminated more than expected. It will fade. On the other hand, when the use concentration of the organic acid according to the present invention is too high, the cleaning effect is not particularly inconvenient, but is not preferable in terms of cost. When the concentration of the complexing agent according to the present invention is too high, the cleaning effect is not particularly disadvantageous, but using a large amount of the complexing agent causes harmful carbon contamination on the surface of the semiconductor substrate and causes electrical There is a problem with the characteristics, and it is not preferable in terms of cost.
【００１８】通常、本発明に係る有機酸は、0.05〜50重
量％、好ましくは１〜30重量％の濃度範囲になるように
用いられる。また、本発明に係る錯化剤は、0.01〜10重
量％、好ましくは0.1〜１重量％の濃度範囲になるよう
に用いられる。Usually, the organic acid according to the present invention is used in a concentration range of 0.05 to 50% by weight, preferably 1 to 30% by weight. The complexing agent according to the present invention is used in a concentration range of 0.01 to 10% by weight, preferably 0.1 to 1% by weight.
【００１９】本発明の処理剤を用いた洗浄処理の方法と
しては、本発明の処理剤が半導体基板表面と接触できる
方法であれば良く、ウェーハを本発明の処理剤に浸漬す
る方法や、ウェーハ表面に本発明の処理剤を噴霧する方
法等が挙げられる。また、本発明の処理剤による洗浄
と、ブラシスクラブやメガソニック等の物理的洗浄とを
併用しても良い。The method of the cleaning treatment using the treatment agent of the present invention may be any method as long as the treatment agent of the present invention can be brought into contact with the surface of the semiconductor substrate. A method of spraying the treating agent of the present invention on the surface is exemplified. Further, the cleaning with the treatment agent of the present invention may be used in combination with the physical cleaning such as brush scrub or megasonic.
【００２０】本発明の処理剤は常温においても洗浄効果
を示すが、高温の方が微粒子の除去効率が高いため一般
的には該溶液を適度に加熱して使用する。尚、本発明の
処理剤は上記構成成分の他に本発明の効果を阻害しない
範囲で各種補助成分（例えば界面活性剤、緩衝剤、有機
溶媒等）が含まれていても一向に差し支えない。Although the treating agent of the present invention exhibits a cleaning effect even at room temperature, the higher the temperature, the higher the efficiency of removing fine particles, so that the solution is generally heated and used appropriately. The treating agent of the present invention may contain various auxiliary components (for example, a surfactant, a buffer, an organic solvent, etc.) in addition to the above-mentioned constituent components as long as the effects of the present invention are not impaired.
【００２１】以下に、実施例、比較例を挙げて本発明を
更に詳細に説明するが、本発明はこれらにより何ら限定
されるものではない。尚、本発明におけるシリコンウェ
ーハ表面に吸着した金属濃度はウェーハ表面の金属を希
フッ酸溶液で洗浄回収し、黒鉛炉原子吸光法（以下、希
フッ酸回収−原子吸光法と略記する。）にて求めた。ま
た、調液する際や分析に使用した水は超純水を使用し、
分析に使用したフッ酸も超高純度試薬を用いた。Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The concentration of the metal adsorbed on the silicon wafer surface in the present invention is determined by washing and recovering the metal on the wafer surface with a diluted hydrofluoric acid solution and using a graphite furnace atomic absorption method (hereinafter abbreviated as dilute hydrofluoric acid recovery-atomic absorption method). I asked. In addition, use ultrapure water when preparing liquids and for analysis.
The hydrofluoric acid used for the analysis also used an ultra-high purity reagent.
【００２２】[0022]
実施例１ ６インチ、Ｐ型（100）シリコンウェーハをFe、Al及びC
u（各硝酸塩溶液）を純水に100ppb添加した液に浸漬
し、その後、スピンドライヤーにて乾燥させた。該ウェ
ーハ表面に吸着した金属汚染量を希フッ酸回収−原子吸
光法により測定したところ、それぞれ、Fe ５×1013ato
ms／cm2、Al ８×1013atoms ／cm2、Cu ２×1013atoms
／cm2がシリコンウェーハ表面に吸着していることが判
った。上記のウェーハを表１のＮｏ.１〜１０の各組成
から成る本発明の処理剤溶液に浸漬し、70℃で、10分間
加熱した。その後、超純水で洗浄し、スピンドライヤー
にて乾燥させ、ウェーハの表面金属量を上記方法で定量
した。結果を表１に示す。Example 1 A 6-inch, P-type (100) silicon wafer was made of Fe, Al and C
u (each nitrate solution) was immersed in a solution obtained by adding 100 ppb to pure water, and then dried with a spin drier. Adsorbed metal contamination quantity dilute hydrofluoric acid recovery on the wafer surface - was measured by atomic absorption method, respectively, Fe 5 × 10 13 ato
ms / cm 2 , Al 8 × 10 13 atoms / cm 2 , Cu 2 × 10 13 atoms
/ Cm 2 was adsorbed on the silicon wafer surface. The above-mentioned wafer was immersed in the treating agent solution of the present invention composed of each composition of Nos. 1 to 10 in Table 1 and heated at 70 ° C. for 10 minutes. Thereafter, the wafer was washed with ultrapure water and dried with a spin drier, and the amount of metal on the surface of the wafer was quantified by the above method. Table 1 shows the results.
【００２３】比較例１ 実施例１で用いたFe、AlそしてCuで汚染させたウェーハ
を表１のＮｏ.１１及び１２の各組成から成る溶液及び
超純水（Ｎｏ．１３）に浸漬し、実施例１と同様にして
処理を行った。結果を表１に併せて示す。Comparative Example 1 A wafer contaminated with Fe, Al and Cu used in Example 1 was immersed in a solution having each composition of Nos. 11 and 12 in Table 1 and ultrapure water (No. 13). The processing was performed in the same manner as in Example 1. The results are shown in Table 1.
【００２４】[0024]
【表１】 [Table 1]
【００２５】表１から明らかな如く、本発明の処理剤を
用いて洗浄処理することにより、ウェーハ表面の金属残
存量を大幅に減少させることができることが判る。As is clear from Table 1, it can be seen that the amount of residual metal on the wafer surface can be significantly reduced by performing the cleaning treatment using the treatment agent of the present invention.
【００２６】実施例２ 実施例１で用いたウェーハと同様にしてFe、AlそしてCu
で汚染させたウェーハを、ポリビニルアルコール製のブ
ラシを用いてブラシスクラブ洗浄する際に、表２のＮ
ｏ.１４〜２３の各組成から成る本発明の処理剤を使用
した。処理温度は25℃、 洗浄時間は１分間とした。洗
浄後、超純水で洗浄し、スピンドライヤーにて乾燥さ
せ、ウェーハ表面の金属量を実施例１と同様の方法によ
り定量した。結果を表２に示す。Example 2 Fe, Al and Cu were prepared in the same manner as in the wafer used in Example 1.
When the wafer contaminated with the above was brush-scrubbed with a polyvinyl alcohol brush, N in Table 2 was used.
o. The treating agents of the present invention having the compositions of 14 to 23 were used. The treatment temperature was 25 ° C., and the washing time was 1 minute. After washing, the substrate was washed with ultrapure water and dried with a spin drier, and the amount of metal on the wafer surface was quantified in the same manner as in Example 1. Table 2 shows the results.
【００２７】比較例２ 実施例１で用いた金属汚染させたウェーハをポリビニル
アルコール製のブラシを用いてブラシスクラブ洗浄する
際、表２のＮｏ．２４及び２５の各組成から成る溶液及
び超純水（Ｎｏ．２６）を使用し、実施例２と同様に処
理して、ウェーハ表面の残存金属量の測定を行った。結
果を表２に併せて示す。Comparative Example 2 When the metal-contaminated wafer used in Example 1 was washed with a brush made of polyvinyl alcohol with a brush scrub, the wafer was subjected to No. 2 in Table 2. Using a solution having each composition of Nos. 24 and 25 and ultrapure water (No. 26), the treatment was performed in the same manner as in Example 2, and the amount of residual metal on the wafer surface was measured. The results are shown in Table 2.
【００２８】[0028]
【表２】 [Table 2]
【００２９】表２から明らかな如く、本発明の処理剤を
用いて物理的洗浄を行った場合も、金属の残存量が顕著
に減少することが判る。また、Ｎｏ．１４〜１８の結果
から、カルボキシル基を１有する有機酸である酢酸よ
り、カルボキシル基を２以上有する有機酸であるシュウ
酸、クエン酸、マロン酸及びコハク酸の方が洗浄効果が
高いことも判る。As is evident from Table 2, when the cleaning agent of the present invention is used for physical cleaning, the residual amount of metal is significantly reduced. In addition, No. From the results of 14 to 18, it is also understood that oxalic acid, citric acid, malonic acid, and succinic acid, which are organic acids having two or more carboxyl groups, have a higher cleaning effect than acetic acid, which is an organic acid having one carboxyl group. .
【００３０】実施例３ Al及びCu配線を施したシリコンウェーハを本発明の処理
剤である上記実施例１に係る表１に記載のＮｏ.１及び
２の組成からなる溶液に70℃で１時間浸漬させた。その
後、超純水で洗浄し、スピンドライヤーにて乾燥させ、
金属配線を顕微鏡にて目視確認し、更にテスターにて金
属配線の断線の有無を確認した。その結果、本発明の処
理剤に浸漬させたウェーハは、金属配線の腐食が無く、
断線も起こっていないことが判った。Example 3 A silicon wafer provided with Al and Cu wirings was treated at 70 ° C. for 1 hour with a solution comprising the compositions of Nos. 1 and 2 shown in Table 1 according to Example 1 as a treating agent of the present invention. It was immersed. After that, wash with ultrapure water and dry with a spin dryer,
The metal wiring was visually checked with a microscope, and further, the presence or absence of disconnection of the metal wiring was checked with a tester. As a result, the wafer immersed in the treatment agent of the present invention has no corrosion of metal wiring,
It turned out that there was no disconnection.
【００３１】比較例３ ＨＰＭ（ＨＣｌ：Ｈ2Ｏ2：Ｈ2Ｏ＝１：１：５）及びＤ
ＨＦ （１％フッ酸溶液）を用い実施例３と同様にして
処理を行い、侵食や断線の有無等の確認を行った。その
結果、Al及びCuの配線が侵食され、ところによって断線
していることが判った。Comparative Example 3 HPM (HCl: H 2 O 2 : H 2 O = 1: 1: 5) and D
The treatment was performed in the same manner as in Example 3 using HF (1% hydrofluoric acid solution), and the presence or absence of erosion or disconnection was confirmed. As a result, it was found that the wiring of Al and Cu was eroded, and the wiring was broken in some places.
【００３２】[0032]
【発明の効果】本発明の洗浄処理剤を使用することによ
り、強酸や強アルカリ性溶液を使用する際に生じる金属
配線の腐食を起こすことなく、また、半導体基板表面の
平坦度を損なうことなしに、半導体基板表面に吸着又は
付着した金属不純物を効率良く除去することが可能とな
るので、本発明は斯業に貢献するところ大なる発明であ
る。By using the cleaning agent of the present invention, the corrosion of metal wiring which occurs when a strong acid or a strong alkaline solution is used is not caused, and the flatness of the surface of the semiconductor substrate is not impaired. Since the metal impurities adsorbed or attached to the surface of the semiconductor substrate can be efficiently removed, the present invention is a major invention that contributes to the industry.
フロントページの続き (56)参考文献 特開 平３−219000（ＪＰ，Ａ) 特開 平４−130100（ＪＰ，Ａ) 特開 平６−291099（ＪＰ，Ａ) 特開 平５−275405（ＪＰ，Ａ) 独国特許出願公開19525521（ＤＥ，Ａ １) (58)調査した分野(Int.Cl.7，ＤＢ名) H01L 21/304 647 C11D 7/26 C11D 7/32 - 7/36 Continuation of the front page (56) References JP-A-3-2199000 (JP, A) JP-A-4-130100 (JP, A) JP-A-6-291099 (JP, A) JP-A-5-275405 (JP) , A) German Patent Application Publication No. 19525521 (DE, A1) (58) Fields investigated (Int. Cl. 7 , DB name) H01L 21/304 647 C11D 7/26 C11D 7/ 32-7/36
Claims (22)
カルボン酸、没食子酸以外のオキシカルボン酸、及びア
スパラギン酸及びグルタミン酸から選ばれたアミノカル
ボン酸から成る群より選ばれた有機酸及び(b)エチレン
ジアミン四酢酸及びトランス-1,2-ジアミノシクロヘキ
サン四酢酸から選ばれたアミノポリカルボン酸、ホスホ
ン酸誘導体、縮合リン酸、ジケトン類、アミン類、及び
ハロゲン化物イオン、シアン化物イオン、チオシアン酸
イオン、チオ硫酸イオン及びアンモニウムイオンから選
ばれた無機イオンから成る群より選ばれた錯化剤を主に
含んで成る、金属配線が施された半導体基板表面の洗浄
処理剤。1. An organic acid selected from the group consisting of (a) monocarboxylic acids, dicarboxylic acids, tricarboxylic acids, oxycarboxylic acids other than gallic acid, and aminocarboxylic acids selected from aspartic acid and glutamic acid. ) Aminopolycarboxylic acids selected from ethylenediaminetetraacetic acid and trans-1,2-diaminocyclohexanetetraacetic acid, phosphonic acid derivatives, condensed phosphoric acid, diketones, amines, and halide ions, cyanide ions, and thiocyanate ions A cleaning agent for a surface of a semiconductor substrate provided with metal wiring, mainly comprising a complexing agent selected from the group consisting of inorganic ions selected from thiosulfate ions and ammonium ions.
カルボン酸及び没食子酸以外のオキシカルボン酸から成
る群より選ばれた化合物及び(b)エチレンジアミン四酢
酸及びトランス-1,2-ジアミノシクロヘキサン四酢酸か
ら選ばれたアミノポリカルボン酸、ホスホン酸誘導体、
縮合リン酸、ジケトン類、アミン類、及びハロゲン化物
イオン、シアン化物イオン、チオシアン酸イオン、チオ
硫酸イオン及びアンモニウムイオンから選ばれた無機イ
オンから成る群より選ばれた化合物を主に含んで成る、
金属配線が施された半導体基板表面の洗浄処理剤。2. Compounds selected from the group consisting of (a) monocarboxylic acids, dicarboxylic acids, tricarboxylic acids and oxycarboxylic acids other than gallic acid, and (b) ethylenediaminetetraacetic acid and trans-1,2-diaminocyclohexanetetracarboxylic acid. Aminopolycarboxylic acids selected from acetic acid, phosphonic acid derivatives,
Mainly comprising a compound selected from the group consisting of condensed phosphoric acid, diketones, amines, and halide ions, cyanide ions, thiocyanate ions, thiosulfate ions, and inorganic ions selected from ammonium ions .
A cleaning agent for the surface of a semiconductor substrate provided with metal wiring .
及びプロピオン酸から成る群より選ばれたものである請
求項１又は２に記載の洗浄処理剤。3. The cleaning agent according to claim 1, wherein the monocarboxylic acid of the component (a) is selected from the group consisting of formic acid, acetic acid and propionic acid.
ロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン
酸、マレイン酸、フマル酸及びフタル酸から成る群より
選ばれたものである請求項１又は２に記載の洗浄処理
剤。4. The dicarboxylic acid of component (a) is selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, fumaric acid and phthalic acid. The cleaning agent according to claim 1.
酸及びトリカルバリリル酸から成る群より選ばれたもの
である請求項１又は２に記載の洗浄処理剤。5. The cleaning agent according to claim 1, wherein the tricarboxylic acid of the component (a) is selected from the group consisting of trimellitic acid and tricarballylic acid.
１〜２個有するものである請求項１又は２に記載の洗浄
処理剤。6. The cleaning agent according to claim 1, wherein the oxycarboxylic acid of the component (a) has one or two hydroxyl groups.
ノカルボン酸、オキシジカルボン酸又はオキシトリカル
ボン酸である請求項６に記載の洗浄処理剤。7. The cleaning agent according to claim 6, wherein the oxycarboxylic acid of the component (a) is oxymonocarboxylic acid, oxydicarboxylic acid or oxytricarboxylic acid.
シ酪酸、乳酸、サリチル酸、リンゴ酸、酒石酸及びクエ
ン酸から成る群より選ばれたものである請求項６に記載
の洗浄処理剤。8. The cleaning agent according to claim 6, wherein the oxycarboxylic acid of the component (a) is selected from the group consisting of hydroxybutyric acid, lactic acid, salicylic acid, malic acid, tartaric acid and citric acid.
ンテトラ（メチレンホスホン酸）、エチレンジアミンジ
（メチレンホスホン酸）、ニトリルトリス（メチレンホ
スホン酸）及び１−ヒドロキシエチリデン−１，１’−
ジホスホン酸から成る群より選ばれたものである請求項
１又は２に記載の洗浄処理剤。9. The phosphonic acid of component (b) is ethylenediaminetetra (methylenephosphonic acid), ethylenediaminedi (methylenephosphonic acid), nitrile tris (methylenephosphonic acid) and 1-hydroxyethylidene-1,1'-
3. The cleaning agent according to claim 1, which is selected from the group consisting of diphosphonic acids.
酸及びヘキサメタリン酸から成る群より選ばれたもので
ある請求項１又は２に記載の洗浄処理剤。10. The cleaning agent according to claim 1, wherein the condensed phosphoric acid of the component (b) is selected from the group consisting of tripolyphosphoric acid and hexametaphosphoric acid.
トン及びヘキサフルオロアセチルアセトンから成る群よ
り選ばれたものである請求項１又は２に記載の洗浄処理
剤。11. The cleaning agent according to claim 1, wherein the diketone of component (b) is selected from the group consisting of acetylacetone and hexafluoroacetylacetone.
ン及びトリエタノールアミンから成る群より選ばれたも
のである請求項１又は２に記載の洗浄処理剤。12. The cleaning agent according to claim 1, wherein the amine of component (b) is selected from the group consisting of ethylenediamine and triethanolamine.
ン酸、酒石酸、コハク酸、酢酸、グルタル酸及びアジピ
ン酸から成る群より選ばれたものである請求項１又は２
に記載の洗浄処理剤。13. The composition of claim 1, wherein component (a) is selected from the group consisting of citric acid, oxalic acid, malonic acid, tartaric acid, succinic acid, acetic acid, glutaric acid and adipic acid.
3. The cleaning agent according to item 1.
（メチレンホスホン酸）、ヘキサメタリン酸、アセチル
アセトン、トランス−１，２−ジアミノシクロヘキサン
四酢酸、エチレンジアミン四酢酸、アンモニウムイオ
ン、フッ素イオン、１−ヒドロキシエチリデン−１，
１’−ジホスホン酸、ニトリロトリス（メチレンホスホ
ン酸）、チオシアン酸イオン及びエチレンジアミンテト
ラ（メチレンホスホン酸）から成る群より選ばれたもの
である請求項１又は２に記載の洗浄処理剤。14. Component (b) is ethylenediaminetetra (methylenephosphonic acid), hexametaphosphoric acid, acetylacetone, trans-1,2-diaminocyclohexanetetraacetic acid, ethylenediaminetetraacetic acid, ammonium ion, fluorine ion, 1-hydroxyethylidene- 1,
3. The cleaning agent according to claim 1, wherein the cleaning agent is selected from the group consisting of 1'-diphosphonic acid, nitrilotris (methylene phosphonic acid), thiocyanate ion, and ethylenediamine tetra (methylene phosphonic acid).
溶媒を含んでなる請求項１〜１４の何れかに記載の洗浄
処理剤。15. The cleaning agent according to claim 1, further comprising a surfactant, a buffer, and / or an organic solvent.
１４の何れかに記載の洗浄処理剤。16. The method according to claim 1, further comprising a surfactant.
14. The cleaning treatment agent according to any one of 14.
記載の洗浄処理剤。17. The cleaning agent according to claim 1, which is an aqueous solution.
れる水溶液からなるものである請求項１〜１４の何れか
に記載の洗浄処理剤。18. The cleaning agent according to claim 1, comprising an aqueous solution obtained by dissolving component (a) and component (b) in water.
理剤を用いることを特徴とする金属配線の施された半導
体基板表面の洗浄処理方法。19. A method for cleaning a surface of a semiconductor substrate provided with metal wiring, comprising using the cleaning agent according to claim 1. Description:
理剤に金属配線の施された半導体基板表面を浸漬する
か、金属配線の施された半導体基板表面に当該洗浄処理
剤を噴霧するものである請求項１９に記載の洗浄処理方
法。20. A cleaning treatment agent according to claim 1, wherein the surface of the semiconductor substrate provided with the metal wiring is immersed or the cleaning treatment agent is sprayed on the surface of the semiconductor substrate provided with the metal wiring. 20. The cleaning method according to claim 19, wherein the cleaning is performed.
は２０に記載の洗浄処理方法。21. The cleaning method according to claim 19, wherein physical cleaning is further used.
物理的研磨工程後のものである請求項１９〜２１の何れ
かに記載の洗浄処理方法。 22. The cleaning method according to any one of claims 19 to 21 semiconductor substrate subjected to the metal wires is that after the chemical physical polishing process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15283497A JP3219020B2 (en) | 1996-06-05 | 1997-05-27 | Cleaning agent |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8-165353 | 1996-06-05 | ||
| JP16535396 | 1996-06-05 | ||
| JP15283497A JP3219020B2 (en) | 1996-06-05 | 1997-05-27 | Cleaning agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1072594A JPH1072594A (en) | 1998-03-17 |
| JP3219020B2 true JP3219020B2 (en) | 2001-10-15 |
Family
ID=26481632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15283497A Expired - Lifetime JP3219020B2 (en) | 1996-06-05 | 1997-05-27 | Cleaning agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3219020B2 (en) |
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1997
- 1997-05-27 JP JP15283497A patent/JP3219020B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7541322B2 (en) | 2004-02-09 | 2009-06-02 | Mitsubishi Chemical Corporation | Cleaning solution for substrate for semiconductor device and cleaning method |
| EP2386623A1 (en) | 2010-05-14 | 2011-11-16 | Fujifilm Corporation | Cleaning composition, method for producing semiconductor device, and cleaning method |
| US8617417B2 (en) | 2010-05-14 | 2013-12-31 | Fujifilm Corporation | Cleaning composition, method for producing semiconductor device, and cleaning method |
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|---|---|
| JPH1072594A (en) | 1998-03-17 |
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