JP4154999B2 - Cleaning method - Google Patents
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- JP4154999B2 JP4154999B2 JP2002320356A JP2002320356A JP4154999B2 JP 4154999 B2 JP4154999 B2 JP 4154999B2 JP 2002320356 A JP2002320356 A JP 2002320356A JP 2002320356 A JP2002320356 A JP 2002320356A JP 4154999 B2 JP4154999 B2 JP 4154999B2
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- cleaning
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- wiring
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- Detergent Compositions (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は化学的機械的研磨した後の半導体デバイスの洗浄方法に関する。更に詳しくは、銅配線半導体デバイスの洗浄方法に関するものである。
【０００２】
【従来の技術】
近年、情報化技術の急速な進展に伴い大規模集積回路（ＬＳＩ、ＵＬＳＩ、ＶＬＳＩ）の微細化、高密度化、高集積化による高速化が成される動向にあり、配線の多層化による技術開発が行われている。配線の多層化を達成するには配線ピッチ幅の縮小及び配線間容量の低減等を行うことが必要となり配線ピッチ幅の縮小解決策として現有の金属配線材料であるタングステン及びアルミニウムをより抵抗率の低い銅に変更する技術開発が精力的に研究されている。
【０００３】
銅はアンモニア又はアミン類に腐食されやすく、従来のアルミ配線に対して使用されてきた洗浄剤も変更が求められている。
【０００４】
例えば、配線形成の際に使用されるレジストを最終的に剥離する際、従来のアルミ配線時に使用されてきたモノエタノールアミン系レジスト剥離剤は銅腐食が極めて高く、その代替が求められている。
【０００５】
また、銅配線は埋め込みによるダマシンプロセスが主流となる傾向にある。ダマシン法により埋め込み形成された配線の平坦化は機械的研摩作用と化学的研摩作用の相乗性を利用した所謂、ＣＭＰ（Ｃｈｅｍｉｃａｌ Ｍｅｃｈａｎｉｃａｌ Ｐｏｌｉｓｈｉｎｇ）法により成されており、銅配線材料も同一方法で研摩が成されている。
【０００６】
しかしながら、このＣＭＰによる方法では、金属研磨を行なった後、研磨剤、研磨屑、金属不純物がウエハーに多数付着するため、ウエハー表面を洗浄する必要がある。アルカリ性溶液で洗浄を行なうと不純物の再付着が抑制できるため、銅以外の金属の場合は、アンモニアが一般的に使用されてきた。ところが、銅の場合は、アンモニアに腐食されやすく、アンモニアを洗浄剤として使用することができなかった。そこで、アンモニアに銅の防食剤を添加し、銅の腐食速度を低減させる方法が提案されている。例えば、特許文献１には、防食剤としてメルカプト基を含む化合物が開示されている。しかし、同公報に記載されているようにメルカプト基を含む化合物は特有の不快臭があり、環境的にも、工業的にも使用するには問題がある。その他の防食剤としてベンゾトリアゾールなどの芳香族化合物が知られているが、有害性が高いなどの環境問題がある。また防食剤を添加する方法では、少量の防食剤で銅の腐食を抑制することはできないため、基本的に銅を腐食しやすいアンモニアを使用しない方法が望まれていた。
【０００７】
このように、従来のアンモニア、アミン類を含む洗浄剤は、銅への腐食性の点で十分なものとはいえなかった。
【０００８】
【特許文献１】
特開２０００−２７３６６３号公報（特許請求の範囲）
【０００９】
【発明が解決しようとする課題】
本発明の目的は、上記の課題に鑑みて、化学的機械的研磨した後の半導体デバイスの洗浄方法において、特に銅を侵さない洗浄方法を提供することにある。
【００１０】
【課題を解決するための手段】
本発明者らは、化学的機械的研磨した後の半導体デバイスの洗浄方法について鋭意検討した結果、エチレン尿素を必須成分とする洗浄剤が銅を侵さない洗浄剤として用いる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。
【００１１】
すなわち、本発明はエチレン尿素を含んでなる洗浄剤を用いる化学的機械的研磨した後の半導体デバイスの洗浄方法であり、銅または銅を含む合金の洗浄に有用である。
【００１２】
以下に本発明をさらに詳細に説明する。
【００１３】
本発明の化学的機械的研磨した後の半導体デバイスの洗浄方法に用いる洗浄剤は、エチレン尿素を含んでなるものである。
【００１４】
本発明で用いる洗浄剤には、エチレン尿素以外の成分を含んでいても良い。一般的には水を添加してエチレン尿素の水溶液として使用するが、洗浄力の向上、あるいはエチレン尿素の溶解性改善のため、例えば、水溶性有機溶媒を添加しても良い。
【００１５】
水溶性有機溶媒としては、洗浄剤として一般に使用しているものを使用することができる。例示するとメタノール、エタノール、１−プロパノール、２−プロパノール、ブタノール、エチレングリコール、プロピレングリコール、ポリエチレングリコール、ベンジルアルコールなどのアルコール類、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルイミダゾリジノン、Ｎ−メチルピロリドンなどのアミド類、ジメチルスルホキシドなどのスルホキシド類、テトラヒドロフラン、ジオキサン、ジグリムなどのエーテル類などが挙げられる。
【００１６】
本発明で用いる洗浄剤には、その他一般に使用されている防食剤、界面活性剤も添加することができる。防食剤については、本発明の洗浄剤は非常に銅の腐食性が低いため、一般的に添加されている量より、少ない量の防食剤の添加で効果が現れる。
【００１７】
また、本発明で用いる洗浄剤には、洗浄性能の向上のため、あるいはｐＨ調整のため、酸、塩類を添加しても良い。
【００１８】
エチレン尿素、水、水溶性有機溶媒の比率は、それぞれ使用する化合物が異なると、変化するため限定することは困難であるがエチレン尿素が０．０１〜８０重量％、水が０〜９９．９９重量％、有機溶媒が０〜９９．９９重量％(混合物の全量を１００重量％として）である。この範囲をはずれても使用できないことはないが、洗浄能力が低下する場合がある。
【００１９】
本発明で用いる洗浄剤は、洗浄する際に各成分を添加して使用しても良いし、あらかじめ各成分を混合しておいてから使用しても良い。
【００２０】
本発明は、銅配線半導体デバイスの洗浄に利用できる。特に、ＣＭＰ後の洗浄に有効である。
【００２２】
また、ＣＭＰの後の半導体デバイス上には、研磨スラリー、パッドかす、銅などの半導体材料のかすが存在するが、本発明は、これらのかすを半導体材料にダメージを与えることなく除去洗浄することができる。
【００２３】
本発明の洗浄方法を使用すると、銅配線に対する腐食性は小さくなる。本発明の洗浄剤を使用する際には、加熱、超音波などで洗浄を促進しても良い。
【００２４】
【実施例】
本発明を以下の実施例により更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。
【００２５】
なお、表記を簡潔にするため、以下の略記号を使用した。
【００２６】
ＮＨ4ＯＨ：アンモニア水
ＭＥＡ：モノエタノールアミン
ＥＵ：エチレン尿素
実施例１、比較例１〜２
表１に示したアミンの１０％水溶液に金属銅のテストピースを５０℃で浸漬、浸漬前と浸漬後の重量変化から銅腐食速度を算出した。この結果を表１に示した。
【００２７】
【表１】
銅メッキしたウェハを、１１７ｎｍの平均粒子径を有するシリカゾルを分散させた純水に３分浸漬した後、ｐＨ６に調整した希硫酸で１分洗浄した。これを乾燥し、シリカ粒子で汚染されたウエハとした。このウエハを表２に示す洗浄液中で室温で１分間、超音波洗浄し、その後水洗、乾燥した。表面を走査型電子顕微鏡で観察し、単位面積あたりのシリカ粒子数を調べた。なお、シリカ粒子の除去性能は以下の様に評価した。
粒子除去率（％）＝１００−（洗浄液で超音波洗浄した場合のシリカ粒子数／純水のみで超音波洗浄した場合のシリカ粒子数）×１００
【００２８】
【表２】
本発明の洗浄剤は、優れた洗浄能力を示すとともに、銅を腐食しない洗浄剤として使用できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for cleaning a semiconductor device after chemical mechanical polishing . More specifically, the present invention relates to a method for cleaning a copper wiring semiconductor device.
[0002]
[Prior art]
In recent years, along with the rapid development of information technology, there is a trend toward miniaturization, higher density, and higher speed of large-scale integrated circuits (LSI, ULSI, VLSI), and technology based on multilayer wiring Development is underway. In order to achieve multi-layer wiring, it is necessary to reduce the wiring pitch width and reduce the inter-wiring capacitance, etc. As a solution for reducing the wiring pitch width, tungsten and aluminum, which are existing metal wiring materials, have a higher resistivity. The development of technology for changing to lower copper is being actively researched.
[0003]
Copper is easily corroded by ammonia or amines, and the cleaning agent used for conventional aluminum wiring is also required to be changed.
[0004]
For example, when the resist used at the time of wiring formation is finally stripped, the monoethanolamine resist stripping agent used at the time of conventional aluminum wiring has extremely high copper corrosion, and its replacement is required.
[0005]
Also, copper wiring tends to become a mainstream damascene process by embedding. The planarization of the wiring formed by the damascene method is performed by a so-called CMP (Chemical Mechanical Polishing) method using the synergistic effect of the mechanical polishing action and the chemical polishing action, and the copper wiring material is also polished by the same method. Is made.
[0006]
However, in this CMP method, after metal polishing, a large number of abrasives, polishing scraps, and metal impurities adhere to the wafer, so it is necessary to clean the wafer surface. When washing with an alkaline solution, reattachment of impurities can be suppressed, so ammonia has generally been used in the case of metals other than copper. However, copper is easily corroded by ammonia, and ammonia cannot be used as a cleaning agent. Therefore, a method has been proposed in which a copper corrosion inhibitor is added to ammonia to reduce the corrosion rate of copper. For example, Patent Document 1 discloses a compound containing a mercapto group as an anticorrosive. However, as described in the publication, a compound containing a mercapto group has a peculiar unpleasant odor and has a problem in using it both environmentally and industrially. Aromatic compounds such as benzotriazole are known as other anticorrosives, but there are environmental problems such as high toxicity. In addition, in the method of adding an anticorrosive agent, since corrosion of copper cannot be suppressed with a small amount of anticorrosive agent, a method that basically does not use ammonia that easily corrodes copper has been desired.
[0007]
Thus, conventional detergents containing ammonia and amines have not been sufficient in terms of corrosiveness to copper.
[0008]
[Patent Document 1]
JP 2000-273663 A (Claims)
[0009]
[Problems to be solved by the invention]
In view of the above problems, an object of the present invention is to provide a cleaning method that does not attack copper , particularly in a method for cleaning a semiconductor device after chemical mechanical polishing .
[0010]
[Means for Solving the Problems]
The present inventors have intensively studied a result the semiconductor device cleaning method after chemical mechanical polishing, found that detergent containing ethylene urea as essential components can be used as a cleaning agent does not attack the copper, the The invention has been completed.
[0011]
That is, the present invention is a method for cleaning a semiconductor device after chemical mechanical polishing using a cleaning agent containing ethylene urea, and is useful for cleaning copper or an alloy containing copper.
[0012]
The present invention is described in further detail below.
[0013]
The cleaning agent used in the method for cleaning a semiconductor device after chemical mechanical polishing according to the present invention comprises ethylene urea.
[0014]
The cleaning agent used in the present invention may contain components other than ethylene urea. In general, water is added to use as an aqueous solution of ethylene urea. However, for example, a water-soluble organic solvent may be added to improve detergency or improve the solubility of ethylene urea.
[0015]
As the water-soluble organic solvent, those generally used as a cleaning agent can be used. Examples include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, butanol, ethylene glycol, propylene glycol, polyethylene glycol, benzyl alcohol, N, N-dimethylformamide, dimethylimidazolidinone, N-methylpyrrolidone, etc. Examples include amides, sulfoxides such as dimethyl sulfoxide, and ethers such as tetrahydrofuran, dioxane, diglyme.
[0016]
Other commonly used anticorrosives and surfactants can also be added to the cleaning agent used in the present invention. As for the anticorrosive, since the cleaning agent of the present invention has very low corrosiveness to copper, the effect appears when the amount of the anticorrosive is less than that generally added.
[0017]
In addition, acids and salts may be added to the cleaning agent used in the present invention in order to improve cleaning performance or adjust pH.
[0018]
The ratio of ethylene urea, water, and water-soluble organic solvent varies depending on the compound used, and is difficult to limit because it varies. However, ethylene urea is 0.01 to 80% by weight and water is 0 to 99.99. The organic solvent is 0 to 99.99% by weight (the total amount of the mixture is 100% by weight). Even if it is out of this range, it cannot be used, but the cleaning ability may decrease.
[0019]
The cleaning agent used in the present invention may be used by adding each component at the time of cleaning, or may be used after mixing each component in advance.
[0020]
The present invention is applicable to the cleaning of the copper wiring semiconductor device. In particular, it is effective for cleaning after CMP.
[0022]
Further, on the semiconductor device after CMP, a polishing slurry, pad cake, but there are dregs of the semiconductor material, such as copper, the invention is able to remove cleaning without damage these dregs the semiconductor material it can.
[0023]
When the cleaning method of the present invention is used, the corrosiveness to the copper wiring is reduced. When using the cleaning agent of the present invention, cleaning may be accelerated by heating, ultrasonic waves, or the like.
[0024]
【Example】
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
[0025]
In order to simplify the notation, the following abbreviations were used.
[0026]
NH 4 OH: ammonia water MEA: monoethanolamine EU: ethylene urea Example 1, Comparative Examples 1-2
The copper corrosion rate was calculated from the weight change before and after immersion of a copper test piece immersed in a 10% aqueous solution of amine shown in Table 1 at 50 ° C. The results are shown in Table 1.
[0027]
[Table 1]
The copper-plated wafer was immersed in pure water in which silica sol having an average particle diameter of 117 nm was dispersed for 3 minutes, and then washed with dilute sulfuric acid adjusted to pH 6 for 1 minute. This was dried to obtain a wafer contaminated with silica particles. This wafer was ultrasonically cleaned in the cleaning liquid shown in Table 2 at room temperature for 1 minute, then washed with water and dried. The surface was observed with a scanning electron microscope, and the number of silica particles per unit area was examined. The silica particle removal performance was evaluated as follows.
Particle removal rate (%) = 100− (number of silica particles when ultrasonically cleaned with a cleaning solution / number of silica particles when ultrasonically cleaned with pure water only) × 100
[0028]
[Table 2]
The cleaning agent of the present invention exhibits excellent cleaning ability and can be used as a cleaning agent that does not corrode copper.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002320356A JP4154999B2 (en) | 2002-11-01 | 2002-11-01 | Cleaning method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002320356A JP4154999B2 (en) | 2002-11-01 | 2002-11-01 | Cleaning method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004155821A JP2004155821A (en) | 2004-06-03 |
| JP4154999B2 true JP4154999B2 (en) | 2008-09-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002320356A Expired - Fee Related JP4154999B2 (en) | 2002-11-01 | 2002-11-01 | Cleaning method |
Country Status (1)
| Country | Link |
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| JP (1) | JP4154999B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101056580B1 (en) * | 2004-12-22 | 2011-08-11 | 재단법인 포항산업과학연구원 | Detergent Composition and Cleaning Method of Heat Exchanger Using Coal Sorbent Oil |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6350838A (en) * | 1986-08-21 | 1988-03-03 | Japan Synthetic Rubber Co Ltd | Removing solution |
| JP3490604B2 (en) * | 1998-01-26 | 2004-01-26 | 多摩化学工業株式会社 | Method for producing quaternary ammonium base type semiconductor surface treating agent |
| JP3891768B2 (en) * | 1999-12-28 | 2007-03-14 | 株式会社トクヤマ | Residual cleaning solution |
| JP4025953B2 (en) * | 2001-01-05 | 2007-12-26 | 荒川化学工業株式会社 | Cleaning composition |
| JP2002205024A (en) * | 2001-01-05 | 2002-07-23 | Arakawa Chem Ind Co Ltd | Method for cleaning article |
| US20030022800A1 (en) * | 2001-06-14 | 2003-01-30 | Peters Darryl W. | Aqueous buffered fluoride-containing etch residue removers and cleaners |
| US6943142B2 (en) * | 2002-01-09 | 2005-09-13 | Air Products And Chemicals, Inc. | Aqueous stripping and cleaning composition |
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| JP2004155821A (en) | 2004-06-03 |
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