JP4277606B2 - Resist stripping solution for substrate process of single wafer cleaning apparatus and stripping method using the same - Google Patents
Resist stripping solution for substrate process of single wafer cleaning apparatus and stripping method using the same Download PDFInfo
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- JP4277606B2 JP4277606B2 JP2003207818A JP2003207818A JP4277606B2 JP 4277606 B2 JP4277606 B2 JP 4277606B2 JP 2003207818 A JP2003207818 A JP 2003207818A JP 2003207818 A JP2003207818 A JP 2003207818A JP 4277606 B2 JP4277606 B2 JP 4277606B2
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- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
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Description
【０００１】
【発明の属する技術分野】
本発明は枚葉式洗浄装置の基板工程用レジストの剥離方法に関する。
【０００２】
【従来の技術】
半導体製造工程で用いられるウェット洗浄装置は２５〜５０枚のウエハを一括処理するバッチ式とウエハを１枚ずつ処理する枚葉式に分類される。バッチ式は多くの洗浄溶液槽と純水リンス槽を装備する多槽式と１槽の中で種々の薬液洗浄と純水リンスを行う単槽式がある。従来、バッチ式の多槽式がマニュアル操作から全自動へと変遷しながら発展してきたが、近年、バッチ式の単槽式と枚葉式洗浄装置が特定の工程後の洗浄に用いられるようになってきた。今後は生産性向上のために大口径Ｓｉウエハ（径３００ｍｍ又は４５０ｍｍ）が用いられていくためにウエハ面内での洗浄均一性が高く、また装置の設置面積が小さい枚葉式洗浄装置が主流となりつつある。
【０００３】
従来、基板工程（Ｆｒｏｎｔ Ｅｎｄ ｏｆ Ｌｉｎｅ 工程）におけるレジスト剥離は、従来はバッチ式洗浄装置において硫酸と過酸化水素水からなる混合溶液（ＳＰＭ洗浄液）により行われてきた。典型的な使用条件としてはＳＰＭ洗浄液（硫酸：過酸化水素水＝４：１）で１０分間、１００〜１２０℃で処理することにより行われる。
【０００４】
しかしながら、枚葉式洗浄装置においては、装置的、コスト的な制限からＳＰＭ洗浄液のような濃厚で高温の溶液を用いることができなかった。また、装置的に引火点を有する薬液も望ましくなく、これまで、この洗浄装置に適した基板工程用のレジスト剥離液はなかった。
【０００５】
これまで、水酸化テトラメチルアンモニウムの過酸化水素化物を含むレジスト剥離剤は知られていた（例えば特許文献１）が、それを枚様式洗浄装置に用いること、並びにそれに適した条件については開示されていなかった。
【０００６】
【特許文献１】
特開２００３−１３７８４８号公報
【０００７】
【発明が解決しようとする課題】
本発明の目的は、高温で長時間剥離剤を使用できない装置、特に枚葉式洗浄装置で使用するのに好適なレジスト及び反射防止膜の剥離方法を提供することである。すなわち、露出している多結晶Ｓｉ（ｐｏｌｙ−Ｓｉ）、Ｓｉ酸化膜（ＳｉＯ２）などにダメージを与えることなく、８０℃以下の温度及び短時間（〜３０秒）の条件下でレジスト及び反射防止膜を除去可能で、更に引火点を持たないレジスト剥離方法を提供することにある。
【０００８】
【課題を解決するための手段】
本発明者らは、枚葉式洗浄装置の基板工程用レジスト剥離液（以後レジスト剥離液）について鋭意検討した結果、ある特定濃度の水酸化テトラメチルアンモニウム、水、及び過酸化水素及び／又は過酸化物の混合溶液がｐｏｌｙ−Ｓｉ、ＳｉＯ2などにダメージを与えることなく、８０℃以下の温度及び短時間（３０秒以内、好ましくは〜１５秒）の条件下でレジスト及び反射防止膜を除去することができ、更に引火点を持たないことを見出し、本発明を完成するに至った。
【０００９】
すなわち、本発明は、水酸化テトラメチルアンモニウム、水、及び過酸化水素及び／又は過酸化物を必須成分とするレジスト剥離液を用いた剥離方法である。
【００１０】
以下に本発明を詳細に説明する。
【００１１】
本発明におけるレジスト剥離液は、高温で長時間剥離剤を使用できない装置、特に枚葉式洗浄装置の基板工程において用いることができる。ここで基板工程とは半導体製造工程の配線構造形成前までのいわゆるＦＥＯＬ（Ｆｒｏｎｔ Ｅｎｄ ｏｆ Ｌｉｎｅ）工程のことである。
【００１２】
本発明において、剥離とは、フォトレジスト及び／又は反射防止膜を基板上に塗布した後、露光、現像し、エッチング、イオン注入などの処理を施し回路を形成した後、残ったレジスト及び／又は反射防止膜を除去することをいう。
【００１３】
本発明のレジスト剥離液はフォトレジスト及び／又は反射防止膜を剥離するのに使用される。すなわち、フォトレジスト及び／又は反射防止膜を基板上に塗布した後、露光、現像し、エッチング、イオン注入などの処理を施し回路を形成した後、本発明のレジスト剥離液で剥離する。
【００１４】
本発明のレジスト剥離液は水酸化テトラメチルアンモニウム、水、及び過酸化水素及び／又は過酸化物を含む水溶液から成る。
【００１５】
本発明のレジスト剥離液に使用する水酸化テトラメチルアンモニウムは、レジスト及び反射防止膜を溶解除去する作用がある。水酸化テトラメチルアンモニウムは一般的に市販されており容易に入手することができるが、ウエハの清浄度を保つため、高純度品を使用するのが好ましい。
【００１６】
本発明のレジスト剥離液に使用する過酸化水素は酸化剤としてウエハに露出したｐｏｌｙ−Ｓｉ、ＳｉＯ2を保護するために添加する。Ｓｉを保護するための酸化剤としては、その他にも過硫酸塩、過ホウ酸塩、過炭酸塩、有機過酸、及び有機ハイドロパーオキシドなどの過酸化物を使用することができる。過酸化水素は無水、水溶液のほかに、尿素や第四級アンモニウム塩などの過酸化水素化物（結晶水における水のように、尿素や第四級アンモニウム塩に過酸化水素が配位したもの）も使用できるが、取り扱いやすさから水溶液が好ましい。過酸化水素水は一般的に市販されており容易に入手することができる。
【００１７】
本発明のレジスト剥離液のｐＨは１１〜１４であることが好ましく、特に好ましくは１２〜１４である。
【００１８】
本発明の洗浄液の組成は必須成分である水酸化テトラメチルアンモニウム、水、及び過酸化水素及び／又は過酸化物の組み合わせで所定のｐＨに調整するが、それぞれ使用する濃度が異なるとｐＨが変化するため、夫々の濃度を限定することは困難であるが、水酸化テトラメチルアンモニウムの含有量は１〜５重量％である。この範囲を超えて水酸化テトラメチルアンモニウムの濃度が増加すると剥離効果に優れるが、引火点を持つ可能性があり、またコスト的に不利である。逆に少なすぎると剥離効果が不十分となる。過酸化水素及び／又は過酸化物の含有量は０．１〜１重量％である。少なすぎるとＳｉのダメージを抑制できなくなり、多すぎると剥離効果が低下する。
【００１９】
本発明のレジスト剥離液は、レジストを剥離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】
本発明のレジスト剥離液は、ネガ型、ポジ型を含めて、アルカリ性水溶液で現像できるｉ線用、ＫｒＦエキシマレーザー用等のレジストの剥離に利用できる。
【００２１】
本発明のレジスト剥離液は、無機質基体上に塗布されたフォトレジスト膜、イオン注入などの処理をしたフォトレジスト層、反射防止膜を剥離する際に最も好適に用いられる。
【００２２】
本発明のレジスト剥離液は枚葉式洗浄装置で使用され、洗浄時の温度は装置上の制限から２０℃〜８０℃が好ましい。また、洗浄時間は生産性の観点から３０秒以内である。
【００２３】
【実施例】
以下、本発明の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。
【００２４】
実施例１〜４、比較例１〜７
ＫｒＦレジストウエハをそれぞれ表１に示す剥離液に８０℃、１５秒浸漬し、その後水洗いし、乾燥した。なお、水酸化テトラメチルアンモニウムは多摩化学工業（株）製（高純度グレード）、過酸化水素及びアンモニアはキシダ化学、炭酸アンモニウムは関東化学のものを使用した。
【００２５】
表面を走査型電子顕微鏡で観察しレジストの剥離性を調べた。また、Ｓｉの侵食については、ｐｏｌｙ−Ｓｉ膜ウエハ、ＳｉＯ2膜ウエハを８０℃、５分間浸漬し、表面観察から評価した。引火点はタグ密閉式およびクリーブランド開放式により測定を行った。なお、表１に剥離液組成を示すが、残部は水である。
ＫｒＦレジストの剥離性、侵食性は以下のように評価した。
＜ＫｒＦレジストの剥離性＞
○：完全剥離、△：一部残存、×：全面に残存
＜Ｓｉの侵食性＞
○：侵食なし、△：一部侵食有り、×：激しい侵食有り
【００２６】
【表１】
本発明のレジスト剥離液は多結晶Ｓｉ（ｐｏｌｙ−Ｓｉ）、Ｓｉ酸化膜（ＳｉＯ2）などにダメージを与えることなく、８０℃以下の温度及び短時間（〜１５秒）の条件下でレジストを除去することができ、更に引火点を持たないため特に枚葉式洗浄装置の基板工程用レジスト剥離液として極めて有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for removing a resist for a substrate process in a single wafer cleaning apparatus.
[0002]
[Prior art]
Wet cleaning apparatuses used in semiconductor manufacturing processes are classified into a batch type that batch-processes 25 to 50 wafers and a single wafer type that processes wafers one by one. The batch type includes a multi-tank type equipped with many cleaning solution tanks and a pure water rinsing tank, and a single tank type for performing various chemical cleaning and pure water rinsing in one tank. In the past, batch-type multi-tank systems have evolved from manual operation to full-automatic operation, but in recent years, batch-type single-tank systems and single wafer cleaning systems have been used for cleaning after specific processes. It has become. In the future, large-diameter Si wafers (diameter 300 mm or 450 mm) will be used to improve productivity, so single-wafer cleaning equipment with high cleaning uniformity within the wafer surface and small equipment installation area will be the mainstream. It is becoming.
[0003]
Conventionally, resist removal in a substrate process (Front End of Line process) has been conventionally performed with a mixed solution (SPM cleaning liquid) composed of sulfuric acid and hydrogen peroxide in a batch type cleaning apparatus. As typical use conditions, it is performed by treating at 100 to 120 ° C. for 10 minutes with an SPM cleaning solution (sulfuric acid: hydrogen peroxide solution = 4: 1).
[0004]
However, in a single wafer cleaning apparatus, a concentrated and high-temperature solution such as an SPM cleaning liquid cannot be used due to limitations in terms of apparatus and cost. Also, a chemical solution having a flash point is not desirable in terms of apparatus, and until now there has been no resist stripping solution for a substrate process suitable for this cleaning apparatus.
[0005]
Until now, a resist stripper containing hydrogen peroxide of tetramethylammonium hydroxide has been known (for example, Patent Document 1). However, the use of the resist stripper in a sheet-type cleaning apparatus and conditions suitable for the resist stripper have been disclosed. It wasn't.
[0006]
[Patent Document 1]
Japanese Patent Laid-Open No. 2003-137848
[Problems to be solved by the invention]
An object of the present invention is to provide a resist and an antireflection film peeling method suitable for use in an apparatus that cannot use a release agent for a long time at a high temperature, particularly a single wafer cleaning apparatus. In other words, resist and reflection under conditions of a temperature of 80 ° C. or less and a short time (˜30 seconds) without damaging the exposed polycrystalline Si (poly-Si), Si oxide film (SiO 2 ), etc. An object of the present invention is to provide a resist stripping method capable of removing the prevention film and having no flash point.
[0008]
[Means for Solving the Problems]
As a result of intensive studies on a resist stripping solution for substrate processing (hereinafter referred to as a resist stripping solution) of a single wafer cleaning apparatus, the present inventors have found that tetramethylammonium hydroxide having a specific concentration, water, and hydrogen peroxide and / or excessive concentration. The resist and antireflection film are removed under conditions of a temperature of 80 ° C. or lower and a short time (within 30 seconds, preferably ˜15 seconds) without damaging the poly-Si, SiO 2, etc. with the mixed oxide solution. And found that it has no flash point, and has completed the present invention.
[0009]
That is, the present invention is a stripping method using a resist stripping solution containing tetramethylammonium hydroxide, water, hydrogen peroxide and / or peroxide as essential components.
[0010]
The present invention is described in detail below.
[0011]
The resist stripping solution in the present invention can be used in a substrate process of a device that cannot use a stripper for a long time at a high temperature, particularly a single wafer cleaning device. Here, the substrate process is a so-called FEOL (Front End of Line) process before the formation of the wiring structure in the semiconductor manufacturing process.
[0012]
In the present invention, peeling refers to the application of a photoresist and / or antireflection film on a substrate, exposure, development, etching, ion implantation, and the like to form a circuit, and then the remaining resist and / or It means removing the antireflection film.
[0013]
The resist stripping solution of the present invention is used for stripping a photoresist and / or an antireflection film. That is, after a photoresist and / or antireflection film is applied on a substrate, exposure, development, etching, ion implantation, and other processes are performed to form a circuit, and then the resist is stripped with the resist stripping solution of the present invention.
[0014]
The resist stripping solution of the present invention comprises an aqueous solution containing tetramethylammonium hydroxide, water, and hydrogen peroxide and / or peroxide.
[0015]
The tetramethylammonium hydroxide used in the resist stripping solution of the present invention has an action of dissolving and removing the resist and the antireflection film. Tetramethylammonium hydroxide is generally commercially available and can be easily obtained, but it is preferable to use a high-purity product in order to maintain the cleanliness of the wafer.
[0016]
Hydrogen peroxide used in the resist stripping solution of the present invention is added as an oxidizing agent to protect poly-Si and SiO 2 exposed on the wafer. As the oxidizing agent for protecting Si, other peroxides such as persulfate, perborate, percarbonate, organic peracid, and organic hydroperoxide can be used. Hydrogen peroxide is anhydrous, in addition to aqueous solution, hydrogen peroxide such as urea or quaternary ammonium salt (hydrogen peroxide is coordinated to urea or quaternary ammonium salt like water in crystal water) Can also be used, but an aqueous solution is preferred for ease of handling. Hydrogen peroxide water is generally commercially available and can be easily obtained.
[0017]
The pH of the resist stripping solution of the present invention is preferably 11-14, particularly preferably 12-14.
[0018]
The composition of the cleaning liquid of the present invention is adjusted to a predetermined pH by a combination of tetramethylammonium hydroxide, which is an essential component, water, and hydrogen peroxide and / or peroxide, but the pH changes depending on the concentration used. Therefore, although it is difficult to limit the respective concentrations, the content of tetramethylammonium hydroxide is 1 to 5 % by weight. When the concentration of tetramethylammonium hydroxide is increased beyond this range, the peeling effect is excellent, but it may have a flash point and is disadvantageous in terms of cost. Conversely, if the amount is too small, the peeling effect becomes insufficient. The content of hydrogen peroxide and / or peroxide is 0.1 to 1 % by weight. If the amount is too small, Si damage cannot be suppressed, and if the amount is too large, the peeling effect decreases.
[0019]
The resist stripping solution of the present invention may be used by adding each component when stripping the resist, or may be used after mixing each component in advance.
[0020]
The resist stripping solution of the present invention can be used for stripping resists for i-line and KrF excimer laser that can be developed with an alkaline aqueous solution, including negative and positive types.
[0021]
The resist stripping solution of the present invention is most preferably used when stripping a photoresist film coated on an inorganic substrate, a photoresist layer treated with ion implantation, or an antireflection film.
[0022]
The resist stripping solution of the present invention is used in a single wafer cleaning apparatus, and the temperature during cleaning is preferably 20 ° C. to 80 ° C. due to limitations on the apparatus. The cleaning time is within 30 seconds from the viewpoint of productivity.
[0023]
【Example】
Hereinafter, the method of the present invention will be described with reference to examples, but the present invention is not limited thereto.
[0024]
Examples 1-4, Comparative Examples 1-7
Each KrF resist wafer was immersed in a stripping solution shown in Table 1 at 80 ° C. for 15 seconds, then washed with water and dried. Tetramethylammonium hydroxide was manufactured by Tama Chemical Industries (high purity grade), hydrogen peroxide and ammonia were Kishida Chemical, and ammonium carbonate was Kanto Chemical.
[0025]
The surface was observed with a scanning electron microscope to examine the peelability of the resist. Also, the erosion of Si, poly-Si film wafer, 80 ° C. The SiO 2 film wafer was immersed for 5 minutes and evaluated the surface observation. The flash point was measured by a closed tag type and a Cleveland open type. In addition, although stripping liquid composition is shown in Table 1, the remainder is water.
The peelability and erodibility of the KrF resist were evaluated as follows.
<Peelability of KrF resist>
○: Completely peeled, Δ: Partially retained, ×: Residual on the entire surface <Si erosion>
○: No erosion, △: Partial erosion, ×: Heavy erosion [0026]
[Table 1]
The resist stripping solution of the present invention does not damage the polycrystalline Si (poly-Si), Si oxide film (SiO 2 ), etc., and resists under a temperature of 80 ° C. or less and for a short time (˜15 seconds). Since it can be removed and has no flash point, it is extremely useful as a resist stripping solution for a substrate process of a single wafer cleaning apparatus.
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| JP2003207818A JP4277606B2 (en) | 2003-08-19 | 2003-08-19 | Resist stripping solution for substrate process of single wafer cleaning apparatus and stripping method using the same |
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|---|---|---|---|
| JP2003207818A JP4277606B2 (en) | 2003-08-19 | 2003-08-19 | Resist stripping solution for substrate process of single wafer cleaning apparatus and stripping method using the same |
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| Publication Number | Publication Date |
|---|---|
| JP2005062260A JP2005062260A (en) | 2005-03-10 |
| JP4277606B2 true JP4277606B2 (en) | 2009-06-10 |
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