JP2007157827A - Method for removing liquid and method for evaluating resist pattern using same - Google Patents
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Abstract
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本発明は、基板上に形成されたホトレジスト膜またはその上に形成される保護膜などの被露光膜上に液体が接触した後に、前記液体を効率的に除去するための液体の除去方法に関するものである。さらに本発明は、前記液体の除去方法を用いて液浸露光プロセスにおけるレジストパターン形成の評価試験を行い、レジストパターンの形状評価を行う、レジストパターンの評価方法に関するものである。 The present invention relates to a liquid removing method for efficiently removing a liquid after the liquid contacts an exposed film such as a photoresist film formed on a substrate or a protective film formed thereon. It is. Furthermore, the present invention relates to a resist pattern evaluation method in which a resist pattern formation evaluation test in an immersion exposure process is performed using the liquid removal method, and a resist pattern shape is evaluated.
半導体デバイス、液晶デバイス等の各種電子デバイスにおける微細構造の製造には、リソグラフィー法が多用されているが、デバイス構造の微細化に伴って、リソグラフィー工程におけるレジストパターンの微細化が要求されている。 Lithography is frequently used to manufacture fine structures in various electronic devices such as semiconductor devices and liquid crystal devices. However, with the miniaturization of device structures, it is required to make resist patterns finer in the lithography process.
現在では、リソグラフィー法により、例えば、最先端の領域では、線幅が９０ｎｍ程度の微細なレジストパターンを形成することが可能となっているが、今後はさらに微細なパターン形成が要求される。 At present, it is possible to form a fine resist pattern having a line width of about 90 nm by the lithography method, for example, in the most advanced region. However, further fine pattern formation is required in the future.
このような９０ｎｍより微細なパターン形成を達成させるためには、露光装置とそれに対応するレジストの開発が第１のポイントとなる。露光装置においては、Ｆ2エキシマレーザー、ＥＵＶ(極端紫外光)、電子線、Ｘ線、軟Ｘ線等の光源波長の短波長化やレンズの開口数（ＮＡ）の増大等が開発ポイントとしては一般的である。 In order to achieve such fine pattern formation of less than 90 nm, the development of an exposure apparatus and a corresponding resist is the first point. Development points for exposure equipment include shortening the wavelength of light sources such as F 2 excimer laser, EUV (extreme ultraviolet light), electron beam, X-ray, soft X-ray, and increasing the numerical aperture (NA) of the lens. It is common.
しかしながら、光源波長の短波長化は高額な新たな露光装置が必要となるし、また、高ＮＡ化では、解像度と焦点深度幅がトレードオフの関係にあるため、解像度を上げても焦点深度幅が低下するという問題がある。 However, shortening the wavelength of the light source requires a new expensive exposure apparatus, and in increasing the NA, there is a trade-off between the resolution and the depth of focus. There is a problem that decreases.
最近、このような問題を解決可能とするリソグラフィー技術として、液浸露光（リキッドイマージョンリソグラフィー）法という方法が報告されている（例えば、非特許文献１、非特許文献２、非特許文献３）。この方法は、露光時に、レンズと基板上の被露光膜との間の少なくとも前記被露光膜上に所定厚さの純水またはフッ素系不活性液体等の液状屈折率媒体（以下、液浸媒体と記す）を介在させるというものである。この方法では、従来は空気や窒素等の不活性ガスであった露光光路空間を屈折率（ｎ）のより大きい液体、例えば純水等で置換することにより、同じ露光波長の光源を用いてもより短波長の光源を用いた場合や高ＮＡレンズを用いた場合と同様に、高解像性が達成されると同時に焦点深度幅の低下もない。 Recently, as a lithography technique capable of solving such a problem, a method called an immersion exposure (liquid immersion lithography) method has been reported (for example, Non-Patent Document 1, Non-Patent Document 2, and Non-Patent Document 3). In this method, during exposure, a liquid refractive index medium (hereinafter referred to as an immersion medium) such as pure water or a fluorine-based inert liquid having a predetermined thickness is formed on at least the film to be exposed between the lens and the film to be exposed on the substrate. And the like). In this method, a light source having the same exposure wavelength can be used by replacing the exposure optical path space, which has conventionally been an inert gas such as air or nitrogen, with a liquid having a higher refractive index (n), such as pure water. Similar to the case of using a light source having a shorter wavelength or the case of using a high NA lens, high resolution is achieved and at the same time, there is no reduction in the depth of focus.
このような液浸露光を用いれば、現存の装置に実装されているレンズを用いて、低コストで、より高解像性に優れ、かつ焦点深度にも優れるレジストパターンの形成を実現できるため、大変注目されている。 By using such immersion exposure, it is possible to realize the formation of a resist pattern that is low in cost, excellent in high resolution, and excellent in depth of focus, using a lens mounted on an existing apparatus. It is attracting a lot of attention.
また、このような液浸露光法を用いた場合、目的とするレジストパターン形状を評価するための評価手法が開示されている（例えば、特許文献１）。 Moreover, when such an immersion exposure method is used, an evaluation method for evaluating a target resist pattern shape is disclosed (for example, Patent Document 1).
しかしながら、上述のような液浸露光プロセスにおけるレジストパターン形成性能の評価においては、被露光膜を直接液浸媒体に接触させる必要があるので、当然ながら被露光膜は液浸媒体による侵襲を受けることになる。したがって、従来使用されてきたレジスト組成物や保護膜材料をそのまま適用可能か否か、さらに実際の液浸露光プロセスにおいて液浸媒体と接触したことによるレジストパターン形成性能への影響を評価するためには、評価実験における結果と実際の液浸露光プロセスにおける結果との誤差をなくす必要がある。 However, in the evaluation of the resist pattern formation performance in the immersion exposure process as described above, since the exposed film needs to be in direct contact with the immersion medium, the exposed film is naturally subject to invasion by the immersion medium. become. Therefore, in order to evaluate whether or not the resist composition and the protective film material that have been conventionally used can be applied as they are, and further the influence on the resist pattern formation performance due to contact with the immersion medium in the actual immersion exposure process. Therefore, it is necessary to eliminate an error between the result in the evaluation experiment and the result in the actual immersion exposure process.
現在では、前述のレジスト膜や保護膜などの被露光膜の液浸露光適性は、主に次のような二通りの評価方法により判断している。 At present, the suitability of immersion exposure for exposed films such as the resist film and the protective film is mainly determined by the following two evaluation methods.
第１の方法は、「露光後に液浸媒体のシャワーをレジスト膜にかける処理を行い、その後、現像し、得られたレジストパターンの解像性を検査する」という評価試験により確認する方法である。 The first method is a method of confirming by an evaluation test that “a process of applying a shower of an immersion medium to the resist film after exposure and then developing and inspecting the resolution of the obtained resist pattern”. .
第２の方法は、露光のパターン光をプリズムによる干渉光をもって代用させて、試料を液浸状態に置き、露光させる構成の「２光束干渉露光法」を用いて、実際の製造工程をシミュレートした評価を行う方法である。 The second method simulates the actual manufacturing process using the “two-beam interference exposure method” in which the exposure pattern light is substituted with interference light from the prism, and the sample is placed in an immersion state and exposed. This is a method for performing the evaluation.
これらのどちらの評価方法においても、被露光膜に液体が接触している時間を正確に制御しなければ、評価に誤差が生じてしまう。この液体接触時間の制御は、被露光膜への液体シャワーを中止、もしくは被露光膜上の液体をスピンナーで迅速に振り落とすことにより行っている。 In any of these evaluation methods, an error occurs in the evaluation unless the time during which the liquid is in contact with the film to be exposed is accurately controlled. The control of the liquid contact time is performed by stopping the liquid shower on the film to be exposed or by quickly shaking off the liquid on the film to be exposed with a spinner.
このスピンナーでの振り落としによって短時間の内に接触液体が完全に被露光膜表面から除去されれば、評価に誤差は生じない。しかし、液体が完全に除去できずに、例えば、微小水滴状態で残留していると、レジスト膜に欠陥が発見された場合、余分な時間残留していた微小水滴の影響によるものか否かの判定が難しく、評価の信頼性が揺らぐことになる。 If the contact liquid is completely removed from the surface of the film to be exposed within a short time by shaking off with the spinner, no error occurs in the evaluation. However, if the liquid cannot be completely removed and remains in a minute water droplet state, for example, if a defect is found in the resist film, whether or not it is due to the influence of the minute water droplet remaining for an extra time. Judgment is difficult and the reliability of the evaluation will be shaken.
現在の液体の除去方法における条件は、加速度を１００００ｒｐｍ／秒として回転数４０００ｒｐｍまで上昇させ、４０００ｒｐｍにて１５秒間保持するという条件で行われている。この条件にて液体の除去を行った場合のレジスト膜に発生する欠陥集合体（デフェクトクラスター）の数がウェーハ当たり３０００〜４０００個発生していることが判明した。このデフェクトクラスター数は、評価時間内の液体接触によるレジスト膜への影響とは異なるもので、評価の誤差に当たると考えられるため、さらなる液体除去率の向上が求められる。 The current liquid removal method is performed under the condition that the acceleration is 10,000 rpm / second, the rotational speed is increased to 4000 rpm, and the pressure is maintained at 4000 rpm for 15 seconds. It was found that 3000 to 4000 defect aggregates (defect clusters) were generated in the resist film when the liquid was removed under these conditions. The number of defect clusters is different from the influence on the resist film due to the liquid contact within the evaluation time, and is considered to be an evaluation error. Therefore, further improvement of the liquid removal rate is required.
かかる経緯は、被露光膜がレジスト膜の上に形成される保護膜であった場合も同様である。 This process is the same when the film to be exposed is a protective film formed on the resist film.
また、前記被露光膜は必要に応じて露光前に液浸媒体により洗浄を行う（プリウェット）場合がある。この場合も被露光膜に影響を与えないように洗浄後は可能な限り迅速に被露光膜から液浸媒体を除去する必要がある。 The exposed film may be washed with an immersion medium (pre-wet) before exposure as necessary. Also in this case, it is necessary to remove the immersion medium from the exposed film as quickly as possible after cleaning so as not to affect the exposed film.
本発明は、かかる従来技術の問題点に鑑みてなされたものであり、その課題は、レジスト膜やその上に形成される保護膜などの被露光膜に液浸媒体や洗浄用液体を接触させた後の液体の膜表面からの除去を十全かつ迅速に行うことのできる液体の除去方法を提供することにあり、さらには、前記液体の除去方法を用いて液浸露光プロセスにおけるレジストパターン形成の評価試験を行い、レジストパターンの形状評価を行う、レジストパターンの評価方法に関するものである。 The present invention has been made in view of the problems of the prior art, and the problem is that an immersion medium or a cleaning liquid is brought into contact with a film to be exposed such as a resist film or a protective film formed thereon. It is another object of the present invention to provide a method for removing a liquid that can be completely and rapidly removed from the surface of the film, and to form a resist pattern in an immersion exposure process using the method for removing a liquid. It is related with the evaluation method of a resist pattern which performs the evaluation test of and performs shape evaluation of a resist pattern.
前記課題を解決するために、本発明に係る液体の除去方法は、被露光膜上から液体を除去するための方法であって、前記液体が付着した基板を、前記液体が付着した基板を、除去工程の始点で回転数を最大となるようにし続いて回転数を減衰させるか、もしくは加速度１０００ｒｐｍ以下で回転数を増大させながら終点で回転数を最大とすることを特徴とする。 In order to solve the above problems, a method for removing a liquid according to the present invention is a method for removing a liquid from a film to be exposed, wherein the substrate to which the liquid is attached is changed to a substrate to which the liquid is attached. The rotational speed is maximized at the starting point of the removal step, and then the rotational speed is attenuated, or the rotational speed is increased at an acceleration of 1000 rpm or less and the rotational speed is maximized at the end point.
前記最大回転数を少なくとも所定時間一定に維持することが好ましい。また、前記最大回転数は、２５００〜５０００ｒｐｍとすることが望ましい。 It is preferable to maintain the maximum rotational speed constant for at least a predetermined time. The maximum rotation speed is preferably 2500 to 5000 rpm.
さらに、前記回転数を減衰させる場合は段階的に行っても良い。前記段階的な回転数の減衰としては、始点で最大回転数を２５００〜５０００ｒｐｍとして１５秒以上保持した後、回転数を５００〜２０００ｒｐｍとして１５秒以上保持し、続いて回転数１００〜３００ｒｐｍとして１５秒以上保持するというプロセスを経ることが望ましい。 Further, when the rotational speed is attenuated, it may be performed stepwise. As the stepwise rotation speed reduction, the maximum rotation speed is maintained at 2500 to 5000 rpm for 15 seconds or more at the starting point, then the rotation speed is maintained at 500 to 2000 rpm for 15 seconds or more, and then the rotation speed is 100 to 300 rpm. It is desirable to go through a process of holding for more than a second.
また、前記加速度１０００ｒｐｍ以下で回転数を増大させながら終点で回転数を最大とする手法としては、加速度を５０〜１０００ｒｐｍとして回転数を徐々に増大させ、終点の最大回転数のまま１５秒以上保持するというプロセスを経ることが望ましい。 As a method of maximizing the rotational speed at the end point while increasing the rotational speed at an acceleration of 1000 rpm or less, the rotational speed is gradually increased at an acceleration of 50 to 1000 rpm, and the maximum rotational speed at the end point is maintained for 15 seconds or more. It is desirable to go through the process of doing.
本発明における前記液体とは、液浸露光プロセスにおいて、露光中に被露光膜とレンズとの間に配置される液体である場合と、被露光膜を露光処理に供する前の表面処理に用いられるプリウェット液である場合と、液浸露光プロセス用被露光膜材料の評価試験に用いられる液体である場合が考えられる。 In the liquid immersion exposure process, the liquid in the present invention is a liquid disposed between an exposed film and a lens during exposure, and used for surface treatment before subjecting the exposed film to exposure processing. A case where it is a pre-wet liquid and a case where it is a liquid used for an evaluation test of an exposed film material for an immersion exposure process are conceivable.
前記液浸露光プロセス用被露光膜の評価試験とは、露光前及び／又は露光後の被露光膜上に液浸露光用液体を接触させることにより、液浸プロセス材料の評価を行う評価試験である場合と、プリズムと被露光膜との間に液浸露光用液体を設けることにより、液浸露光プロセス材料の評価を行う二光束干渉法による評価試験である場合が考えられる。 The evaluation test of the exposed film for the immersion exposure process is an evaluation test for evaluating the immersion process material by bringing the immersion exposure liquid into contact with the exposed film before and / or after the exposure. In some cases, there may be an evaluation test by the two-beam interference method in which an immersion exposure process material is evaluated by providing an immersion exposure liquid between the prism and the film to be exposed.
前記被露光膜とは、ホトレジスト膜、あるいはその上層に保護膜が設けられた積層膜である。 The film to be exposed is a photoresist film or a laminated film provided with a protective film thereon.
本発明にかかる液体の除去方法は、レジスト膜やその上の保護膜などの被露光膜に接触し、付着した液体を迅速かつ十全に除去可能で、液体の影響を最小限に抑えることができ、そのために被露光膜の液体接触による特性変化の評価を正確に行うことが可能となる。よって、液体が被露光膜に接触するプロセスを有するフォトリソグラフィー技術の高精度化に効果的な寄与を行うことができる。 The method for removing a liquid according to the present invention is capable of quickly and fully removing the adhered liquid in contact with a film to be exposed such as a resist film or a protective film thereon, and minimizing the influence of the liquid. Therefore, it is possible to accurately evaluate the change in characteristics of the film to be exposed due to liquid contact. Therefore, it is possible to make an effective contribution to increasing the accuracy of the photolithography technique that includes a process in which the liquid contacts the film to be exposed.
以下に、本発明にかかる液体の除去方法の実施例を詳細に説明する。なお、この実施例によりこの発明が限定されるものではない。 Below, the Example of the removal method of the liquid concerning this invention is described in detail. Note that the present invention is not limited to the embodiments.
有機系反射防止膜組成物「ＡＲＣ−２９Ａ」（商品名、ＢｒｅｗｅｒＳｃｉｅｎｃｅ社製）を、スピナーを用いてシリコンウェーハ上に塗布し、ホットプレート上で２２５℃、６０秒間焼成して乾燥させることにより、膜厚７７ｎｍの有機系反射防止膜を形成した。そして、この反射防止膜上に、ポジ型レジストである「ＴＡｒＦ−Ｐ６ａ１９３（東京応化工業社製）」をスピナーを用いて塗布し、ホットプレート上で１２５℃、６０秒間プレベークして、乾燥させることにより、前記反射防止膜上に膜厚２２５ｎｍのレジスト膜を形成した。 An organic antireflection film composition “ARC-29A” (trade name, manufactured by Brewer Science) was applied on a silicon wafer using a spinner, and baked on a hot plate at 225 ° C. for 60 seconds to dry. An organic antireflection film having a thickness of 77 nm was formed. Then, on this antireflection film, “TArF-P6a193 (manufactured by Tokyo Ohka Kogyo Co., Ltd.)” which is a positive resist is applied using a spinner, prebaked on a hot plate at 125 ° C. for 60 seconds, and dried. Thus, a resist film having a film thickness of 225 nm was formed on the antireflection film.
次に、露光装置ＮＳＲ−Ｓ３０６（ニコン社製）により、ＡｒＦエキシマレーザー（波長１９３ｎｍ）を用いて、パターン露光した。露光処理後、基板を回転させながら、保護膜上に２３℃にて純水を２分間滴下し続け、擬似液浸環境下においた。 Next, pattern exposure was performed using an ArF excimer laser (wavelength: 193 nm) with an exposure apparatus NSR-S306 (manufactured by Nikon Corporation). After the exposure treatment, pure water was continuously dropped on the protective film at 23 ° C. for 2 minutes while rotating the substrate, and the substrate was placed in a simulated liquid immersion environment.
前記基板をスピンナーにて、以下の実施例１、２および比較例の液体除去条件にて、レジスト膜上の純水を振り落とした。 Using the spinner, the pure water on the resist film was shaken off under the liquid removal conditions of Examples 1 and 2 and Comparative Examples below.
前記純水の滴下工程および除去工程の後、１３０℃、９０秒間の条件でＰＥＢ処理した後、各レジスト膜を２３℃にてアルカリ現像液で６０秒間現像した。アルカリ現像液としては、２．３８質量％テトラメチルアンモニウムヒドロキシド水溶液（ＴＭＡＨ）を用いた。 After the pure water dropping step and removing step, PEB treatment was performed at 130 ° C. for 90 seconds, and then each resist film was developed with an alkaline developer at 23 ° C. for 60 seconds. As the alkaline developer, a 2.38 mass% tetramethylammonium hydroxide aqueous solution (TMAH) was used.
このようにして得たライン部が１２０ｎｍでスペース部が１２０ｎｍのライン・アンド・スペースのレジストパターンをＫＬＡ２３５１（ＫＬＡテンコール社製装置）により欠陥クラスター数を測定した。 The number of defect clusters of the line-and-space resist pattern having a line portion of 120 nm and a space portion of 120 nm thus obtained was measured using KLA2351 (KLA Tencor Co., Ltd. apparatus).
（実施例１）
最大回転数を４０００ｒｐｍとして１５秒間保持した後、回転数を５００ｒｐｍとして１５秒間保持し、続いて回転数１００ｒｐｍとして１５秒間保持した。この場合の欠陥クラスター数の平均値は４５１個であった。
Example 1
After maintaining the maximum number of rotations at 4000 rpm for 15 seconds, the number of rotations was maintained at 500 rpm for 15 seconds, and then the number of rotations was maintained at 100 rpm for 15 seconds. In this case, the average number of defect clusters was 451.
（実施例２）
回転加速度１００ｒｐｍ／秒で連続的に増大させ、回転数を４０００ｒｐｍとして１５秒間保持させた。この場合の欠陥クラスター数の平均値は６１６個であった。
(Example 2)
The rotational acceleration was continuously increased at 100 rpm / second, and the rotational speed was set to 4000 rpm and held for 15 seconds. In this case, the average number of defect clusters was 616.
（比較例）
回転加速度１００００ｒｐｍ／秒で回転数を４０００ｒｐｍまで増大させて、そのまま１５秒間保持した。この場合の欠陥クラスター数の平均値は３３２９個であった。
(Comparative example)
The rotational speed was increased to 4000 rpm at a rotational acceleration of 10000 rpm / second, and held there for 15 seconds. In this case, the average number of defect clusters was 3329.
すなわち、液体の除去方法を変更したことにより、欠陥クラスター数は大幅に低減され、これは評価試験における液体の振り切り方法に起因するものであることが分かり、さらには実施例に記載した評価方法によれば、この液体の振り切り工程に起因する欠陥クラスターを大幅に削減可能で、パターン形成本来の欠陥クラスター数の評価が可能になることが判明した。 In other words, by changing the liquid removal method, the number of defect clusters was greatly reduced, which was attributed to the liquid shaking method in the evaluation test, and further to the evaluation method described in the examples. According to this, it has been found that the defect clusters resulting from this liquid shaking-off process can be greatly reduced, and the number of defect clusters inherent in pattern formation can be evaluated.
以上のように、本発明にかかる液体の除去方法は、レジスト膜やその上層に形成された保護膜などの被露光膜に接触し、付着した液体を迅速かつ十全に除去可能であり、そのために被露光膜の液体接触による特性変化の評価や、液体の接触による影響を最小限に抑えることができ、液体が被露光膜に接触するプロセスを有するフォトリソグラフィー技術の高精度化に効果的な寄与を行うことができる。 As described above, the method for removing a liquid according to the present invention makes it possible to quickly and fully remove the attached liquid in contact with an exposed film such as a resist film or a protective film formed thereon. In addition, it is possible to evaluate changes in characteristics of exposed films due to liquid contact and to minimize the effects of liquid contact, and is effective for improving the accuracy of photolithography technology that has a process in which liquid contacts the exposed film. You can make a contribution.
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