JP2006227174A - Resist developing solution and pattern forming method - Google Patents
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Abstract
Description
本発明は、レジスト膜を形成するためのレジスト現像液及びパターン形成方法に関する。 The present invention relates to a resist developer and a pattern forming method for forming a resist film.
近年、ＬＳＩのさらなる微細化や単電子トランジスタに代表されるよういなナノデバイスの研究開発の活発化に伴い、構造体を１００ｎｍ以下の高精度で加工する技術が使用されている。このような加工は、リソグラフィ技術により実現される。リソグラフィ技術とは、レジストを被加工基板に塗布してレジスト膜を形成し、レジスト膜を選択的に感光させて領域内に潜像を形成した後、現像液に浸漬することにより、照射領域と被照射領域との現像液に対する溶解速度の差に基づいて、レジスト膜にパターンを形成する技術である。 In recent years, with further miniaturization of LSIs and active research and development of nanodevices such as single-electron transistors, techniques for processing structures with high accuracy of 100 nm or less have been used. Such processing is realized by a lithography technique. Lithography technology is to apply a resist to a substrate to be processed to form a resist film, selectively expose the resist film to form a latent image in the area, and then immerse it in a developing solution, thereby irradiating the irradiated area. This is a technique for forming a pattern on a resist film based on a difference in dissolution rate with respect to a developing solution from an irradiated region.
なお、照射領域内側が溶解除去されるタイプをポジ型という。１００ｎｍ以下の寸法をなす微細なパターンをレジスト膜に形成する場合には、パターンの側壁の表面の微小な凸凹（ラインエッジラフネス）を無視することができず、パターンの寸法揺らぎ（パターンの寸法の最大値と最小値との差）を生じてしまう。この寸法揺らぎは、素子特性のバラつきにそのまま結びついてしまうため、素子の許容度以下に抑える必要がある。 A type in which the inside of the irradiation region is dissolved and removed is called a positive type. When a fine pattern having a dimension of 100 nm or less is formed on a resist film, minute unevenness (line edge roughness) on the surface of the pattern side wall cannot be ignored, and pattern dimension fluctuation (pattern dimension fluctuation) Difference between the maximum value and the minimum value). This dimensional fluctuation is directly linked to variations in element characteristics, and therefore must be suppressed to an element tolerance or less.
半導体素子におけるＩＴＲＳ（International Technology Roadmap for Semiconductors）のロードマップでは、パターンサイズ１００ｎｍ、ラインエッジラフネスは、５ｎｍ以下が求められている。また、一般的にラインエッジラフネスとは、パターン側面の寸法揺らぎの主原因については、特許文献１で寸法揺らぎを低減するため、電子散乱を抑制する技術が開示されている。
In the ITRS (International Technology Roadmap for Semiconductors) roadmap for semiconductor devices, a pattern size of 100 nm and a line edge roughness of 5 nm or less are required. In general, line edge roughness is a technique that suppresses electron scattering in order to reduce dimensional fluctuation in
さらに、特許文献２では、ＰＭＭＡ（ポリメチルメタクリレート）やα−クロロアクリル酸メチルとα−メチルスチレンとの共重合体（商品名：ＺＥＰ５２０（日本ゼオン株式会社））等の有機高分子からなる一般的なレジストを用いたレジスト膜中には２０〜３０ｎｍ径の高分子集合体が存在し、これらの高分子集合体が現像時に集合体脱離現象を起こしてパターンの側壁に露出して、ラインエッジラフネスを生じてしまうことが寸法揺らぎの主原因であると述べており、集合体脱離現象を防ぐために集合体同士を結合させることにより、ラインエッジラフネスを低減する技術が開示されている。
Further, in
同様に、特許文献３では、高分子集合体を小径化するレジスト材料により、ラインエッジラフネスを低減する技術が開示されている。このような材料の小径化は、レジスト材料として、ＰＭＭＡのような有機高分子でなく、カリックスアレーン、ＳｉＯ2等の無機材料を含有する材料により実現されている。しかし、このような材料は有機高分子に比べて感度が著しく低い問題があるため、用途が非常に限られる問題を有する。 Similarly, Patent Document 3 discloses a technique for reducing line edge roughness using a resist material that reduces the diameter of a polymer assembly. Such a reduction in the diameter of the material is realized not by an organic polymer such as PMMA as a resist material but by a material containing an inorganic material such as calixarene or SiO 2 . However, since such a material has a problem that sensitivity is remarkably lower than that of an organic polymer, it has a problem that its use is very limited.
さらに、実際に形成したパターンを切断してＳＥＭ（走査型電子顕微鏡）で観察すると、特許文献３（図１を参照）に示すようにレジスト内部（レジスト破断面）に高分子集合体が観察され、同様な周期の凹凸がパターン側面にも観察されていることから、これらの高分子集合体が寸法揺らぎの一因であると考えられる。ただし、パターン側面に観察される凹凸は、レジスト破断面での凹凸の高さに比べて明らかに小さく、露光現像条件により変化することから、レジスト材料だけでなく、現像条件によってもラインエッジラフネスが発生すると考えられる。 Further, when the actually formed pattern is cut and observed with an SEM (scanning electron microscope), a polymer aggregate is observed inside the resist (resist fracture surface) as shown in Patent Document 3 (see FIG. 1). Since similar irregularities are also observed on the side surface of the pattern, it is considered that these polymer aggregates contribute to dimensional fluctuation. However, the unevenness observed on the side surface of the pattern is clearly smaller than the height of the unevenness on the resist fracture surface, and changes depending on the exposure and development conditions, so the line edge roughness depends not only on the resist material but also on the development conditions. It is thought to occur.
上記のような電子ビーム等の放射線を照射して現像してパターンを形成する技術で、現像液に特徴があるものとしては、特許文献４、特許文献５に記載されており、特許文献４には、ケトン系溶剤を使用し、特許文献５には、ケトン系溶剤とエーテル系溶剤の混液を用いている。
しかしながら、特許文献１〜５には、以下に示す問題を有する。
特許文献１に記載されている発明では、電子散乱を低減することは可能であるが、ラインエッジラフネスは電子散乱ではなく高分子集合体に起因するために、ラインエッジラフネスを低減することはできない。
However,
In the invention described in
また、特許文献２に記載されている発明は、高分子集合体同士をリンクさせて高分子集合体と高分子集合体の隙間への溶剤の新というを防止し、ラインエッジラフネスを低減することは可能であるが、感度の低下が著しといった問題が発生してしまう。
In addition, the invention described in
また、特許文献３に記載されている発明は、高分子集合体を小径化するレジスト材料により、ラインエッジラフネスを低減することが可能であるが、このような材料は有機高分子に比べて感度が著しく低い問題があるため、用途が非常に限られてしまうといった問題を有する。 In addition, the invention described in Patent Document 3 can reduce line edge roughness by using a resist material that reduces the diameter of a polymer aggregate. However, such a material is more sensitive than an organic polymer. However, there is a problem that usage is very limited.
また、特許文献４に記載されている発明は、ケトン系溶剤を使用しているため、分子量を大きくすると溶解性が下がってしまうためにラインエッジラフネスを低減することができない。 In addition, since the invention described in Patent Document 4 uses a ketone solvent, if the molecular weight is increased, the solubility is lowered, so that the line edge roughness cannot be reduced.
また、特許文献５に記載されている発明は、ケトン系溶剤とエーテル系溶剤との混液現像液を使用することで、混合した場合でも高分子への浸透作用は単独で作用することから、溶解度の高い溶剤に溶解度の低い溶剤を混合することは溶解度の調整にはなるが、同じ分子サイズの現像液の溶解度を下げたことと等価であることから、ラインエッジラフネスを低減させることができない。
Further, the invention described in
本発明は係る問題に鑑みてなされたものであり、高分子集合体と高分子集合体との隙間への浸透力を弱め、十分な溶解速度を有するレジスト現像液と該レジスト現像液を使用して、低いラインエッジラフネスのパターンを形成可能としたパターン形成方法を提供することを目的とする。 The present invention has been made in view of the above problems, and uses a resist developer having a sufficient dissolution rate and a resist developer that weakens the penetration force into the gap between the polymer aggregate and the polymer aggregate. An object of the present invention is to provide a pattern forming method capable of forming a low line edge roughness pattern.
上記目的を達成するために、請求項１記載のレジスト現像液は、電子ビーム等の放射線の照射により、ポリマー鎖が切断されて低分子化することにより、溶剤に対して溶解するレジスト材料の現像液において、現像液は、酢酸基またはケトン基、エーテル基、フェニル基を少なくとも２つ以上有し、かつ分子量が１５０以上であることを特徴とする。
In order to achieve the above object, the resist developer according to
請求項２記載の発明は、請求項１記載のレジスト現像液であって、現像液はベンゼン系溶剤であり、該ベンゼン系溶剤は、酸素を１つ以上有し、かつ、分子量が１５０以上であることを特徴とする。
The invention according to
請求項３記載の発明は、請求項１記載のレジスト現像液であって、現像液は、酢酸系の溶剤で、酢酸基とは別に酸素を１つ以上有し、かつ分子量が１５０以上であることを特徴とする。
The invention described in claim 3 is the resist developer according to
請求項４記載の発明は、請求項１記載のレジスト現像液であって、現像液は、エーテル系の溶剤で、エーテル基とは別に酸素を１つ以上有し、かつ分子量が１５０以上であることを特徴とする。
The invention according to claim 4 is the resist developer according to
請求項５記載のパターン形成方法は、基板上に電子ビーム等の放射線を照射する工程と、照射する工程によって、ポリマーの鎖が切断されて低分子化することにより、溶剤に対して溶解するレジスト材料を塗布し、焼付けする工程と、焼付けする工程によって得られたレジスト膜に、選択的に電子ビーム、遠紫外線、イオンビームまたはＸ線を照射し露光する工程と、請求項１から４のいずれか１項に記載のレジスト現像液で現像する工程とを有することを特徴とする。
The pattern forming method according to
請求項６記載のパターン形成方法は、現像する工程では、レジスト現像液を加熱することで現像速度を高めて現像することを特徴とする。
The pattern forming method according to
請求項７記載のパターン形成方法は、現像する工程では、レジスト現像液を冷却することで現像速度を下げて現像することを特徴とする。
The pattern forming method according to
本発明によれば、大きな分子量で高分子集合体と高分子集合体との隙間への浸透力を弱め、かつ２つ以上の溶解性を高める官能基を有するので、十分な感度を有し、かつラインエッジラフネスの低い１００ｎｍ以下のパターンを形成することができるレジスト現像液を実現できる。
また、高分子量でかつ十分な溶解性を有する現像液で現像することにより、十分な感度を有し、かつラインエッジラフネスの低い１００ｎｍ以下のパターンを形成することができる。
According to the present invention, since it has a functional group that weakens the penetrating power into the gap between the polymer aggregate and the polymer aggregate with a large molecular weight and increases the solubility of two or more, it has sufficient sensitivity, In addition, a resist developer that can form a pattern of 100 nm or less with low line edge roughness can be realized.
Further, by developing with a developer having a high molecular weight and sufficient solubility, a pattern of 100 nm or less having sufficient sensitivity and low line edge roughness can be formed.
次に、図面を参照して、本実施形態を説明する。
ＰＭＭＡ、ＰＭＩＰＫ（ポリメチルイソプロピルケトン）、ＰＢＳ（ポリブタジエンスチレン）、ポリ（２，２，２−トリフルオロエチル−２−クロロアクリレート）、α−クロロアクリル酸メチルとα−メチルスチレンとの共重合体に代表される有機高分子からなるポジ型レジストは、１０００〜１００万程度の分子量を有する糸状のポリマーが数個〜数１００程度凝集した数１０ｎｍの高分子集合体からなる。
Next, this embodiment will be described with reference to the drawings.
PMMA, PMIPK (polymethyl isopropyl ketone), PBS (polybutadiene styrene), poly (2,2,2-trifluoroethyl-2-chloroacrylate), copolymer of methyl α-chloroacrylate and α-methylstyrene A positive resist made of an organic polymer represented by (1) consists of a polymer aggregate of several tens of nm in which several to several hundreds of filamentous polymers having a molecular weight of about 1,000 to 1,000,000 are aggregated.
実際には高分子集合体は糸球のようなものなので、高分子集合体同士もお互いに有る程度からみあっている。レジストに電子線等の放射線が照射されると高分子の鎖が切断され、分子量が減少する。ＰＭＭＡの場合の露光量（Ｄｏｓｅ量）と分子量の関係を図３に示す。分子量が小さくなると溶剤に対する溶解性が高くなるので、露光されたレジストを溶剤で現像すると照射領域が溶解して除去されパターンが形成される。 Actually, the polymer aggregates are like a ball, so the polymer aggregates are in agreement with each other. When the resist is irradiated with radiation such as an electron beam, the polymer chain is cut and the molecular weight is reduced. The relationship between the exposure amount (Dose amount) and the molecular weight in the case of PMMA is shown in FIG. Since the solubility in a solvent increases as the molecular weight decreases, when the exposed resist is developed with a solvent, the irradiated region dissolves and is removed to form a pattern.
ＰＭＭＡの場合の分子量と４−メチル−２−ペンタノンに対する溶解速度の関係を図４に示す。溶剤の種類と溶解速度の関係は、同じ種類の溶剤の場合、図５のように分子量が大きくなるほど（溶剤の分子サイズが大きくなるほど）溶解速度が遅くなる。 The relationship between the molecular weight in the case of PMMA and the dissolution rate with respect to 4-methyl-2-pentanone is shown in FIG. Regarding the relationship between the type of solvent and the dissolution rate, in the case of the same type of solvent, the dissolution rate decreases as the molecular weight increases (as the solvent molecular size increases) as shown in FIG.
これは、溶剤の分子サイズが大きくなるほど有機高分子への溶剤の浸透力が弱くなるためで、有機高分子の溶解現象は、浸透した溶剤により糸状の有機高分子の絡み合いが解かれ、溶剤側に引き離されていくことによって説明される。 This is because as the solvent molecular size increases, the penetration of the solvent into the organic polymer becomes weaker. The organic polymer dissolution phenomenon is caused by the entanglement of the filamentous organic polymer by the permeated solvent and the solvent side. It is explained by being separated.
この有機高分子への溶剤の浸透は、当然のことながら高分子集合体への浸透に比べ、高分子集合体と高分子集合体との隙間への浸透の方が高速に起きるため、図１、図２のようにパターンの側面に高分子集合体と同様な周期の凹凸が形成され、ラインエッジラフネスが発生する。 Naturally, the permeation of the solvent into the organic polymer is faster in the permeation of the gap between the polymer assembly and the polymer assembly than in the polymer assembly. As shown in FIG. 2, irregularities having the same period as the polymer aggregate are formed on the side surface of the pattern, and line edge roughness is generated.
高分子集合体と高分子集合体との隙間へ溶剤が浸透と同等な速度で高分子集合体へ溶剤が浸透して溶解すれば、ラインエッジラフネスを低減することが可能になる。すなわち、溶剤の分子サイズが同じ場合には、溶剤の溶解速度を高めることにより、ラインエッジラフネスを低減することが可能になる。 If the solvent penetrates and dissolves into the polymer aggregate at a rate equivalent to the penetration of the solvent into the gap between the polymer aggregate, the line edge roughness can be reduced. That is, when the molecular size of the solvent is the same, the line edge roughness can be reduced by increasing the dissolution rate of the solvent.
しかし、溶剤の溶解速度を高めると、電子線が照射されていない領域の溶解速度も高くなるため、パターン形状の悪化、未露光領域の面粗さの悪化などの問題が生じるため、実際には溶剤の溶解速度を高めることにより、ラインエッジラフネスを低減することはできない。さらに、未露光領域の面粗さの悪化は、ランドラフネスも悪化させるので、すなわち、現像液としては、溶解速度はある範囲に限定される。 However, when the dissolution rate of the solvent is increased, the dissolution rate of the region that is not irradiated with the electron beam also increases, which causes problems such as deterioration of the pattern shape and deterioration of the surface roughness of the unexposed region. The line edge roughness cannot be reduced by increasing the dissolution rate of the solvent. Furthermore, the deterioration of the surface roughness of the unexposed area also deteriorates the land roughness. That is, as a developer, the dissolution rate is limited to a certain range.
また、高分子集合体と高分子集合体との隙間への浸透を抑えることにより、ラインエッジラフネスを低減することが可能になる。すなわち、溶剤の高分子集合体を溶解する速度が同じ場合には、溶剤の分子量を大きくして分子サイズを大きくして、高分子集合体と高分子集合体との隙間への浸透を抑えることにより、ラインエッジラフネスを低減することが可能になる。 In addition, it is possible to reduce the line edge roughness by suppressing the permeation into the gap between the polymer aggregate and the polymer aggregate. That is, when the solvent polymer aggregate dissolution rate is the same, increase the molecular weight of the solvent to increase the molecular size and suppress penetration into the gap between the polymer aggregate and the polymer aggregate. Thus, the line edge roughness can be reduced.
ただし、溶剤の分子量を大きくすると、前述に示すように溶解速度が低下して、ラインエッジラフネスを悪化させるばかりでなく、パターニングの感度が悪くなる問題が生じる。
よって、ラインエッジラフネスを低減するためには、溶解速度を低下させることなく、溶剤の分子量を大きくする必要がある有機高分子への溶解速度は、ベンゼン環と、酸素の存在が大きく影響する。また、水酸基ＯＨが存在すると逆に溶解速度が著しく低下する。また、溶解速度は、溶媒の温度によっても大きく変化する。
すなわち、フェニル基、酢酸基、ケトン基、エーテル基を複数有し、かつ大きな分子量を有する溶剤を含有する現像液により、ラインエッジラフネスを低減することが可能になる。
However, when the molecular weight of the solvent is increased, the dissolution rate is lowered as described above, and not only the line edge roughness is deteriorated, but also the problem of poor patterning sensitivity arises.
Therefore, in order to reduce line edge roughness, the benzene ring and the presence of oxygen have a great influence on the dissolution rate in an organic polymer where the molecular weight of the solvent needs to be increased without reducing the dissolution rate. On the other hand, when the hydroxyl group OH is present, the dissolution rate is significantly reduced. In addition, the dissolution rate varies greatly depending on the temperature of the solvent.
That is, the line edge roughness can be reduced by a developer containing a solvent having a plurality of phenyl groups, acetic acid groups, ketone groups, and ether groups and having a large molecular weight.
図１、図２に示すようにＰＭＭＡ、ＰＭＩＰＫ（ポリメチルイソプロピルケトン）、ＰＢＳ（ポリブタジエンスチレン）、ポリ（２，２，２−トリフルオロエチル−２−クロロアクリレート）、α−クロロアクリル酸メチルとα−メチルスチレンとの共重合体に代表される有機高分子からなるポジ型レジストは、数１０ｎｍの高分子集合体からなり、ラインエッジラフネスの発生に関与する。 As shown in FIG. 1 and FIG. 2, PMMA, PMIPK (polymethyl isopropyl ketone), PBS (polybutadiene styrene), poly (2,2,2-trifluoroethyl-2-chloroacrylate), methyl α-chloroacrylate and A positive resist made of an organic polymer typified by a copolymer with α-methylstyrene is made of a polymer aggregate of several tens of nanometers and is involved in the generation of line edge roughness.
これらの有機高分子からなるポジ型レジストは、電子ビーム、遠紫外線、イオンビームまたはＸ線等の放射線が照射されると高分子の鎖が切断され、図３に示すように分子量が減少し、図４に示すように現像液に対する溶解速度が増加し、放射線の照射部が現像液に溶解してパターンが形成される。 Positive type resists made of these organic polymers have polymer chains cut when irradiated with radiation such as electron beam, far ultraviolet ray, ion beam or X-ray, and the molecular weight decreases as shown in FIG. As shown in FIG. 4, the dissolution rate with respect to the developer increases, and the radiation irradiated portion dissolves in the developer to form a pattern.
図３、図４では、ＰＭＭＡを４−メチル−２−ペンタノンで現像した場合の溶解速度を示す。
溶剤の種類と溶解速度の関係は、同じ種類の溶剤の場合図５のように分子量が大きくなるほど溶剤の分子サイズが大きくなるほど）溶解速度が遅くなる。これは、溶剤の分子サイズが大きくなるほど有機高分子への溶剤の浸透力が弱くなるためで、有機高分子の溶解現象は、新党した溶剤により糸状の有機高分子の絡み合いが解かれ、溶剤側に引き離されていくことによって説明される。
3 and 4 show the dissolution rate when PMMA is developed with 4-methyl-2-pentanone.
Regarding the relationship between the type of solvent and the dissolution rate, in the case of the same type of solvent, the dissolution rate becomes slower as the molecular weight increases and the molecular size of the solvent increases as shown in FIG. This is because, as the molecular size of the solvent increases, the penetration of the solvent into the organic polymer becomes weaker. The dissolution phenomenon of the organic polymer is untangled by the new party solvent, and the solvent side It is explained by being separated.
この有機高分子への溶剤の浸透は、当然のことながら高分子集合体への浸透に比べ、高分子集合体と高分子集合体の隙間への浸透の方が高速に起きるため、図１、図２のようにパターンの側面に高分子集合体と同様な周期の凹凸が形成され、ラインエッジラフネスが発生する。 Since the permeation of the solvent into the organic polymer naturally occurs faster in the gap between the polymer assembly and the polymer assembly than in the polymer assembly, FIG. As shown in FIG. 2, irregularities having the same period as the polymer aggregate are formed on the side surface of the pattern, and line edge roughness is generated.
このことは、高分子集合体と高分子集合体との隙間への浸透を抑えることにより、ラインエッジラフネスを低減することが可能であることを意味する。すなわち、溶剤の高分子集合体を溶解する速度が同じ場合には、溶剤の分子量を大きくして分子サイズを大きくして、高分子集合体と高分子集合体との隙間への浸透を抑えることにより、ラインエッジラフネスを低減することが可能になる。 This means that the line edge roughness can be reduced by suppressing penetration of the polymer aggregate into the gap between the polymer aggregate. That is, when the solvent polymer aggregate dissolution rate is the same, increase the molecular weight of the solvent to increase the molecular size and suppress penetration into the gap between the polymer aggregate and the polymer aggregate. Thus, the line edge roughness can be reduced.
実際には、α−クロロアクリル酸メチルとα−メチルスチレンとの共重合体（商品名：ＺＥＰ−５２０Ａ）を電子ビームで完全露光し（露光量：１５０μＣ／ｃｍ2）、各種現像液で現像した場合の溶解速度を図６に示す。 Actually, a copolymer of α-methyl chloroacrylate and α-methylstyrene (trade name: ZEP-520A) is completely exposed with an electron beam (exposure amount: 150 μC / cm 2 ), and developed with various developers. The dissolution rate in this case is shown in FIG.
ラインエッジラフネスは、加速電圧５０ｋＶ、ビーム径２０ｎｍでライン＆スペースパターンを複数の露光量で描画し、溝とスペースがともに１００ｎｍになった領域のパターンをＳＥＭ（走査型電子顕微鏡）で撮影し、撮影された画像から溝のエッジを画像処理で検出してエッジ座標から測定した。 Line edge roughness is a line & space pattern drawn with multiple exposures at an acceleration voltage of 50 kV and a beam diameter of 20 nm, and a pattern of a region where both grooves and spaces are 100 nm is photographed with an SEM (scanning electron microscope). The edge of the groove was detected by image processing from the photographed image and measured from the edge coordinates.
図７は、溶解速度が２００〜３００ｎｍと５００〜６００ｎｍに分類して現像液分子量と、ラインエッジラフネスの関係をグラフ化した。酢酸ｎアミルが、一般的に使用されている標準現像液である。
図６、図７から明らかなようにラインエッジラフネスは、現像液の分子量を大きくすることにより、低減される。同様に、分子量４９５０００のＰＭＭＡを電子ビームで完全露光し（露光量：３００μＣ／ｃｍ2）、各種現像液で現像した場合の溶解速度を図１１に示す（ラインエッジラフネスの測定は、前述の通り）。
FIG. 7 is a graph showing the relationship between the developer molecular weight and the line edge roughness by classifying the dissolution rate into 200 to 300 nm and 500 to 600 nm. N-amyl acetate is a commonly used standard developer.
As apparent from FIGS. 6 and 7, the line edge roughness is reduced by increasing the molecular weight of the developer. Similarly, PMMA having a molecular weight of 495,000 is completely exposed with an electron beam (exposure amount: 300 μC / cm 2 ) and developed with various developing solutions. FIG. 11 shows the dissolution rate (measurement of line edge roughness is as described above). ).
図１２は、溶解速度が１５０〜２５０ｎｍの場合の現像液分子量とラインエッジラフネスの関係をグラフ化した。
図１１、図１２から明らかなようにＰＭＭＡの場合にもラインエッジラフネスは５ｎｍ以下が求められており、図７、図１２から明らかなように、現像液分子量は、１５０以上が必要条件となる。ただし、前述のように現像液の分子量を大きくすると、溶解速度が落ち、大きな露光量で露光しないとパターン形成できなくなる問題がある。
FIG. 12 is a graph showing the relationship between the developer molecular weight and the line edge roughness when the dissolution rate is 150 to 250 nm.
As is clear from FIGS. 11 and 12, the line edge roughness is also required to be 5 nm or less in the case of PMMA. As is clear from FIGS. 7 and 12, the molecular weight of the developer is 150 or more. . However, when the molecular weight of the developer is increased as described above, there is a problem that the dissolution rate decreases, and the pattern cannot be formed unless the exposure is performed with a large exposure amount.
実際には、完全露光された状態で溶解速度が１００Å／ｓｅｃ以上なければパターン形成困難である。また、逆に、７００Å／ｓｅｃを超える溶解速度では、未露光部（露光しない領域）が溶解して、ランド部の膜減り、ランド部の荒れの発生が起きるので、パターン形成困難である。すなわち、分子量を大きくしても、溶解速度は所定領域に存在しないと現像液としては使用できないので、分子量を大きくすることによって低下する溶解性を官能基等で補う必要がある。 Actually, it is difficult to form a pattern unless the dissolution rate is 100 Å / sec or more in a completely exposed state. On the other hand, at a dissolution rate exceeding 700 liters / sec, the unexposed portion (non-exposed region) is dissolved, the land portion is reduced in film thickness, and the land portion is roughened, making it difficult to form a pattern. That is, even if the molecular weight is increased, the dissolution rate cannot be used as a developer unless the dissolution rate is in a predetermined region. Therefore, it is necessary to supplement the solubility, which decreases with increasing molecular weight, with a functional group or the like.
実際には、有機高分子からなるポジ型レジストの溶解性には、酸素の存在が大きく寄与する。よって、酢酸基、ケトン基、エーテル基、フェニル基のうち１つ以上の官能基を複数有することにより、溶解速度を低下させることなく、１５０以上の分子量を実現することができ、ラインエッジラフネスを５ｎｍ以下にさせることが可能となる。 Actually, the presence of oxygen greatly contributes to the solubility of a positive resist made of an organic polymer. Therefore, by having a plurality of one or more functional groups of acetic acid group, ketone group, ether group, and phenyl group, it is possible to realize a molecular weight of 150 or more without lowering the dissolution rate, thereby reducing the line edge roughness. It becomes possible to make it 5 nm or less.
[実施例１]
α−クロロアクリル酸メチルとα−メチルスチレンとの共重合体（商品名ＺＥＰ−５２０Ａ）を加速電圧５０ｋＶ、ビーム径２０ｎｍの電子ビームで露光して１００ｎｍのライン＆スペースパターンの潜像を形成し、酢酸基とエーテル基を１つづつ有し、分子量が１６０．２の酢酸２ブトキシエチルで現像した。
パターンをＳＥＭにより、ラインエッジラフネスを測定したところ４．７ｎｍであった。
[Example 1]
A copolymer of methyl α-chloroacrylate and α-methylstyrene (trade name ZEP-520A) is exposed with an electron beam having an acceleration voltage of 50 kV and a beam diameter of 20 nm to form a latent image having a 100 nm line and space pattern. Developed with 2-butoxyethyl acetate having one acetic acid group and one ether group and a molecular weight of 160.2.
When the line edge roughness of the pattern was measured by SEM, it was 4.7 nm.
[比較例１]
α−クロロアクリル酸メチルとα−メチルスチレンとの共重合体（商品名ＺＥＰ−５２０Ａ）を加速電圧５０ｋＶ、ビーム径２０ｎｍの電子ビームで露光し、１００ｎｍのライン＆スペースパターンの潜像を形成し、酢酸基１つを有し、分子量が１３０の酢酸ｎアミルで現像したところラインエッジラフネスは、５．５ｎｍであった。
[Comparative Example 1]
A copolymer of methyl α-chloroacrylate and α-methylstyrene (trade name ZEP-520A) is exposed with an electron beam having an acceleration voltage of 50 kV and a beam diameter of 20 nm to form a latent image having a 100 nm line and space pattern. When developed with n-amyl acetate having one acetic acid group and a molecular weight of 130, the line edge roughness was 5.5 nm.
[実施例２]
α−クロロアクリル酸メチルとα−メチルスチレンとの共重合体（商品名ＺＥＰ−５２０Ａ）を加速電圧５０ｋＶ、ビーム径２０ｎｍの電子ビームで露光し、１２０ｎｍのライン＆スペースパターンの潜像を形成し、ベンゼン環とエーテル基を１つづつ有し、分子量が１６４．２のペンチルフェニルエーテルで現像したところラインエッジラフネスは４．７ｎｍであった。
[Example 2]
A copolymer of methyl α-chloroacrylate and α-methylstyrene (trade name ZEP-520A) is exposed with an electron beam having an acceleration voltage of 50 kV and a beam diameter of 20 nm to form a latent image having a 120 nm line and space pattern. When developed with pentylphenyl ether having one benzene ring and one ether group and a molecular weight of 164.2, the line edge roughness was 4.7 nm.
[比較例２]
α−クロロアクリル酸メチルとα−メチルスチレンとの共重合体（商品名ＺＥＰ−５２０Ａ）を加速電圧５０ｋＶ、ビーム径２０ｎｍの電子ビームで露光し、１２０ｎｍのライン＆スペースパターンの潜像を形成し、酢酸基１つを分子量が１３０の酢酸ｎアミルで現像したところラインエッジラフネスは、５．４ｎｍであった。
[Comparative Example 2]
A copolymer of methyl α-chloroacrylate and α-methylstyrene (trade name ZEP-520A) is exposed with an electron beam having an acceleration voltage of 50 kV and a beam diameter of 20 nm to form a latent image having a 120 nm line and space pattern. When one acetic acid group was developed with n-amyl acetate having a molecular weight of 130, the line edge roughness was 5.4 nm.
[実施例３]
α−クロロアクリル酸メチルとα−メチルスチレンとの共重合体（商品名ＺＥＰ−５２０Ａ）を加速電圧５０ｋＶ、ビーム径２０ｎｍの電子ビームで露光し、６０ｎｍのライン＆スペースパターンの潜像を形成し、ベンゼン環と２個の酸素を有し、分子量が１６６．２のフェニルアセトアルデヒドジメチルアセタールで現像したところラインエッジラフネスは、４．５ｎｍであった。
[Example 3]
A copolymer of methyl α-chloroacrylate and α-methylstyrene (trade name ZEP-520A) is exposed with an electron beam having an acceleration voltage of 50 kV and a beam diameter of 20 nm to form a latent image having a 60 nm line and space pattern. When developed with phenylacetaldehyde dimethyl acetal having a benzene ring and two oxygens and a molecular weight of 166.2, the line edge roughness was 4.5 nm.
[比較例３]
α−クロロアクリル酸メチルとα−メチルスチレンとの共重合体（商品名ＺＥＰ−５２０Ａ）を加速電圧５０ｋＶ、ビーム径２０ｎｍの電子ビームで露光し、６０ｎｍのライン＆スペースパターンの潜像を形成し、酢酸基１つを有し、分子量が１３０の酢酸ｎアミルで現像したところラインエッジラフネスは５．５ｎｍであった。
[Comparative Example 3]
A copolymer of methyl α-chloroacrylate and α-methylstyrene (trade name ZEP-520A) is exposed with an electron beam having an acceleration voltage of 50 kV and a beam diameter of 20 nm to form a latent image having a 60 nm line and space pattern. When developed with n-amyl acetate having one acetic acid group and a molecular weight of 130, the line edge roughness was 5.5 nm.
[実施例４]
分子量４９５０００のＰＭＭＡを加速電圧５０ｋＶ、ビーム径２０ｎｍの電子ビームで露光し、１００ｎｍのライン＆スペースパターンの潜像を形成し、酢酸基とエーテル基を１つづつ有し、分子量が１６０．２の酢酸２ブトキシエチルで現像したところラインエッジラフネスは、４．６ｎｍであった。
[Example 4]
A PMMA having a molecular weight of 495,000 is exposed with an electron beam having an acceleration voltage of 50 kV and a beam diameter of 20 nm to form a latent image having a line and space pattern of 100 nm, having one acetate group and one ether group, and having a molecular weight of 160.2. When developed with 2-butoxyethyl acetate, the line edge roughness was 4.6 nm.
[比較例４]
分子量４９５０００のＰＭＭＡを加速電圧５０ｋＶ、ビーム径２０ｎｍの電子ビームで露光し、１００ｎｍのライン＆スペースパターンの潜像を形成し、分子量１００の４−メチル−２−ペンタノンと分子量６０のＩＰＡの混液で現像したところラインエッジラフネスは、５．８ｎｍであった。
[Comparative Example 4]
A PMMA with a molecular weight of 495,000 is exposed with an electron beam with an acceleration voltage of 50 kV and a beam diameter of 20 nm to form a latent image with a 100 nm line and space pattern, and a mixture of 4-methyl-2-pentanone with a molecular weight of 100 and IPA with a molecular weight of 60 When developed, the line edge roughness was 5.8 nm.
[実施例５]
分子量４９５０００のＰＭＭＡを加速電圧５０ｋＶ、ビーム径２０ｎｍの電子ビームで露光し、１２０ｎｍのライン＆スペースパターンの潜像を形成し、酢酸基１個とエーテル基２個を有し、分子量１７６．２の酢酸２（エトキシエトキシ）エチルで現像したところラインエッジラフネスは、４．４ｎｍであった。
[Example 5]
A PMMA having a molecular weight of 495,000 is exposed with an electron beam having an acceleration voltage of 50 kV and a beam diameter of 20 nm to form a latent image having a 120 nm line and space pattern, having one acetic acid group and two ether groups, and having a molecular weight of 176.2. When developed with 2 (ethoxyethoxy) ethyl acetate, the line edge roughness was 4.4 nm.
[比較例５]
分子量４９５０００のＰＭＭＡを加速電圧５０ｋＶ、ビーム径２０ｎｍの電子ビームで露光し、１２０ｎｍのライン＆スペースパターンの潜像を形成し、分子量１００の４−メチル−２−ペンタノンと分子量６０のＩＰＡの混液で現像したところラインエッジラフネスは、５．８ｎｍであった。
[Comparative Example 5]
A PMMA with a molecular weight of 495000 is exposed to an electron beam with an acceleration voltage of 50 kV and a beam diameter of 20 nm to form a latent image with a 120 nm line and space pattern, and a mixture of 4-methyl-2-pentanone with a molecular weight of 100 and IPA with a molecular weight of 60 When developed, the line edge roughness was 5.8 nm.
現像液は、上記に限定されるものではなく、酢酸基、ケトン棋、エーテル基、フェニル基のうち１つ以上の官能基を複数有し、かつ分子量が１５０以上の溶剤が該当する。また、上記レジスト材料に限定されるわけではなく、電子ビーム等放射線の照射により、ポリマーの鎖が切断されて低分子化することにより、溶剤に対して溶解するレジスト材料が該当する。 The developer is not limited to the above, and corresponds to a solvent having a plurality of one or more functional groups of acetic acid group, ketone cage, ether group, and phenyl group and having a molecular weight of 150 or more. The resist material is not limited to the above resist material, and corresponds to a resist material that dissolves in a solvent when a polymer chain is cut and its molecular weight is reduced by irradiation with radiation such as an electron beam.
以上の説明から、本実施形態では、大きな分子量で高分子集合体と高分子集合体の隙間への浸透力を弱め、かつ２つ以上の溶解性を高める官能基を有するので、十分な感度を有し、かつラインエッジラフネスの低い１００ｎｍ以下のパターンを形成できる現像液を実現することができる。 From the above description, in this embodiment, since it has a functional group that weakens the penetrating power into the gap between the polymer aggregate and the polymer aggregate with a large molecular weight and enhances the solubility of two or more, sufficient sensitivity is obtained. A developer capable of forming a pattern of 100 nm or less having low line edge roughness can be realized.
また、大きな分子量で高分子集合体と高分子集合体の隙間への浸透力を弱め、かつベンゼン環と酸素により、十分な感度を有し、かつラインエッジラフネスの低い１００ｎｍ以下のパターンを形成できる現像液を実現できる。 In addition, a large molecular weight can weaken the penetration force into the gap between the polymer aggregates, and the benzene ring and oxygen can form a pattern of 100 nm or less with sufficient sensitivity and low line edge roughness. A developer can be realized.
また、大きな分子量で高分子集合体と高分子集合体との隙間への浸透力を弱め、かつ酢酸基と酸素により、十分な感度を有し、かつラインエッジラフネスの低い１００ｎｍ以下のパターンを形成できる現像液を実現することができる。 In addition, with a large molecular weight, the penetration force into the gap between polymer aggregates is weakened, and with acetic acid groups and oxygen, a pattern with 100 nm or less is formed with sufficient sensitivity and low line edge roughness. A developer that can be produced can be realized.
また、大きな分子量で高分子集合体と高分子集合体との隙間への浸透力を弱め、かつエーテル基と酸素により、十分な感度を有し、かつラインエッジラフネスの低い１００ｎｍ以下のパターンを形成できる現像液を実現することができる。 In addition, with a large molecular weight, the penetration force into the gap between polymer aggregates is weakened, and with ether groups and oxygen, a pattern of 100 nm or less with sufficient sensitivity and low line edge roughness is formed. A developer that can be produced can be realized.
また、溶解速度の不足する現像液に対し、低いラインエッジラフネスの１００ｎｍ以下のパターンを形成することができる。 Further, a pattern having a low line edge roughness of 100 nm or less can be formed for a developing solution having a short dissolution rate.
さらに、溶解速度が大きすぎて未露光部の荒れが発生する現像液に対し、低いラインエッジラフネスの１００ｎｍ以下のパターンを形成することができる。 Furthermore, a pattern having a low line edge roughness of 100 nm or less can be formed for a developing solution in which the dissolution rate is too high and the unexposed portions are roughened.
Claims (7)
前記現像液は、酢酸基またはケトン基、エーテル基、フェニル基を少なくとも２つ以上有し、かつ分子量が１５０以上であることを特徴とするレジスト現像液。 In the developer of the resist material that dissolves in the solvent by cutting the polymer chain and reducing the molecular weight by irradiation with radiation such as an electron beam,
The resist developer has at least two acetic acid groups or ketone groups, ether groups, and phenyl groups, and has a molecular weight of 150 or more.
前記照射する工程によって、ポリマーの鎖が切断されて低分子化することにより、溶剤に対して溶解するレジスト材料を塗布し、焼付けする工程と、
前記焼付けする工程によって得られたレジスト膜に、選択的に電子ビーム、遠紫外線、イオンビームまたはＸ線を照射し露光する工程と、
請求項１から４のいずれか１項に記載のレジスト現像液で現像する工程とを有することを特徴とするパターン形成方法。 Irradiating the substrate with radiation such as an electron beam;
Applying and baking a resist material that dissolves in a solvent by cutting the polymer chain and reducing the molecular weight by the irradiation step;
A step of selectively irradiating the resist film obtained by the baking step with an electron beam, a deep ultraviolet ray, an ion beam or an X-ray;
A pattern forming method comprising: developing with the resist developer according to claim 1.
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| EP1980911A2 (en) | 2007-04-13 | 2008-10-15 | FUJIFILM Corporation | Pattern forming method, resist composition to be used in the pattern forming method, negative developing solution to be used in the pattern forming method and rinsing solution for negative development to be used in the pattern forming method |
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