JP2007328060A - Pattern forming method, and radiation-sensitive resin composition and radiation-sensitive acid generation group-containing resin for use in the same - Google Patents

Pattern forming method, and radiation-sensitive resin composition and radiation-sensitive acid generation group-containing resin for use in the same Download PDF

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JP2007328060A
JP2007328060A JP2006157873A JP2006157873A JP2007328060A JP 2007328060 A JP2007328060 A JP 2007328060A JP 2006157873 A JP2006157873 A JP 2006157873A JP 2006157873 A JP2006157873 A JP 2006157873A JP 2007328060 A JP2007328060 A JP 2007328060A
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JP2007328060A5 (en
JP4725427B2 (en
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Daisuke Shimizu
大輔 清水
Toshiyuki Kai
敏之 甲斐
Shinji Matsumura
信司 松村
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JSR Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography

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Abstract

<P>PROBLEM TO BE SOLVED: To provide a pattern forming method suitable for fine pattern formation with an electron beam, X-ray or extreme ultraviolet radiation, and a radiation-sensitive resin composition and a radiation-sensitive acid generation group-containing resin for use in the same. <P>SOLUTION: In this pattern forming method, a resist pattern is formed by generating an acid from a radiation-sensitive acid generation group-containing resin contained as a resin component in a radiation-sensitive resin composition by irradiation with an actinic ray or radiation to increase the solubility of the radiation-sensitive acid generation group-containing resin in a developer. This radiation-sensitive resin composition contains as a resin component only an acid generation group-containing resin which comprises a repeating unit containing an acid generation group capable of generating an acid upon irradiation with an actinic ray or radiation and a non-acid-dissociative repeating unit. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、微細加工に好適なパターン形成方法並びにそれに用いられる感放射線性樹脂組成物及び感放射線性酸発生基含有樹脂に関する。更に詳しくは、電子線（以下、「ＥＢ」という）、Ｘ線、極紫外線（以下、「ＥＵＶ」という）による微細パターン形成に好適なパターン形成方法並びにそれに用いられる感放射線性樹脂組成物及び感放射線性酸発生基含有樹脂に関する。   The present invention relates to a pattern forming method suitable for fine processing, a radiation-sensitive resin composition used therefor, and a radiation-sensitive acid-generating group-containing resin. More specifically, a pattern forming method suitable for forming a fine pattern using an electron beam (hereinafter referred to as “EB”), X-rays, or extreme ultraviolet rays (hereinafter referred to as “EUV”), and a radiation-sensitive resin composition and sensitivity The present invention relates to a resin containing a radioactive acid generating group.

集積回路素子の製造に代表される微細加工の分野においては、集積回路のより高い集積度を得るために、リソグラフィーにおけるデザインルールの微細化が急速に進行しており、微細加工を安定して行なうことができるリソグラフィープロセスの開発が強く推し進められている。しかしながら、従来のＫｒＦ、ＡｒＦエキシマレーザーを用いる方法では１００ｎｍ以下の微細パターンを高精度に形成することが困難であるため、ＥＢ、ＥＵＶを使用する方法が提案されている。   In the field of microfabrication represented by the manufacture of integrated circuit elements, in order to obtain a higher degree of integration of integrated circuits, miniaturization of design rules in lithography is progressing rapidly, and microfabrication is performed stably. The development of lithographic processes that can do this is strongly promoted. However, since it is difficult to form a fine pattern of 100 nm or less with high accuracy by the conventional method using KrF or ArF excimer laser, a method using EB or EUV has been proposed.

このような超微細加工に使用されるＥＢ又はＥＵＶ用ポジ型レジスト材として用いられる感放射線性樹脂組成物としては、（１）酸解離性官能基で部分的に保護されたポリヒドロキシスチレン系樹脂（ＫｒＦエキシマ用樹脂）及びノボラック（ｉ線用樹脂）と酸発生剤を有する化学増幅型感放射線性樹脂組成物、（２）ＰＭＭＡ（ポリメチルメタクリレート）等のメタクリル系主鎖切断型感放射線性樹脂組成物などが提案されている。
上記（１）の化学増幅型感放射線性樹脂組成物としては、例えば、感度、解像度、エッチング耐性のバランスに優れ、部分アセタール保護ポリヒドロキシスチレン樹脂＋酸発生剤（特許文献３参照）、各種酸解離性部分保護ポリヒドロキシスチレン樹脂＋フッ素含有芳香族スルホン酸発生オニウム塩＋フッ素系又はシリコン系界面活性剤（特許文献４参照）、カチオン部の置換基として少なくとも１つの電子吸引基（Ｆ、シアノ基、ニトロ基）を有するオニウム塩（特許文献５参照）、ジスルホニル基を有する樹脂（特許文献６参照）、Ｎ−オキシイミドスルホニル基を有する樹脂（特許文献７参照）等各種特許が出願されている。
しかし、微細なパターン形成時の膜面荒れ（ラフネス）、感度、解像度において、実用レベルには至っていないのが現状である。 As a radiation sensitive resin composition used as a positive resist material for EB or EUV used in such ultrafine processing, (1) a polyhydroxystyrene resin partially protected with an acid-dissociable functional group (KrF excimer resin) and novolak (i-line resin) and chemically amplified radiation-sensitive resin composition having an acid generator, (2) methacrylic main chain-cutting radiation sensitivity such as PMMA (polymethyl methacrylate) Resin compositions have been proposed.
As the chemical amplification type radiation sensitive resin composition of (1) above, for example, it has an excellent balance of sensitivity, resolution and etching resistance, partially acetal-protected polyhydroxystyrene resin + acid generator (see Patent Document 3), various acids Dissociative partially protected polyhydroxystyrene resin + fluorine-containing aromatic sulfonic acid-generating onium salt + fluorine-based or silicon-based surfactant (see Patent Document 4), at least one electron-withdrawing group (F, cyano as a cation moiety substituent) Various patents such as an onium salt having a nitro group (see Patent Document 5), a resin having a disulfonyl group (see Patent Document 6), a resin having an N-oxyimidosulfonyl group (see Patent Document 7), etc. ing.
However, the present situation is that the film surface roughness (roughness), sensitivity, and resolution at the time of forming a fine pattern have not reached a practical level.

また、上記（２）のメタクリル系主鎖切断型感放射線性樹脂組成物は、解像度には優れるが、エッチング耐性、感度、アウトガスに問題があり実用化は困難である。更に、解像度と感度のバランスに優れるポリｔ−ブチルα−クロロメチルスチレン（特許文献１参照）や、樹脂末端に電子線により切断され易い原子（Ｎ、Ｏ、Ｓ）を導入した特許出願（特許文献２参照）がされている。
しかし、感度の改良は認められるが、感度、エッチング耐性、アウトガスにおいて、実用レベルには至っていないのが現状である。 The methacrylic main chain-cutting radiation sensitive resin composition (2) is excellent in resolution, but has problems in etching resistance, sensitivity, and outgas, and is difficult to put into practical use. Furthermore, a patent application (patent application) in which poly t-butyl α-chloromethylstyrene (see Patent Document 1), which has an excellent balance between resolution and sensitivity, and atoms (N, O, S) that are easily cleaved by an electron beam at the resin end are introduced. Reference 2).
However, although an improvement in sensitivity is recognized, at present, the sensitivity, etching resistance, and outgas have not reached the practical level.

特開２０００−１４７７７７号公報JP 2000-147777 A 特開平１１−２９６１２号公報JP 11-29612 A 特開平６−１９４８４２号公報JP-A-6-194842 特開２０００−１８７３３０号公報JP 2000-187330 A 特開２００１−０７５２８３号公報JP 2001-075283 A 特開２００２−０７２４８３号公報JP 2002-072483 A 特開２００２−１０７９２０号公報JP 2002-107920 A

本発明は、上記問題に対処するためになされたものであり、感度、エッチング耐性、解像度に優れ、アウトガスを低減でき、微細パターンを高精度にかつ安定して形成することができる、パターン形成方法並びにそれに用いられる感放射線性樹脂組成物及び感放射線性酸発生基含有樹脂の提供を目的とする。   The present invention has been made in order to address the above-described problems, and has a high sensitivity, etching resistance, resolution, can reduce outgas, and can form a fine pattern with high accuracy and stability. Another object is to provide a radiation-sensitive resin composition and a radiation-sensitive acid-generating group-containing resin used therefor.

上記の課題を達成するための手段として、請求項１に記載の発明は、感放射線性樹脂組成物の樹脂成分として含有されている感放射線性酸発生基含有樹脂から、活性光線又は放射線の照射によって酸を発生させ、該感放射線性酸発生基含有樹脂の現像液に対する溶解性を増大させることにより、レジストパターンを形成することを特徴とするパターン形成方法である。   As a means for achieving the above object, the invention according to claim 1 irradiates actinic rays or radiation from a radiation-sensitive acid-generating group-containing resin contained as a resin component of the radiation-sensitive resin composition. In this pattern forming method, a resist pattern is formed by generating acid by increasing the solubility of the radiation-sensitive acid-generating group-containing resin in a developer.

請求項２に記載の発明は、請求項１に記載のパターン形成方法に使用され、活性光線又は放射線の照射により酸が発生し、現像液に対する溶解性が増大する感放射線性酸発生基含有樹脂であって、上記活性光線又は放射線の照射により酸を発生する酸発生基を含有する、下記一般式（１）及び（２）で表される繰り返し単位のうちの少なくとも一方を含むことを特徴とする感放射線性酸発生基含有樹脂である。

Figure 2007328060

〔一般式（１）において、Ｒ１は水素原子又はメチル基を表し、Ｒ２は水素原子、ヒドロキシル基、ハロゲン基、ニトロ基、カルボキシル基、アルキル基、アルコキシ基を表し、ｎは０〜３の整数であり、ｎが２又は３の場合、Ｒ２は相互に同一でも異なっていてもよい。Ａは単結合又は−ＯＲ３−基を示し、Ｒ３はメチレン基又はアルキレン基を示す。Ｍ＋は一価のオニウムカチオンを表す。〕
〔一般式（２）において、Ｒ４は水素原子又はメチル基を表し、Ｄは−Ｏ−基、又は−ＮＲ５−基を表し、Ｒ５は水素原子又はアルキル基を示す。Ｅはメチレン基、アルキレン基又はアリーレン基を表し、Ｍ＋は一価のオニウムカチオンを表す。〕 The invention according to claim 2 is used in the pattern forming method according to claim 1, and a radiation-sensitive acid-generating group-containing resin that generates acid upon irradiation with actinic rays or radiation and increases solubility in a developer. It contains at least one of the repeating units represented by the following general formulas (1) and (2), which contains an acid generating group that generates an acid upon irradiation with actinic rays or radiation. It is a radiation-sensitive acid generating group-containing resin.
Figure 2007328060
[In General Formula (1), R 1 represents a hydrogen atom or a methyl group, R 2 represents a hydrogen atom, a hydroxyl group, a halogen group, a nitro group, a carboxyl group, an alkyl group, or an alkoxy group, and n is 0 to 3 When n is 2 or 3, R 2 may be the same or different from each other. A represents a single bond or —OR 3 — group, and R 3 represents a methylene group or an alkylene group. M + represents a monovalent onium cation. ]
[In General Formula (2), R 4 represents a hydrogen atom or a methyl group, D represents an —O— group or an —NR 5 — group, and R 5 represents a hydrogen atom or an alkyl group. E represents a methylene group, an alkylene group, or an arylene group, and M + represents a monovalent onium cation. ]

請求項３に記載の発明は、下記一般式（３）、（４）及び（５）で表される非酸解離性繰り返し単位のうちの少なくとも一種を更に含む請求項２に記載の感放射線性酸発生基含有樹脂である。

Figure 2007328060

〔一般式（３）において、Ｒ６は水素原子又はメチル基を表し、Ｇは単結合、メチレン基又はアルキレン基を表し、Ｒ７はアルキル基、水素原子、ヒドロキシル基、アルコキシル基、−ＣＯＯＨ、パーフルオロアルキル基又は芳香族基を表す。ここでＲ７が−ＣＯＯＨ又は芳香族基である場合、Ｇはメチレン基又はアルキレン基を示す。〕
〔一般式（４）において、Ｒ８は水素原子又はメチル基を表し、Ｊは単結合、メチレン基又はアルキレン基を表し、Ｒ９は水素原子、アルキル基、ヒドロキシル基、アルコキシル基、−ＣＯＯＨ、パーフルオロアルキル基、芳香族基又はアミノ基を表す。ここでＲ９がアミノ基、ヒドロキシル基、アルコキシル基、−ＣＯＯＨ、パーフルオロアルキル基又は芳香族基である場合、Ｊはメチレン基又はアルキレン基を示す。〕
〔一般式（５）において、Ｒ１０は水素原子又はメチル基を表し、Ｌはメチレン基又はアルキレン基を表し、Ｒ１１は水素原子、ヒドロキシル基、アルコキシル基、−ＣＯＯＨ、パーフルオロアルキル基、芳香族基又はアミノ基を表す。〕 The invention according to claim 3 further includes at least one of non-acid dissociable repeating units represented by the following general formulas (3), (4) and (5). It is an acid generating group-containing resin.
Figure 2007328060
[In General Formula (3), R 6 represents a hydrogen atom or a methyl group, G represents a single bond, a methylene group or an alkylene group, R 7 represents an alkyl group, a hydrogen atom, a hydroxyl group, an alkoxyl group, —COOH, Represents a perfluoroalkyl group or an aromatic group. Here, when R 7 is —COOH or an aromatic group, G represents a methylene group or an alkylene group. ]
[In General Formula (4), R 8 represents a hydrogen atom or a methyl group, J represents a single bond, a methylene group or an alkylene group, and R 9 represents a hydrogen atom, an alkyl group, a hydroxyl group, an alkoxyl group, —COOH, Represents a perfluoroalkyl group, an aromatic group or an amino group. Here, when R 9 is an amino group, a hydroxyl group, an alkoxyl group, —COOH, a perfluoroalkyl group or an aromatic group, J represents a methylene group or an alkylene group. ]
[In the general formula (5), R 10 represents a hydrogen atom or a methyl group, L represents a methylene group or an alkylene group, R 11 represents a hydrogen atom, a hydroxyl group, an alkoxyl group, —COOH, a perfluoroalkyl group, an aromatic group. Represents a group or an amino group. ]

請求項４に記載の発明は、本感放射線性酸発生基含有樹脂を構成する全繰り返し単位の合計を１００モル％とした場合に、上記一般式（１）及び（２）で表される繰り返し単位の含有率の合計は、１０〜１００モル％である請求項２又は３に記載の感放射線性酸発生基含有樹脂である。   The invention according to claim 4 is a repeating represented by the above general formulas (1) and (2) when the total of all repeating units constituting the radiation-sensitive acid generating group-containing resin is 100 mol%. 4. The radiation-sensitive acid generating group-containing resin according to claim 2, wherein the total content of the units is 10 to 100 mol%.

請求項５に記載の発明は、請求項１に記載のパターン形成方法に使用される感放射線性樹脂組成物であって、樹脂成分として、請求項２乃至４のうちのいずれかに記載の感放射線性酸発生基含有樹脂のみを含有することを特徴とする感放射線性樹脂組成物である。   Invention of Claim 5 is a radiation sensitive resin composition used for the pattern formation method of Claim 1, Comprising: The feeling in any one of Claims 2 thru | or 4 is used as a resin component. It is a radiation sensitive resin composition characterized by containing only a radiation acid generating group-containing resin.

本発明によれば、ＥＢ、Ｘ線又はＥＵＶを用いてパターニングされる場合において、感度、エッチング耐性、解像度に優れ、微細パターンを高精度にかつ安定して形成することができる。更には、本発明における感放射線性樹脂組成物は主鎖切断型ではなく樹脂側鎖の極性変化によって現像液への溶解性が増大するため、アウトガスの低減、高感度化が期待できる。   According to the present invention, when patterning is performed using EB, X-rays, or EUV, it is excellent in sensitivity, etching resistance, and resolution, and a fine pattern can be formed with high accuracy and stability. Furthermore, since the radiation-sensitive resin composition in the present invention is not a main chain cleavage type, and the solubility in a developer increases due to the change in polarity of the resin side chain, reduction of outgas and higher sensitivity can be expected.

以下、本発明の実施の形態について詳細に説明する。
<パターン形成方法>
本発明のパターン形成方法は、感放射線性樹脂組成物の樹脂成分として含有されている感放射線性酸発生基含有樹脂から、活性光線又は放射線（例えば、ＥＢ、Ｘ線、ＥＵＶ等）の照射によって酸（例えば、スルホン酸等）を発生させ、該感放射線性酸発生基含有樹脂の現像液に対する溶解性を増大させることにより、レジストパターンを形成することを特徴とする。即ち、従来のような、（１）酸解離性官能基で部分的に保護された樹脂と、酸発生剤と、を有するような化学増幅型感放射線性樹脂組成物、（２）ＰＭＭＡ等のメタクリル系主鎖切断型の組成物を用いたものではなく、樹脂側鎖の極性変化によって現像液への溶解性が増大する感放射線性樹脂組成物を用いることを特徴とするパターン形成方法である。 Hereinafter, embodiments of the present invention will be described in detail.
<Pattern formation method>
The pattern forming method of the present invention is performed by irradiation with actinic rays or radiation (for example, EB, X-ray, EUV, etc.) from a radiation-sensitive acid-generating group-containing resin contained as a resin component of the radiation-sensitive resin composition. A resist pattern is formed by generating an acid (for example, sulfonic acid) and increasing the solubility of the radiation-sensitive acid-generating group-containing resin in a developer. That is, as in the past, (1) a chemically amplified radiation sensitive resin composition having a resin partially protected with an acid-dissociable functional group and an acid generator, (2) PMMA, etc. It is a pattern forming method characterized by using a radiation-sensitive resin composition whose solubility in a developer is increased by changing the polarity of a resin side chain, rather than using a methacrylic main chain cleavage type composition. .

<感放射線性酸発生基含有樹脂>
本発明における感放射線性酸発生基含有樹脂（以下、「酸発生基含有樹脂」ともいう。）は、上記パターン形成方法に使用されるものであり、オニウムカチオンによる溶解禁止効果によって現像液不溶性又は現像液難溶性となっており、活性光線又は放射線の照射によってオニウムカチオンが分解し、スルホン酸を発生することにより、現像液に対する溶解性が増大する樹脂である。 <Resistance-containing acid-generating group-containing resin>
The radiation-sensitive acid-generating group-containing resin in the present invention (hereinafter also referred to as “acid-generating group-containing resin”) is used in the above pattern forming method, and is insoluble in the developer due to the dissolution inhibiting effect by the onium cation. It is a resin that is hardly soluble in a developing solution, and is decomposed by irradiation with actinic rays or radiation to generate sulfonic acid, thereby increasing the solubility in the developing solution.

上記酸発生基含有樹脂は、下記一般式（１）で表される繰り返し単位（以下、「繰り返し単位（１）」という）及び下記一般式（２）で表される繰り返し単位（以下、「繰り返し単位（２）」という）のうちの少なくとも一方の繰り返し単位を含むものである。   The acid generating group-containing resin includes a repeating unit represented by the following general formula (1) (hereinafter referred to as “repeating unit (1)”) and a repeating unit represented by the following general formula (2) (hereinafter referred to as “repeating” Unit (2) ") at least one repeating unit.

Figure 2007328060
〔一般式（１）において、Ｒ１は水素原子又はメチル基を表し、Ｒ２は水素原子、ヒドロキシル基、ハロゲン基、ニトロ基、カルボキシル基、アルキル基、アルコキシ基を表し、ｎは０〜３の整数であり、ｎが２又は３の場合、Ｒ２は相互に同一でも異なっていてもよい。Ａは単結合又は−ＯＲ３−基を示し、Ｒ３はメチレン基又はアルキレン基を示す。Ｍ＋は一価のオニウムカチオンを表す。〕
〔一般式（２）において、Ｒ４は水素原子又はメチル基を表し、Ｄは−Ｏ−基、又は−ＮＲ５−基を表し、Ｒ５は水素原子又はアルキル基を示す。Ｅはメチレン基、アルキレン基又はアリーレン基を表し、Ｍ＋は一価のオニウムカチオンを表す。〕
Figure 2007328060
 [In General Formula (1), R 1 represents a hydrogen atom or a methyl group, R 2 represents a hydrogen atom, a hydroxyl group, a halogen group, a nitro group, a carboxyl group, an alkyl group, or an alkoxy group, and n is 0 to 3 When n is 2 or 3, R 2 may be the same or different from each other. A represents a single bond or —OR 3 — group, and R 3 represents a methylene group or an alkylene group. M + represents a monovalent onium cation. ]
[In General Formula (2), R 4 represents a hydrogen atom or a methyl group, D represents an —O— group or an —NR 5 — group, and R 5 represents a hydrogen atom or an alkyl group. E represents a methylene group, an alkylene group, or an arylene group, and M + represents a monovalent onium cation. ]

上記一般式（１）におけるＲ２のアルキル基としては、例えば、メチル基、トリフルオロメチル基、エチル基、プロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基、ヘキシル基、オクチル基のような炭素数１〜８個の直鎖状、分岐状アルキル基、又はシクロプロピル基、シクロペンチル基、シクロヘキシル基のような炭素数３〜８個の環状アルキル基等が挙げられる。
また、上記Ｒ２のアルコキシ基としては、例えば、メトキシ基、エトキシ基、プトポキシ基、ｎ−ブトキシ基、イソブトキシ基、ｓｅｃ−ブトキシ基、ヘキシルオキシ基、オクチルオキシ基のような炭素数１〜８個の直鎖状、分岐状アルコキシ基等が挙げられる。 Examples of the alkyl group represented by R 2 in the general formula (1) include a methyl group, a trifluoromethyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a hexyl group, and an octyl group. Examples thereof include a linear or branched alkyl group having 1 to 8 carbon atoms such as a group, or a cyclic alkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group.
In addition, examples of the alkoxy group of R 2 include 1 to 8 carbon atoms such as methoxy group, ethoxy group, ptopoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, hexyloxy group, and octyloxy group. Linear, branched alkoxy groups and the like.

また、一般式（１）におけるＲ３のアルキレン基としては、例えば、エチレン基、１，３−プロピレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基、ヘプタメチレン基、オクタメチレン基、ノナメチレン基、デカメチレン基等の炭素数２〜１０個のアルキレン基、更には、水素原子が部分的に又は全てフッ素原子で置換された炭素数２〜１０個のアルキレン基等が挙げられる。
また、一般式（１）におけるＲ３がメチレン基である場合においても、水素原子が部分的に又は全てフッ素原子で置換されていてもよい。 Examples of the alkylene group represented by R 3 in the general formula (1) include an ethylene group, a 1,3-propylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, and a nonamethylene group. And an alkylene group having 2 to 10 carbon atoms such as a decamethylene group, and an alkylene group having 2 to 10 carbon atoms in which hydrogen atoms are partially or entirely substituted with fluorine atoms.
Even when R 3 in the general formula (1) is a methylene group, the hydrogen atoms may be partially or entirely substituted with fluorine atoms.

上記一般式（２）におけるＲ５のアルキル基としては、例えば、メチル基、エチル基、プロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基のような炭素数１〜４のアルキル基等が挙げられる。 Examples of the alkyl group represented by R 5 in the general formula (2) include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, and a t-butyl group. Groups and the like.

また、一般式（２）におけるＥのアルキレン基としては、例えば、エチレン基、１，３−プロピレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基、ヘプタメチレン基、オクタメチレン基、ノナメチレン基、デカメチレン基、２−メチル−１，３−プロピレン基、２−メチル−１，２−プロピレン基、２−メチル−１，４−ブチレン基等の炭素数２〜１０個の直鎖状、分岐状アルキレン基、１，３−シクロペンチレン基などのシクロペンチレン基、１，４−シクロヘキシレン基などのシクロヘキシレン基、１，５−シクロオクチレン基などのシクロオクチレン基等の炭素数４〜１０の単環式アルキレン基、１，４−ノルボルニレン基若しくは２，５−ノルボルニレン基などのノルボルニレン基、１，３−アダマンチレン基、２，６−アダマンチレン基などのアダマンチレン基等の２〜４環式の炭素数４〜３０の架橋環式炭化水素環基等が挙げられる。尚、このアルキレン基は置換基を有していてもよく、好ましい置換基としては、例えば、炭素数１〜４個のアルコキシ基、ハロゲン基、シアノ基、ヒドロキシ基、カルボキシ基、アルコキシカルボニル基、ニトロ基が挙げられる。   Examples of the alkylene group of E in the general formula (2) include an ethylene group, a 1,3-propylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, Linear or branched chain having 2 to 10 carbon atoms such as decamethylene group, 2-methyl-1,3-propylene group, 2-methyl-1,2-propylene group, 2-methyl-1,4-butylene group 4 carbon atoms such as alkylene group, cyclopentylene group such as 1,3-cyclopentylene group, cyclohexylene group such as 1,4-cyclohexylene group, cyclooctylene group such as 1,5-cyclooctylene group, etc. To 10 monocyclic alkylene group, norbornylene group such as 1,4-norbornylene group or 2,5-norbornylene group, 1,3-adamantylene group, 2 Etc. 2-4 cyclic bridged cyclic hydrocarbon ring group having 4 to 30 carbon atoms, such as adamantylene groups such as 6-adamantylene group. In addition, this alkylene group may have a substituent. Examples of the preferable substituent include an alkoxy group having 1 to 4 carbon atoms, a halogen group, a cyano group, a hydroxy group, a carboxy group, an alkoxycarbonyl group, A nitro group is mentioned.

また、上記Ｅのアリーレン基としては、例えば、フェニレン基、ベンジレン基、ナフチレン基等のような炭素数６〜１４個のものが挙げられる。尚、このアリーレン基は置換基を有していてもよく、好ましい置換基としては、例えば、炭素数１〜４個のアルキル基、炭素数１〜４個のアルコキシ基、ハロゲン基、シアノ基、ヒドロキシ基、カルボキシ基、アルコキシカルボニル基、ニトロ基が挙げられる。   Moreover, as said arylene group of E, a C6-C14 thing like a phenylene group, a benzylene group, a naphthylene group etc. is mentioned, for example. The arylene group may have a substituent, and preferred substituents include, for example, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen group, a cyano group, Examples thereof include a hydroxy group, a carboxy group, an alkoxycarbonyl group, and a nitro group.

また、一般式（１）及び（２）におけるＭ＋の一価のオニウムカチオンとしては、スルホニウムカチオン、ヨードニウムカチオン、ホスホニウムカチオン、ジアゾニウムカチオン、アンモニウムカチオン、ピリジニウムカチオン等が挙げられる。
これらのなかでも、下記一般式（１ａ）で表されるスルホニウムカチオン、下記一般式（１ｂ）で表されるヨードニウムカチオンが好ましい。 In addition, examples of the monovalent onium cation of M + in the general formulas (1) and (2) include a sulfonium cation, an iodonium cation, a phosphonium cation, a diazonium cation, an ammonium cation, and a pyridinium cation.
Among these, a sulfonium cation represented by the following general formula (1a) and an iodonium cation represented by the following general formula (1b) are preferable.

Figure 2007328060
〔一般式（１ａ）において、Ｒ１２、Ｒ１３及びＲ１４は、相互に独立に置換若しくは非置換の炭素数１〜１０のアルキル基、又は置換若しくは非置換の炭素数６〜１８のアリール基を表すか、或いはＲ１２、Ｒ１３及びＲ１４のうちのいずれか２つ以上が相互に結合して式中の硫黄原子と共に環を形成している。〕
〔一般式（１ｂ）において、Ｒ１５及びＲ１６は、相互に独立に置換若しくは非置換の炭素数１〜１０のアルキル基、又は置換若しくは非置換の炭素数６〜１８のアリール基を表すか、或いはＲ１５及びＲ１６が相互に結合して式中のヨウ素原子と共に環を形成している。〕
Figure 2007328060
 [In General Formula (1a), R 12 , R 13 and R 14 are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 18 carbon atoms. Or any two or more of R 12 , R 13 and R 14 are bonded to each other to form a ring together with the sulfur atom in the formula. ]
[In General Formula (1b), each of R 15 and R 16 independently represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 18 carbon atoms. Alternatively, R 15 and R 16 are bonded to each other to form a ring together with the iodine atom in the formula. ]

一般式（１ａ）及び（１ｂ）において、非置換の炭素数１〜１０のアルキル基としては、直鎖状若しくは分岐状のアルキル基が挙げられ、例えば、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、１−メチルプロピル基、２−メチルプロピル基、ｔ−ブチル基、ｎ−ペンチル基、ｉ−ペンチル基、１，１−ジメチルプロピル基、１−メチルブチル基、ｎ−ヘキシル基、ｉ−ヘキシル基、１，１−ジメチルブチル基、ｎ−ヘプチル基、ｎ−オクチル基、ｉ−オクチル基、２−エチルヘキシル基、ｎ−ノニル基、ｎ−デシル基等を挙げることができる。
また、アルキル基の置換基としては、例えば、炭素数６〜３０のアリール基、炭素数２〜３０の直鎖状、分岐状若しくは環状のアルケニル基や、ハロゲン原子、酸素原子、窒素原子、硫黄原子、リン原子、ケイ素原子等のヘテロ原子を含む原子数１〜３０の基等を挙げることができる。 In the general formulas (1a) and (1b), examples of the unsubstituted alkyl group having 1 to 10 carbon atoms include linear or branched alkyl groups such as a methyl group, an ethyl group, and an n-propyl group. I-propyl group, n-butyl group, 1-methylpropyl group, 2-methylpropyl group, t-butyl group, n-pentyl group, i-pentyl group, 1,1-dimethylpropyl group, 1-methylbutyl group N-hexyl group, i-hexyl group, 1,1-dimethylbutyl group, n-heptyl group, n-octyl group, i-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, etc. Can be mentioned.
Examples of the substituent of the alkyl group include, for example, an aryl group having 6 to 30 carbon atoms, a linear, branched or cyclic alkenyl group having 2 to 30 carbon atoms, a halogen atom, an oxygen atom, a nitrogen atom, and sulfur. Examples thereof include groups having 1 to 30 atoms including heteroatoms such as atoms, phosphorus atoms, and silicon atoms.

また、一般式（１ａ）及び（１ｂ）において、置換の炭素数１〜１０の直鎖状若しくは分岐状のアルキル基としては、例えば、ベンジル基、メトキシメチル基、メチルチオメチル基、エトキシメチル基、エチルチオメチル基、フェノキシメチル基、メトキシカルボニルメチル基、エトキシカルボニルメチル基、アセチルメチル基、フルオロメチル基、トリフルオロメチル基、クロロメチル基、トリクロロメチル基、２−フルオロプロピル基、（トリフルオロアセチル）メチル基、（トリクロロアセチル）メチル基、（ペンタフルオロベンゾイル）メチル基、アミノメチル基、（シクロヘキシルアミノ）メチル基、（トリメチルシリル）メチル基、２−フェニルエチル基、２−アミノエチル基、３−フェニルプロピル基等を挙げることができる。   In the general formulas (1a) and (1b), examples of the substituted linear or branched alkyl group having 1 to 10 carbon atoms include a benzyl group, a methoxymethyl group, a methylthiomethyl group, an ethoxymethyl group, Ethylthiomethyl group, phenoxymethyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, acetylmethyl group, fluoromethyl group, trifluoromethyl group, chloromethyl group, trichloromethyl group, 2-fluoropropyl group, (trifluoroacetyl group) ) Methyl group, (trichloroacetyl) methyl group, (pentafluorobenzoyl) methyl group, aminomethyl group, (cyclohexylamino) methyl group, (trimethylsilyl) methyl group, 2-phenylethyl group, 2-aminoethyl group, 3- And phenylpropyl group

また、一般式（１ａ）及び（１ｂ）において、非置換の炭素数６〜１８のアリール基としては、例えば、フェニル基、１−ナフチル基、２−ナフチル基、１−アントリル基、１−フェナントリル基等を挙げることができる。これらアリール基の置換基としては、例えば、炭素数１〜３０の直鎖状、分岐状若しくは環状のアルキル基や、ハロゲン原子、酸素原子、窒素原子、硫黄原子、リン原子、ケイ素原子等のヘテロ原子を含む原子数１〜３０の基等を挙げることができる。また、置換の炭素数６〜１８のアリール基としては、例えば、ｏ−トリル基、ｍ−トリル基、ｐ−トリル基、４−ヒドロキシフェニル基、４−メトキシフェニル基、メシチル基、ｏ−クメニル基、２，３−キシリル基、２，４−キシリル基、２，５−キシリル基、２，６−キシリル基、３，４−キシリル基、３，５−キシリル基、４−フルオロフェニル基、４−トリフルオロメチルフェニル基、４−クロロフェニル基、４−ブロモフェニル基、４−ヨードフェニル基等を挙げることができる。   In the general formulas (1a) and (1b), examples of the unsubstituted aryl group having 6 to 18 carbon atoms include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, and 1-phenanthryl. Groups and the like. Examples of substituents for these aryl groups include linear, branched or cyclic alkyl groups having 1 to 30 carbon atoms, and hetero atoms such as halogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, and silicon atoms. Examples thereof include groups having 1 to 30 atoms including atoms. Examples of the substituted aryl group having 6 to 18 carbon atoms include, for example, o-tolyl group, m-tolyl group, p-tolyl group, 4-hydroxyphenyl group, 4-methoxyphenyl group, mesityl group, and o-cumenyl. Group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 4-fluorophenyl group, A 4-trifluoromethylphenyl group, a 4-chlorophenyl group, a 4-bromophenyl group, a 4-iodophenyl group, and the like can be given.

また、一般式（１ａ）において、いずれか２つ以上のＲ１２、Ｒ１３及びＲ１４が相互に結合して形成される環としては、例えば、５〜７員の環構造等を挙げることができる。
更に、一般式（１ｂ）において、Ｒ１５及びＲ１６が相互に結合して形成される環としては、例えば、５〜７員の環構造等を挙げることができる。 In the general formula (1a), examples of the ring formed by bonding any two or more of R 12 , R 13, and R 14 include a 5- to 7-membered ring structure. it can.
Furthermore, in the general formula (1b), examples of the ring formed by bonding R 15 and R 16 to each other include a 5- to 7-membered ring structure.

一般式（１ａ）で表される好ましいスルホニウムカチオンの具体例（１ａ−１）〜（１ａ−６４）、及び、一般式（１ｂ）で表される好ましいヨードニウムカチオンの具体例（１ｂ−１）〜（１ｂ−３９）を以下に示す。   Specific examples (1a-1) to (1a-64) of preferred sulfonium cations represented by general formula (1a) and specific examples (1b-1) of preferred iodonium cations represented by general formula (1b) (1b-39) is shown below.

Figure 2007328060
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ここで、上記繰り返し単位（１）の好ましい例としては、以下に示す（１−１）〜（１−２４）等の単位が挙げられる。尚、これらの繰り返し単位（１）は単独で又は２種類以上を混合して使用することができる。   Here, preferred examples of the repeating unit (1) include units such as (1-1) to (1-24) shown below. In addition, these repeating units (1) can be used individually or in mixture of 2 or more types.

Figure 2007328060
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また、上記繰り返し単位（２）の好ましい例としては、以下に示す（２−１）〜（２−３０）等の単位が挙げられる。尚、これらの繰り返し単位（２）は単独で又は２種類以上を混合して使用することができる。   Moreover, as a preferable example of the said repeating unit (2), units, such as (2-1)-(2-30) shown below, are mentioned. In addition, these repeating units (2) can be used individually or in mixture of 2 or more types.

Figure 2007328060
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ここで、本発明における酸発生基含有樹脂は、上記繰り返し単位（１）及び（２）のうちの少なくとも一方のみから構成されていてもよいし、下記一般式（３）で表される繰り返し単位（以下、「繰り返し単位（３）」という）、下記一般式（４）で表される繰り返し単位（以下、「繰り返し単位（４）」という）及び（５）で表される繰り返し単位（以下、「繰り返し単位（５）」という）のうちの少なくとも一種の非酸解離性繰り返し単位を酸発生基含有樹脂の構成単位として、更に含んでいてもよい。
尚、上記非解離性繰り返し単位とは、酸発生基含有樹脂から発生する酸の作用によって、繰り返し単位中の側鎖等が切断されたりするなどの構造変化が生じない単位、或いは殆ど生じない単位を示す。 Here, the acid generating group-containing resin in the present invention may be composed of at least one of the above repeating units (1) and (2), or a repeating unit represented by the following general formula (3). (Hereinafter referred to as “repeating unit (3)”), a repeating unit represented by the following general formula (4) (hereinafter referred to as “repeating unit (4)”) and a repeating unit represented by (5) (hereinafter referred to as “repeating unit (3)”). At least one non-acid dissociable repeating unit of “repeating unit (5)” may be further included as a constituent unit of the acid-generating group-containing resin.
The non-dissociative repeating unit is a unit in which a structural change such as a side chain in the repeating unit is not cut by the action of an acid generated from an acid-generating group-containing resin, or a unit that hardly occurs. Indicates.

Figure 2007328060
〔一般式（３）において、Ｒ６は水素原子又はメチル基を表し、Ｇは単結合、メチレン基又はアルキレン基を表し、Ｒ７はアルキル基、水素原子、ヒドロキシル基、アルコキシル基、−ＣＯＯＨ、パーフルオロアルキル基又は芳香族基を表す。ここでＲ７が−ＣＯＯＨ又は芳香族基である場合、Ｇはメチレン基又はアルキレン基を示す。〕
〔一般式（４）において、Ｒ８は水素原子又はメチル基を表し、Ｊは単結合、メチレン基又はアルキレン基を表し、Ｒ９は水素原子、アルキル基、ヒドロキシル基、アルコキシル基、−ＣＯＯＨ、パーフルオロアルキル基、芳香族基又はアミノ基を表す。ここでＲ９がアミノ基、ヒドロキシル基、アルコキシル基、−ＣＯＯＨ、パーフルオロアルキル基又は芳香族基である場合、Ｊはメチレン基又はアルキレン基を示す。〕
〔一般式（５）において、Ｒ１０は水素原子又はメチル基を表し、Ｌはメチレン基又はアルキレン基を表し、Ｒ１１は水素原子、ヒドロキシル基、アルコキシル基、−ＣＯＯＨ、パーフルオロアルキル基、芳香族基又はアミノ基を表す。〕
Figure 2007328060
 [In General Formula (3), R 6 represents a hydrogen atom or a methyl group, G represents a single bond, a methylene group or an alkylene group, R 7 represents an alkyl group, a hydrogen atom, a hydroxyl group, an alkoxyl group, —COOH, Represents a perfluoroalkyl group or an aromatic group. Here, when R 7 is —COOH or an aromatic group, G represents a methylene group or an alkylene group. ]
[In General Formula (4), R 8 represents a hydrogen atom or a methyl group, J represents a single bond, a methylene group or an alkylene group, and R 9 represents a hydrogen atom, an alkyl group, a hydroxyl group, an alkoxyl group, —COOH, Represents a perfluoroalkyl group, an aromatic group or an amino group. Here, when R 9 is an amino group, a hydroxyl group, an alkoxyl group, —COOH, a perfluoroalkyl group or an aromatic group, J represents a methylene group or an alkylene group. ]
[In the general formula (5), R 10 represents a hydrogen atom or a methyl group, L represents a methylene group or an alkylene group, R 11 represents a hydrogen atom, a hydroxyl group, an alkoxyl group, —COOH, a perfluoroalkyl group, an aromatic group. Represents a group or an amino group. ]

また、上記一般式（３）におけるＧのアルキレン基としては、例えば、エチレン基、１，３−プロピレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基、ヘプタメチレン基、オクタメチレン基、ノナメチレン基、デカメチレン基、２−メチル−１，３−プロピレン基、２−メチル−１，２−プロピレン基、２−メチル−１，４−ブチレン基等の炭素数２〜１０直鎖状、分岐状アルキレン基、１，３−シクロブチレン基などのシクロブチレン基、１，３−シクロペンチレン基などのシクロペンチレン基、１，４−シクロヘキシレン基などのシクロヘキシレン基、１，５−シクロオクチレン基などのシクロオクチレン基等の炭素数３〜１０のシクロアルキレン基などの単環式炭化水素環基、１，４−ノルボルニレン基若しくは２，５−ノルボルニレン基などのノルボルニレン基、１，３−アダマンチレン基、２，６−アダマンチレン基などのアダマンチレン基等の２〜４環式の炭素数４〜３０の炭化水素環基などの架橋環式炭化水素環基等が挙げられる。   Examples of the alkylene group of G in the general formula (3) include an ethylene group, a 1,3-propylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, and a nonamethylene group. , A decamethylene group, a 2-methyl-1,3-propylene group, a 2-methyl-1,2-propylene group, a 2-methyl-1,4-butylene group, etc. Group, cyclobutylene group such as 1,3-cyclobutylene group, cyclopentylene group such as 1,3-cyclopentylene group, cyclohexylene group such as 1,4-cyclohexylene group, 1,5-cyclooctylene A monocyclic hydrocarbon ring group such as a cycloalkylene group having 3 to 10 carbon atoms such as a cyclooctylene group such as a group, 1,4-norbornylene group or 2, -Bridged ring such as a 2-4 cyclic hydrocarbon ring group having 4 to 30 carbon atoms such as a norbornylene group such as a norbornylene group, an adamantylene group such as a 1,3-adamantylene group or a 2,6-adamantylene group And a hydrocarbon ring group.

上記一般式（３）におけるＲ７のアルコキシル基としては、例えば、メトキシ基、エトキシ基、プトポキシ基、ｎ−ブトキシ基、イソブトキシ基、ｓｅｃ−ブトキシ基、ヘキシルオキシ基、オクチルオキシ基のような炭素数１〜８個のものなどが挙げられる。
また、上記Ｒ７の芳香族基としては、例えば、フェニル基、ナフチル基等の炭素数６〜１０個のものなどが挙げられる。尚、この芳香族基は置換基を有してもよく、好ましい置換基としては、炭素数１〜４個のアルキル基、炭素数１〜４個のアルコキシ基、ハロゲン基、シアノ基、ヒドロキシ基、カルボキシ基、アルコキシカルボニル基、ニトロ基が挙げられる。
尚、上記Ｒ７が、−ＣＯＯＨ又は芳香族基である場合、上記Ｇはメチレン基又はアルキレン基である。 Examples of the alkoxyl group of R 7 in the general formula (3) include carbons such as a methoxy group, an ethoxy group, a topoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a hexyloxy group, and an octyloxy group. The thing of several 1-8 etc. are mentioned.
Examples of the aromatic group for R 7 include those having 6 to 10 carbon atoms such as a phenyl group and a naphthyl group. The aromatic group may have a substituent, and preferred substituents include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen group, a cyano group, and a hydroxy group. , A carboxy group, an alkoxycarbonyl group, and a nitro group.
When R 7 is —COOH or an aromatic group, G is a methylene group or an alkylene group.

上記一般式（４）におけるＪのアルキレン基としては、上記一般式（３）におけるＧと同様のアルキレン基を挙げることができる。
また、一般式（４）におけるＲ９のアルコキシル基としては、上記一般式（３）におけるＲ７と同様のアルコキシル基を挙げることができる。
尚、上記Ｒ９が、アミノ基、ヒドロキシル基、アルコキシル基、−ＣＯＯＨ、パーフルオロアルキル基又は芳香族基である場合、上記Ｊはメチレン基又はアルキレン基である。 As an alkylene group of J in the said General formula (4), the alkylene group similar to G in the said General formula (3) can be mentioned.
As the alkoxyl group of R 9 in the general formula (4) include the same alkoxyl groups as R 7 in the general formula (3).
When R 9 is an amino group, a hydroxyl group, an alkoxyl group, —COOH, a perfluoroalkyl group or an aromatic group, J is a methylene group or an alkylene group.

上記一般式（５）におけるＬのアルキレン基としては、上記一般式（３）におけるＧと同様のアルキレン基を挙げることができる。
また、一般式（５）におけるＲ１１のアルコキシル基としては、上記一般式（３）におけるＲ７と同様のアルコキシル基を挙げることができる。 As an alkylene group of L in the said General formula (5), the alkylene group similar to G in the said General formula (3) can be mentioned.
As the alkoxyl group of R 11 in the general formula (5) include the same alkoxyl groups as R 7 in the general formula (3).

ここで、上記繰り返し単位（３）の好ましい例としては、スチレン、α−メチルスチレン、４−ヒドロキシスチレン、４−ヒドロキシ−α−メチルスチレン、４-メチルスチレン、４-メチル−α−スチレン、４-メトキシスチレン、４-メトキシ−α−スチレン等の重合性不飽和結合が開裂した単位を挙げることができる。尚、これらの繰り返し単位（３）は単独で又は２種類以上を混合して使用することができる。   Here, preferred examples of the repeating unit (3) include styrene, α-methylstyrene, 4-hydroxystyrene, 4-hydroxy-α-methylstyrene, 4-methylstyrene, 4-methyl-α-styrene, 4 Examples include units having a polymerizable unsaturated bond cleaved, such as -methoxystyrene and 4-methoxy-α-styrene. In addition, these repeating units (3) can be used individually or in mixture of 2 or more types.

また、上記繰り返し単位（４）の好ましい例としては、（メタ）アクリル酸ノルボルニル、（メタ）アクリル酸イソボルニル、（メタ）アクリル酸トリシクロデカニル、（メタ）アクリル酸テトラシクロデカニル、（メタ）アクリル酸ジシクロペンテニル、（メタ）アクリル酸アダマンチル、（メタ）アクリル酸ヒドロキシアダマンチル等、の有橋式炭化水素骨格を有する（メタ）アクリル酸エステル類；
（メタ）アクリル酸カルボキシノルボルニル、（メタ）アクリル酸カルボキシトリシクロデカニル、（メタ）アクリル酸カルボキシテトラシクロデカニル等の不飽和カルボン酸の有橋式炭化水素骨格を有するカルボキシル基含有エステル類； Preferred examples of the repeating unit (4) include norbornyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, tetracyclodecanyl (meth) acrylate, (meth ) (Meth) acrylic acid esters having a bridged hydrocarbon skeleton such as dicyclopentenyl acrylate, adamantyl (meth) acrylate, hydroxyadamantyl (meth) acrylate;
Carboxyl group-containing ester having a bridged hydrocarbon skeleton of unsaturated carboxylic acid such as carboxynorbornyl (meth) acrylate, carboxytricyclodecanyl (meth) acrylate, and carboxytetracyclodecanyl (meth) acrylate Kind;

（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ−プロピル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸２−メチルプロピル、（メタ）アクリル酸１−メチルプロピル、（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸２−ヒドロキシプロピル、（メタ）アクリル酸３−ヒドロキシプロピル、（メタ）アクリル酸シクロプロピル、（メタ）アクリル酸シクロペンチル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸４−メトキシシクロヘキシル、（メタ）アクリル酸２−シクロペンチルオキシカルボニルエチル、（メタ）アクリル酸２−シクロヘキシルオキシカルボニルエチル、（メタ）アクリル酸２−（４−メトキシシクロヘキシル）オキシカルボニルエチル等の有橋式炭化水素骨格をもたない（メタ）アクリル酸エステル類；   Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, 2-methylpropyl (meth) acrylate, 1-methyl (meth) acrylate Propyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, cyclopropyl (meth) acrylate, cyclopentyl (meth) acrylate, (meth) Cyclohexyl acrylate, 4-methoxycyclohexyl (meth) acrylate, 2-cyclopentyloxycarbonylethyl (meth) acrylate, 2-cyclohexyloxycarbonylethyl (meth) acrylate, 2- (4-methoxycyclohexyl) (meth) acrylate ) Bridge type such as oxycarbonylethyl No hydrogen skeleton (meth) acrylic acid esters;

（メタ）アクリル酸、クロトン酸、マレイン酸、無水マレイン酸、フマル酸、イタコン酸、無水イタコン酸、シトラコン酸、無水シトラコン酸、メサコン酸等の不飽和カルボン酸（無水物）類；（メタ）アクリル酸２−カルボキシエチル、（メタ）アクリル酸２−カルボキシプロピル、（メタ）アクリル酸３−カルボキシプロピル、（メタ）アクリル酸４−カルボキシブチル、（メタ）アクリル酸４−カルボキシシクロヘキシル等の不飽和カルボン酸の有橋式炭化水素骨格をもたないカルボキシル基含有エステル類；   (Meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid and other unsaturated carboxylic acids (anhydrides); Unsaturation such as 2-carboxyethyl acrylate, 2-carboxypropyl (meth) acrylate, 3-carboxypropyl (meth) acrylate, 4-carboxybutyl (meth) acrylate, 4-carboxycyclohexyl (meth) acrylate Carboxyl group-containing esters having no bridged hydrocarbon skeleton of carboxylic acid;

１，２−アダマンタンジオールジ（メタ）アクリレート、１，３−アダマンタンジオールジ（メタ）アクリレート、１，４−アダマンタンジオールジ（メタ）アクリレート、トリシクロデカニルジメチロールジ（メタ）アクリレート等の有橋式炭化水素骨格を有する多官能性化合物；有橋式炭化水素骨格をもたない多官能性化合物等の重合性不飽和結合が開裂した単位を挙げることができる。尚、これらの繰り返し単位（４）は単独で又は２種類以上を混合して使用することができる。   1,2-adamantanediol di (meth) acrylate, 1,3-adamantanediol di (meth) acrylate, 1,4-adamantanediol di (meth) acrylate, tricyclodecanyl dimethylol di (meth) acrylate, etc. Examples thereof include a polyfunctional compound having a bridged hydrocarbon skeleton; a unit in which a polymerizable unsaturated bond is cleaved, such as a polyfunctional compound having no bridged hydrocarbon skeleton. In addition, these repeating units (4) can be used individually or in mixture of 2 or more types.

また、上記繰り返し単位（５）の好ましい例としては、Ｎ，Ｎ−ジメチルアミノプロピルアクリルアミド、Ｎ−イソプロピルアクリルアミド等の重合性不飽和結合が開裂した単位を挙げることができる。尚、これらの繰り返し単位（５）は単独で又は２種類以上を混合して使用することができる。   Moreover, as a preferable example of the said repeating unit (5), the unit which cleaved polymerizable unsaturated bonds, such as N, N-dimethylaminopropyl acrylamide and N-isopropyl acrylamide, can be mentioned. In addition, these repeating units (5) can be used individually or in mixture of 2 or more types.

本発明の酸発生基含有樹脂において、上記繰り返し単位（１）及び（２）の含有率の合計は、酸発生基含有樹脂を構成する全繰り返し単位の合計を１００モル％とした場合に、１０〜１００モル％であることが好ましく、より好ましくは２０〜１００モル％である。この繰り返し単位（１）及び（２）の含有率の合計が１０〜１００モル％の場合には、パターン形成方法において、感度、エッチング耐性、解像度に優れ、微細パターンを高精度にかつより安定して形成することができる。   In the acid generating group-containing resin of the present invention, the total content of the repeating units (1) and (2) is 10 when the total of all repeating units constituting the acid generating group-containing resin is 100 mol%. It is preferable that it is -100 mol%, More preferably, it is 20-100 mol%. When the total content of the repeating units (1) and (2) is 10 to 100 mol%, the pattern forming method is excellent in sensitivity, etching resistance and resolution, and the fine pattern is highly accurate and more stable. Can be formed.

また、本発明における酸発生基含有樹脂のゲルパーミエーションクロマトグラフィ（ＧＰＣ）により測定されるポリスチレン換算重量分子量（以下、「Ｍｗ」という）は、好ましくは１，０００〜１５０，０００、より好ましくは３，０００〜１００，０００、更に好ましくは５，０００〜３０，０００である。
また、酸発生基含有樹脂のＭｗと、ＧＰＣで測定したポリスチレン換算数分子量（以下、「Ｍｎ」という。）との比（Ｍｗ／Ｍｎ）は、通常、１〜１０であり、好ましくは１〜５である。 Moreover, the polystyrene conversion weight molecular weight (henceforth "Mw") measured by the gel permeation chromatography (GPC) of acid generating group containing resin in this invention becomes like this. Preferably it is 1,000-150,000, More preferably, it is 3 1,000 to 100,000, more preferably 5,000 to 30,000.
The ratio (Mw / Mn) of the Mw of the acid-generating group-containing resin to the polystyrene equivalent number molecular weight (hereinafter referred to as “Mn”) measured by GPC is usually 1 to 10, preferably 1 to 1. 5.

<感放射線性樹脂組成物>
本発明の感放射線性樹脂組成物は、樹脂成分として、酸発生基含有樹脂のみを含有することを特徴とする。
上記酸発生基含有樹脂については、前述の説明をそのまま適用することができる。尚、この酸発生基含有樹脂は、単独で又は２種以上を混合して使用することができる。 <Radiation sensitive resin composition>
The radiation-sensitive resin composition of the present invention is characterized by containing only an acid-generating group-containing resin as a resin component.
The above description can be applied as it is to the acid generating group-containing resin. In addition, this acid generating group containing resin can be used individually or in mixture of 2 or more types.

また、本発明における感放射線性樹脂組成物には、他の成分として、界面活性剤、増感剤、溶剤等の添加剤が配合されていてもよい。
尚、本発明における感放射線性樹脂組成物は、前述のように樹脂側鎖の極性変化によって現像液への溶解性が増大するものであり、酸発生剤が発生する酸の拡散を利用した従来の化学増幅型感放射線性樹脂組成物とは異なっているため、添加剤としての酸発生剤や酸拡散制御剤は必要とせず、これらを含有しないものとすることができる。 Moreover, additives, such as surfactant, a sensitizer, and a solvent, may be mix | blended with the radiation sensitive resin composition in this invention as another component.
Incidentally, the radiation-sensitive resin composition in the present invention has increased solubility in the developer due to the change in the polarity of the resin side chain as described above, and conventionally uses diffusion of acid generated by the acid generator. Therefore, an acid generator or an acid diffusion control agent as an additive is not required and can be excluded from the chemical amplification type radiation sensitive resin composition.

〔界面活性剤〕
本発明の感放射線性樹脂組成物に界面活性剤を配合した場合、感放射線性樹脂組成物の塗布性やストリエーション、レジストとしての現像性等を向上させることができる。
このような界面活性剤としては、例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンｎ−オクチルフェノールエーテル、ポリオキシエチレンｎ−ノニルフェノールエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート等を挙げることができる。また、市販品としては、例えば、エフトップＥＦ３０１、同ＥＦ３０３、同ＥＦ３５２（トーケムプロダクツ社製）、メガファックスＦ１７１、同Ｆ１７３（以上、大日本インキ化学工業（株）製）、フロラードＦＣ４３０、同ＦＣ４３１（以上、住友スリーエム（株）製）、アサヒガードＡＧ７１０、サーフロンＳ−３８２、同ＳＣ１０１、同ＳＣ１０２、同ＳＣ１０３、同ＳＣ１０４、同ＳＣ１０５、同ＳＣ１０６（以上、旭硝子（株）製）、ＫＰ３４１（信越化学工業（株）製）、ポリフローＮｏ．７５、同Ｎｏ．９５（以上、共栄社化学（株）製）等が挙げられる。尚、これらの界面活性剤は、単独で又は２種以上を混合して使用することができる。 [Surfactant]
When a surfactant is blended in the radiation-sensitive resin composition of the present invention, the coating property and striation of the radiation-sensitive resin composition, the developability as a resist, and the like can be improved.
Examples of such surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenol ether, polyoxyethylene n-nonylphenol ether, polyethylene glycol dilaurate, polyethylene Examples include glycol distearate. Commercially available products include, for example, F-top EF301, EF303, EF352 (manufactured by Tochem Products), Megafax F171, F173 (above, manufactured by Dainippon Ink and Chemicals), Fluorad FC430, FC431 (above, manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.), KP341 ( Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.). In addition, these surfactant can be used individually or in mixture of 2 or more types.

また、上記界面活性剤の配合量は、感放射線性樹脂組成物における酸解離性基含有樹脂１００質量部に対して、２質量部以下であることが好ましい。   Moreover, it is preferable that the compounding quantity of the said surfactant is 2 mass parts or less with respect to 100 mass parts of acid dissociable group containing resin in a radiation sensitive resin composition.

〔増感剤〕
上記増感剤の好ましい例としては、例えば、カルバゾール類、ベンゾフェノン類、ローズベンガル類、アントラセン類等が挙げられる。尚、これらの増感剤は、単独で又は２種以上を混合して使用することができる。
また、上記増感剤の配合量は、感放射線性樹脂組成物における酸解離性基含有樹脂１００質量部に対して、５０質量部以下であることが好ましい。 [Sensitizer]
Preferable examples of the sensitizer include carbazoles, benzophenones, rose bengals, anthracene and the like. In addition, these sensitizers can be used individually or in mixture of 2 or more types.
Moreover, it is preferable that the compounding quantity of the said sensitizer is 50 mass parts or less with respect to 100 mass parts of acid dissociable group containing resin in a radiation sensitive resin composition.

〔溶剤〕
本発明における感放射線性樹脂組成物は、その使用に際して、全固形分の濃度が、通常、０．１〜５０質量％、好ましくは１〜３０質量％になるように、溶剤に均一に溶解したのち、例えば孔径０．２μｍ程度のフィルターでろ過することにより、組成物溶液として調製される。
上記組成物溶液の調製に使用される溶剤としては、例えば、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノ−ｎ−プロピルエーテルアセテート、エチレングリコールモノ−ｎ−ブチルエーテルアセテート等のエチレングリコールモノアルキルエーテルアセテート類；プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノ−ｎ−プロピルエーテル、プロピレングリコールモノ−ｎ−ブチルエーテル等のプロピレングリコールモノアルキルエーテル類；プロピレングリコールジメチルエーテル、プロピレングリコールジエチルエーテル、プロピレングリコールジ−ｎ−プロピルエーテル、プロピレングリコールジ−ｎ−ブチルエーテル等のプロピレングリコールジアルキルエーテル類；プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノ−ｎ−プロピルエーテルアセテート、プロピレングリコールモノ−ｎ−ブチルエーテルアセテート等のプロピレングリコールモノアルキルエーテルアセテート類；乳酸メチル、乳酸エチル、乳酸ｎ−プロピル、乳酸ｉ−プロピル等の乳酸エステル類；ぎ酸ｎ−アミル、ぎ酸ｉ−アミル、酢酸エチル、酢酸ｎ−プロピル、酢酸ｉ−プロピル、酢酸ｎ−ブチル、酢酸ｉ−ブチル、酢酸ｎ−アミル、酢酸ｉ−アミル、プロピオン酸ｉ−プロピル、プロピオン酸ｎ−ブチル、プロピオン酸ｉ−ブチル等の脂肪族カルボン酸エステル類；ヒドロキシ酢酸エチル、２−ヒドロキシ−２−メチルプロピオン酸エチル、２−ヒドロキシ−３−メチル酪酸メチル、メトキシ酢酸エチル、エトキシ酢酸エチル、３−メトキシプロピオン酸メチル、３−メトキシプロピオン酸エチル、３−エトキシプロピオン酸メチル、３−エトキシプロピオン酸エチル、３−メトキシブチルアセテート、３−メチル−３−メトキシブチルアセテート、３−メチル−３−メトキシブチルプロピオネート、３−メチル−３−メトキシブチルブチレート、アセト酢酸メチル、アセト酢酸エチル、ピルビン酸メチル、ピルビン酸エチル等の他のエステル類；トルエン、キシレン等の芳香族炭化水素類；メチルエチルケトン、メチルプロピルケトン、メチルブチルケトン、２−ヘプタノン、３−ヘプタノン、４−ヘプタノン、シクロヘキサノン等のケトン類；Ｎ−メチルホルムアミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチルアセトアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルピロリドン等のアミド類；γ−ブチロラクン等のラクトン類等が挙げられる。
これらの溶剤は、単独で又は２種以上を混合して使用することができる。 〔solvent〕
The radiation-sensitive resin composition in the present invention was uniformly dissolved in a solvent so that the concentration of the total solid content was usually 0.1 to 50% by mass, preferably 1 to 30% by mass when used. Thereafter, it is prepared as a composition solution by, for example, filtering with a filter having a pore size of about 0.2 μm.
Examples of the solvent used for the preparation of the composition solution include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate and the like. Glycol monoalkyl ether acetates; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether; propylene glycol dimethyl ether, propylene glycol diethyl Ether, propylene glycol di-n-propyl ether, propylene Propylene glycol dialkyl ethers such as recall di-n-butyl ether; propylene glycol monoalkyl such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate Ether acetates; lactate esters such as methyl lactate, ethyl lactate, n-propyl lactate, i-propyl lactate; n-amyl formate, i-amyl formate, ethyl acetate, n-propyl acetate, i-propyl acetate, Aliphatic carboxylates such as n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, i-propyl propionate, n-butyl propionate and i-butyl propionate Ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutyl Other esters such as butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate; aromatic hydrocarbons such as toluene, xylene; methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4 -Ketones such as heptanone and cyclohexanone; Amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; Lactones such as γ-butyrolacun Is mentioned.
These solvents can be used alone or in admixture of two or more.

<レジストパターンの形成>
感放射線性樹脂組成物からレジストパターンを形成する際には、前述したようにして調製された組成物溶液を、回転塗布、流延塗布、ロール塗布等の適宜の塗布手段によって、例えば、シリコンウエハ、アルミニウムで被覆されたウエハ等の基板上に塗布し、場合により予め７０℃〜１６０℃程度の温度で加熱処理（以下、「ＰＢ」という。）を行なって、レジスト被膜を形成したのち、ＥＢ、Ｘ線、ＥＵＶ等の放射線、好ましくはＥＢを照射することにより描画する。この描画条件は、感放射線性樹脂組成物の配合組成、各添加剤の種類等に応じて、適宜選定される。 <Formation of resist pattern>
When forming a resist pattern from a radiation-sensitive resin composition, the composition solution prepared as described above is applied, for example, to a silicon wafer by an appropriate application means such as spin coating, cast coating, roll coating or the like. EB is coated on a substrate such as a wafer coated with aluminum, and in some cases, a heat treatment (hereinafter referred to as “PB”) is performed in advance at a temperature of about 70 ° C. to 160 ° C. to form a resist film, and then EB Drawing is performed by irradiating radiation such as X-ray, EUV, preferably EB. The drawing conditions are appropriately selected according to the composition of the radiation sensitive resin composition, the type of each additive, and the like.

その後、アルカリ現像液、又は水により、通常、１０〜５０℃で１０〜２００秒、好ましくは１５〜３０℃で１５〜１００秒の条件で現像することにより、所定のレジストパターンを形成する。
上記アルカリ現像液としては、例えば、アルカリ金属水酸化物、アンモニア水、モノ−、ジ−或いはトリ−アルキルアミン類、モノ−、ジ−或いはトリ−アルカノールアミン類、複素環式アミン類、テトラアルキルアンモニウムヒドロキシド類、コリン、１，８−ジアザビシクロ−［５．４．０］−７−ウンデセン、１，５−ジアザビシクロ−［４．３．０］−５−ノネン等のアルカリ性化合物を、通常、１〜１０質量％、好ましくは１〜５質量％、特に好ましくは１〜３質量％の濃度となるよう溶解したアルカリ性水溶液が使用される。
また、上記アルカリ性水溶液からなる現像液には、例えば、メタノール、エタノール等の水溶性有機溶剤や界面活性剤を適宜添加することもできる。
更に、レジストパターンの形成に際しては、環境雰囲気中に含まれる塩基性不純物等の影響や被膜中の帯電を防止するため、レジスト被膜上に保護膜や帯電防止膜を設けることができる。 Then, a predetermined resist pattern is formed by developing with an alkali developer or water at 10 to 50 ° C. for 10 to 200 seconds, preferably 15 to 30 ° C. for 15 to 100 seconds.
Examples of the alkali developer include alkali metal hydroxide, aqueous ammonia, mono-, di- or tri-alkylamines, mono-, di- or tri-alkanolamines, heterocyclic amines, and tetraalkyl. Alkaline compounds such as ammonium hydroxides, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0] -5-nonene are usually used. An alkaline aqueous solution dissolved so as to have a concentration of 1 to 10% by mass, preferably 1 to 5% by mass, particularly preferably 1 to 3% by mass is used.
Further, for example, a water-soluble organic solvent such as methanol or ethanol, or a surfactant can be appropriately added to the developer composed of the alkaline aqueous solution.
Further, when forming the resist pattern, a protective film or an antistatic film can be provided on the resist film in order to prevent the influence of basic impurities contained in the environmental atmosphere and the charge in the film.

以下、実施例を挙げて、本発明を更に具体的に説明する。但し、本発明は、これらの実施例に何ら制約されるものではない。
ここで、「％」及び「部」は特記しない限り質量基準である。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
Here, “%” and “part” are based on mass unless otherwise specified.

［１］酸発生基含有樹脂の合成
（１−１）オニウム塩構造を有する単量体の合成
合成例１：オニウム塩構造を有する単量体（Ｚ−１）の合成
２−アクリルアミド−２−メチル−１−プロパンスルホン酸８．３ｇ（４０ｍｍｏｌ）と水酸化ナトリウム１．６ｇ（４０ｍｍｏｌ）を４００ｍｌの水に溶解させ、１時間攪拌した。そこに４００ｍｌの塩化メチレンに溶解させたトリス（４−ｔ−ブチルフェニル）スルホニウムブロマイド２０．５ｇ（４０ｍｍｏｌ）を加え２時間攪拌した。その後、得られた反応溶液を分液ロートに入れ、静置させた後、２層溶液の水相側を除去した。更に、有機層（塩化メチレン層）を４００ｍｌの水で１０回洗浄した。次いで、洗浄後の有機層を濃縮し、乾燥することで白色個体１９．２ｇを得た。
この白色固体を、オニウム塩構造を有する単量体（Ｚ−１）とし、その化学構造式を以下に示す。 [1] Synthesis of acid-generating group-containing resin (1-1) Synthesis of monomer having onium salt structure Synthesis example 1: Synthesis of monomer (Z-1) having onium salt structure 2-acrylamide-2- 8.3 g (40 mmol) of methyl-1-propanesulfonic acid and 1.6 g (40 mmol) of sodium hydroxide were dissolved in 400 ml of water and stirred for 1 hour. Thereto was added 20.5 g (40 mmol) of tris (4-t-butylphenyl) sulfonium bromide dissolved in 400 ml of methylene chloride, followed by stirring for 2 hours. Thereafter, the obtained reaction solution was put in a separating funnel and allowed to stand, and then the aqueous phase side of the two-layer solution was removed. Furthermore, the organic layer (methylene chloride layer) was washed 10 times with 400 ml of water. Next, the washed organic layer was concentrated and dried to obtain 19.2 g of a white solid.
Let this white solid be the monomer (Z-1) which has an onium salt structure, and the chemical structural formula is shown below.

Figure 2007328060
Figure 2007328060

合成例２：オニウム塩構造を有する単量体（Ｚ−２）の合成
４−メタクロイルオキシ−ｎ−ブタンスルホン酸ナトリウム９．８ｇ（４０ｍｍｏｌ）を４００ｍｌの水に溶解させ、そこに４００ｍｌの塩化メチレンに溶解させたトリス（４−ｔ−ブチルフェニル）スルホニウムブロマイド２０．５ｇ（４０ｍｍｏｌ）を加え２時間攪拌した。その後、得られた反応溶液を分液ロートに入れ、静置させた後、２層溶液の水層側を除去した。更に、有機層（塩化メチレン層）を４００ｍｌの水で１０回洗浄した。次いで、洗浄後の有機層を濃縮し、乾燥することで白色個体２１．８ｇを得た。
この白色固体を、オニウム塩構造を有する単量体（Ｚ−２）とし、その化学構造式を以下に示す。 Synthesis Example 2: Synthesis of monomer (Z-2) having onium salt structure 9.8 g (40 mmol) of sodium 4-methacryloyloxy-n-butanesulfonate was dissolved in 400 ml of water, and 400 ml of chloride was added thereto. 20.5 g (40 mmol) of tris (4-t-butylphenyl) sulfonium bromide dissolved in methylene was added and stirred for 2 hours. Thereafter, the obtained reaction solution was put in a separating funnel and allowed to stand, and then the aqueous layer side of the two-layer solution was removed. Furthermore, the organic layer (methylene chloride layer) was washed 10 times with 400 ml of water. Next, the washed organic layer was concentrated and dried to obtain 21.8 g of a white solid.
Let this white solid be the monomer (Z-2) which has an onium salt structure, and the chemical structural formula is shown below.

Figure 2007328060
Figure 2007328060

合成例３：オニウム塩構造を有する単量体（Ｚ−３）の合成
１，１，２，２−テトラフルオロ−５−メタクロイルオキシ−ｎ−ペンタンスルホン酸ナトリウム、６．３ｇ（２０ｍｍｏｌ）を３０ｍｌの水に溶解させ、そこに６０ｍｌの塩化メチレンに溶解させたトリフェニルスルホニウムブロマイド６．８ｇ（２０ｍｍｏｌ）を加え２時間攪拌した。その後、得られた反応溶液を分液ロートに入れ、静置させた後、２層溶液の水層側を除去した。更に、有機層（塩化メチレン層）を３０ｍｌの水で１０回洗浄した。次いで、洗浄後の有機層を濃縮し、乾燥することで白色個体８．５ｇを得た。
この白色固体を、オニウム塩構造を有する単量体（Ｚ−３）とし、その化学構造式を以下に示す。 Synthesis Example 3: Synthesis of monomer (Z-3) having onium salt structure 1,1,2,2-tetrafluoro-5-methacryloyloxy-sodium n-pentanesulfonate, 6.3 g (20 mmol) 6.8 g (20 mmol) of triphenylsulfonium bromide dissolved in 30 ml of water and dissolved in 60 ml of methylene chloride was added thereto and stirred for 2 hours. Thereafter, the obtained reaction solution was put in a separating funnel and allowed to stand, and then the aqueous layer side of the two-layer solution was removed. Furthermore, the organic layer (methylene chloride layer) was washed 10 times with 30 ml of water. Next, the organic layer after washing was concentrated and dried to obtain 8.5 g of a white solid.
Let this white solid be the monomer (Z-3) which has an onium salt structure, and the chemical structural formula is shown below.

Figure 2007328060
Figure 2007328060

（１−２）酸発生基含有樹脂の合成
合成例４：酸発生基含有樹脂（Ａ−１）の合成
前記単量体（Ｚ−１）３．０ｇ、２，２，２−トリフルオロエチルアクリレート２．８ｇ、アゾビスイソブチロニトリル０．１７ｇをプロピレングリコールモノメチルエーテル１１．６ｇに溶解したのち、窒素雰囲気下、反応温度を６５℃に保持して、６時間重合させた。重合後、反応溶液を大量の水中に滴下して、生成共重合体を凝固させ、減圧下４０℃にて乾燥することにより、オニウム塩構造を有する単量体（Ｚ−１）と２，２，２−トリフルオロエチルアクリレートのモル比が２０：８０である共重合体（Ｍｗ：１５，０００、Ｍｗ／Ｍｎ：２．０）を得た。
この化合物を酸発生基含有樹脂（Ａ−１）とし、その化学構造式を以下に示す。 (1-2) Synthesis of acid-generating group-containing resin Synthesis Example 4: Synthesis of acid-generating group-containing resin (A-1) 3.0 g of the monomer (Z-1), 2,2,2-trifluoroethyl After 2.8 g of acrylate and 0.17 g of azobisisobutyronitrile were dissolved in 11.6 g of propylene glycol monomethyl ether, polymerization was carried out for 6 hours while maintaining the reaction temperature at 65 ° C. in a nitrogen atmosphere. After the polymerization, the reaction solution is dropped into a large amount of water to solidify the produced copolymer, and dried at 40 ° C. under reduced pressure, whereby the monomer (Z-1) having an onium salt structure and 2, 2 Thus, a copolymer (Mw: 15,000, Mw / Mn: 2.0) having a molar ratio of 2,2-trifluoroethyl acrylate of 20:80 was obtained.
This compound is referred to as an acid generating group-containing resin (A-1), and the chemical structural formula thereof is shown below.

Figure 2007328060
Figure 2007328060

合成例５：酸発生基含有樹脂（Ａ−２）の合成
前記単量体（Ｚ−２）７．４ｇ、３−ヒドロキシ−１−アダマンチルアクリレート２．７ｇ、アゾビスイソブチロニトリル０．２ｇをプロピレングリコールモノメチルエーテル３０ｇに溶解したのち、窒素雰囲気下、反応温度を８０℃に保持して、６時間重合させた。重合後、反応溶液を大量のアセトン中に滴下して、生成共重合体を凝固させ、減圧下４０℃にて乾燥することにより、オニウム塩構造を有する単量体（Ｚ−２）と３−ヒドロキシ−１−アダマンチルアクリレートのモル比が５０：５０である共重合体（Ｍｗ：１０，０００、Ｍｗ／Ｍｎ：１．９）を得た。
この化合物を酸発生基含有樹脂（Ａ−２）とし、その化学構造式を以下に示す。 Synthesis Example 5: Synthesis of acid generating group-containing resin (A-2) 7.4 g of the monomer (Z-2), 2.7 g of 3-hydroxy-1-adamantyl acrylate, 0.2 g of azobisisobutyronitrile Was dissolved in 30 g of propylene glycol monomethyl ether, followed by polymerization for 6 hours while maintaining the reaction temperature at 80 ° C. in a nitrogen atmosphere. After the polymerization, the reaction solution is dropped into a large amount of acetone to solidify the produced copolymer, and dried at 40 ° C. under reduced pressure, whereby the monomer (Z-2) having an onium salt structure and 3- A copolymer having a molar ratio of hydroxy-1-adamantyl acrylate of 50:50 (Mw: 10,000, Mw / Mn: 1.9) was obtained.
This compound is referred to as acid-generating group-containing resin (A-2), and the chemical structural formula thereof is shown below.

Figure 2007328060
Figure 2007328060

合成例６：酸発生基含有樹脂（Ａ−３）の合成
前記単量体（Ｚ−３）６．４ｇ、３−ヒドロキシ−１−アダマンチルアクリレート２．７ｇ、アゾビスイソブチロニトリル０．２ｇをプロピレングリコールモノメチルエーテル２７ｇに溶解したのち、窒素雰囲気下、反応温度を７０℃に保持して、６時間重合させた。重合後、反応溶液を大量のアセトン中に滴下して、生成共重合体を凝固させ、減圧下４０℃にて乾燥することにより、オニウム塩構造を有する単量体（Ｚ−３）と３−ヒドロキシ−１−アダマンチルアクリレートのモル比が５０：５０である共重合体（Ｍｗ：９，０００、Ｍｗ／Ｍｎ：１．９）を得た。
この化合物を酸発生基含有樹脂（Ａ−３）とし、その化学構造式を以下に示す。 Synthesis Example 6: Synthesis of acid generating group-containing resin (A-3) 6.4 g of the monomer (Z-3), 2.7 g of 3-hydroxy-1-adamantyl acrylate, 0.2 g of azobisisobutyronitrile Was dissolved in 27 g of propylene glycol monomethyl ether, followed by polymerization for 6 hours while maintaining the reaction temperature at 70 ° C. in a nitrogen atmosphere. After the polymerization, the reaction solution is dropped into a large amount of acetone to solidify the produced copolymer, and dried at 40 ° C. under reduced pressure, whereby the monomer (Z-3) having an onium salt structure and 3- A copolymer (Mw: 9,000, Mw / Mn: 1.9) in which the molar ratio of hydroxy-1-adamantyl acrylate was 50:50 was obtained.
This compound is referred to as acid-generating group-containing resin (A-3), and the chemical structural formula thereof is shown below.

Figure 2007328060
Figure 2007328060

尚、上記各合成例におけるＭｗ及びＭｗ／Ｍｎは以下の方法により測定した。
東ソー（株）製高速ＧＰＣ装置（型式「ＨＬＣ−８１２０」）に東ソー（株）製のＧＰＣカラム（商品名「Ｇ２０００ＨＸＬ」；２本、「Ｇ３０００ＨＸＬ」；１本、「Ｇ４０００ＨＸＬ」；１本）を用い、流量１．０ミリリットル／分、溶出溶剤テトラヒドロフラン、カラム温度４０℃の分析条件で、単分散ポリスチレンを標準とするゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定した。 In addition, Mw and Mw / Mn in each said synthesis example were measured with the following method.
Tosoh Co., Ltd. high-speed GPC device (model “HLC-8120”) is equipped with Tosoh Co., Ltd. GPC columns (trade name “G2000HXL”; 2, “G3000HXL”; 1, “G4000HXL”; 1). It was measured by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under the analysis conditions of a flow rate of 1.0 ml / min, an elution solvent tetrahydrofuran, and a column temperature of 40 ° C.

［２］レジスト溶液（感放射線性樹脂組成物）の調製
表１に示すように各成分を混合して均一溶液とした後、孔径２００ｎｍのメンブランフィルターでろ過し、異物を除去して、実施例１〜３及び比較例１のレジスト溶液を調製した（但し、表１において、「部」は質量に基づく）。 [2] Preparation of resist solution (radiation sensitive resin composition) As shown in Table 1, each component was mixed to make a uniform solution, and then filtered through a membrane filter having a pore size of 200 nm to remove foreign matters. 1 to 3 and Comparative Example 1 were prepared (however, in Table 1, “parts” are based on mass).

Figure 2007328060
Figure 2007328060

尚、表１における各実施例及び比較例に用いた成分の詳細を以下に示す。
（Ａ）酸発生基含有樹脂
Ａ−１；オニウム塩構造を有する単量体（Ｚ−１）／２，２，２−トリフルオロエチルアクリレート（モル比で２０／８０）共重合体 （合成例４）
Ａ−２；オニウム塩構造を有する単量体（Ｚ−２）／３−ヒドロキシ−１−アダマンチルアクリレート（モル比で５０／５０）共重合体 （合成例５）
Ａ−３；オニウム塩構造を有する単量体（Ｚ−３）／３−ヒドロキシ−１−アダマンチルアクリレート（モル比で５０／５０）共重合体 （合成例６）
Ａ−４；メタクリル酸メチルエステルホモポリマー（Ｍｗ：４００００、Ｍｗ／Ｍｎ：２．５）
（Ｂ）溶剤
Ｂ−１；乳酸エチル
Ｂ−２；プロピレングリコールモノメチルエーテルアセテート In addition, the detail of the component used for each Example and comparative example in Table 1 is shown below.
(A) Acid generating group-containing resin A-1; Monomer (Z-1) / 2,2,2-trifluoroethyl acrylate (20/80 in molar ratio) copolymer having an onium salt structure (Synthesis Example) 4)
A-2; Monomer (Z-2) / 3-hydroxy-1-adamantyl acrylate (50/50 in molar ratio) copolymer having an onium salt structure (Synthesis Example 5)
A-3: Monomer (Z-3) / 3-hydroxy-1-adamantyl acrylate (50/50 in molar ratio) copolymer having an onium salt structure (Synthesis Example 6)
A-4; Methacrylic acid methyl ester homopolymer (Mw: 40000, Mw / Mn: 2.5)
(B) Solvent B-1; Ethyl lactate B-2; Propylene glycol monomethyl ether acetate

［３］レジストパターンの形成
上記のようにして得られた実施例１〜３及び比較例１の各レジスト溶液を８インチのシリコンウエハに回転塗布し、膜厚１００ｎｍのレジスト被膜を形成した。
次いで、簡易型の電子線描画装置（日立社製、型式「ＨＬ８００Ｄ」、出力；５０ＫｅＶ、電流密度；５．０アンペア／ｃｍ２）を用いてレジスト被膜に電子線を照射した。照射後、表２に示す各種現像液、条件にて現像を行い、その後、水で３０秒間洗浄し、乾燥してレジストパターンを形成した。 [3] Formation of Resist Pattern Each of the resist solutions of Examples 1 to 3 and Comparative Example 1 obtained as described above was spin-coated on an 8-inch silicon wafer to form a resist film having a thickness of 100 nm.
Subsequently, the resist film was irradiated with an electron beam using a simple electron beam drawing apparatus (manufactured by Hitachi, model “HL800D”, output: 50 KeV, current density: 5.0 ampere / cm 2 ). After the irradiation, development was carried out under various developing solutions and conditions shown in Table 2, and then washed with water for 30 seconds and dried to form a resist pattern.

Figure 2007328060
Figure 2007328060

［４］実施例の評価
レジスト溶液の評価（感度）を下記に従い行なった。その結果を表２に併記する。
<感度（Ｅｔｈ）の測定>
シリコンウエハ上に形成したレジスト被膜に電子線照射し、ただちに現像したのち、水洗し、乾燥して、レジストパターンを形成した。３ｍｍ×３ｍｍのエリア各露光量で露光し、膜がなくなった露光量をＥｔｈとした。 [4] Evaluation of Examples Evaluation (sensitivity) of the resist solution was performed as follows. The results are also shown in Table 2.
<Measurement of sensitivity (Eth)>
The resist film formed on the silicon wafer was irradiated with an electron beam, immediately developed, washed with water, and dried to form a resist pattern. Exposure was performed with each exposure amount of 3 mm × 3 mm, and the exposure amount at which the film disappeared was defined as Eth.

Claims (5)

感放射線性樹脂組成物の樹脂成分として含有されている感放射線性酸発生基含有樹脂から、活性光線又は放射線の照射によって酸を発生させ、該感放射線性酸発生基含有樹脂の現像液に対する溶解性を増大させることにより、レジストパターンを形成することを特徴とするパターン形成方法。   From the radiation-sensitive acid generating group-containing resin contained as the resin component of the radiation-sensitive resin composition, an acid is generated by irradiation with actinic rays or radiation, and the radiation-sensitive acid generating group-containing resin is dissolved in the developer. A pattern forming method comprising forming a resist pattern by increasing the property. 請求項１に記載のパターン形成方法に使用され、活性光線又は放射線の照射により酸が発生し、現像液に対する溶解性が増大する感放射線性酸発生基含有樹脂であって、
上記活性光線又は放射線の照射により酸を発生する酸発生基を含有する、下記一般式（１）及び（２）で表される繰り返し単位のうちの少なくとも一方を含むことを特徴とする感放射線性酸発生基含有樹脂。
Figure 2007328060
〔一般式（１）において、Ｒ１は水素原子又はメチル基を表し、Ｒ２は水素原子、ヒドロキシル基、ハロゲン基、ニトロ基、カルボキシル基、アルキル基、アルコキシ基を表し、ｎは０〜３の整数であり、ｎが２又は３の場合、Ｒ２は相互に同一でも異なっていてもよい。Ａは単結合又は−ＯＲ３−基を示し、Ｒ３はメチレン基又はアルキレン基を示す。Ｍ＋は一価のオニウムカチオンを表す。〕
〔一般式（２）において、Ｒ４は水素原子又はメチル基を表し、Ｄは−Ｏ−基、又は−ＮＲ５−基を表し、Ｒ５は水素原子又はアルキル基を示す。Ｅはメチレン基、アルキレン基又はアリーレン基を表し、Ｍ＋は一価のオニウムカチオンを表す。〕 A radiation-sensitive acid-generating group-containing resin that is used in the pattern forming method according to claim 1, wherein an acid is generated by irradiation with actinic rays or radiation, and solubility in a developer increases.
Radiation sensitivity characterized by containing at least one of the repeating units represented by the following general formulas (1) and (2) containing an acid generating group that generates an acid upon irradiation with actinic rays or radiation. Acid generating group-containing resin.
Figure 2007328060
[In General Formula (1), R 1 represents a hydrogen atom or a methyl group, R 2 represents a hydrogen atom, a hydroxyl group, a halogen group, a nitro group, a carboxyl group, an alkyl group, or an alkoxy group, and n is 0 to 3 When n is 2 or 3, R 2 may be the same or different from each other. A represents a single bond or —OR 3 — group, and R 3 represents a methylene group or an alkylene group. M + represents a monovalent onium cation. ]
[In General Formula (2), R 4 represents a hydrogen atom or a methyl group, D represents an —O— group or an —NR 5 — group, and R 5 represents a hydrogen atom or an alkyl group. E represents a methylene group, an alkylene group, or an arylene group, and M + represents a monovalent onium cation. ] 下記一般式（３）、（４）及び（５）で表される非酸解離性繰り返し単位のうちの少なくとも一種を更に含む請求項２に記載の感放射線性酸発生基含有樹脂。
Figure 2007328060
〔一般式（３）において、Ｒ６は水素原子又はメチル基を表し、Ｇは単結合、メチレン基又はアルキレン基を表し、Ｒ７はアルキル基、水素原子、ヒドロキシル基、アルコキシル基、−ＣＯＯＨ、パーフルオロアルキル基又は芳香族基を表す。ここでＲ７が−ＣＯＯＨ又は芳香族基である場合、Ｇはメチレン基又はアルキレン基を示す。〕
〔一般式（４）において、Ｒ８は水素原子又はメチル基を表し、Ｊは単結合、メチレン基又はアルキレン基を表し、Ｒ９は水素原子、アルキル基、ヒドロキシル基、アルコキシル基、−ＣＯＯＨ、パーフルオロアルキル基、芳香族基又はアミノ基を表す。ここでＲ９がアミノ基、ヒドロキシル基、アルコキシル基、−ＣＯＯＨ、パーフルオロアルキル基又は芳香族基である場合、Ｊはメチレン基又はアルキレン基を示す。〕
〔一般式（５）において、Ｒ１０は水素原子又はメチル基を表し、Ｌはメチレン基又はアルキレン基を表し、Ｒ１１は水素原子、ヒドロキシル基、アルコキシル基、−ＣＯＯＨ、パーフルオロアルキル基、芳香族基又はアミノ基を表す。〕 The radiation sensitive acid generating group containing resin of Claim 2 which further contains at least 1 type of the non-acid dissociable repeating unit represented by following General formula (3), (4) and (5).
Figure 2007328060
[In General Formula (3), R 6 represents a hydrogen atom or a methyl group, G represents a single bond, a methylene group or an alkylene group, R 7 represents an alkyl group, a hydrogen atom, a hydroxyl group, an alkoxyl group, —COOH, Represents a perfluoroalkyl group or an aromatic group. Here, when R 7 is —COOH or an aromatic group, G represents a methylene group or an alkylene group. ]
[In General Formula (4), R 8 represents a hydrogen atom or a methyl group, J represents a single bond, a methylene group or an alkylene group, and R 9 represents a hydrogen atom, an alkyl group, a hydroxyl group, an alkoxyl group, —COOH, Represents a perfluoroalkyl group, an aromatic group or an amino group. Here, when R 9 is an amino group, a hydroxyl group, an alkoxyl group, —COOH, a perfluoroalkyl group or an aromatic group, J represents a methylene group or an alkylene group. ]
[In the general formula (5), R 10 represents a hydrogen atom or a methyl group, L represents a methylene group or an alkylene group, R 11 represents a hydrogen atom, a hydroxyl group, an alkoxyl group, —COOH, a perfluoroalkyl group, an aromatic group. Represents a group or an amino group. ] 本感放射線性酸発生基含有樹脂を構成する全繰り返し単位の合計を１００モル％とした場合に、上記一般式（１）及び（２）で表される繰り返し単位の含有率の合計は、１０〜１００モル％である請求項２又は３に記載の感放射線性酸発生基含有樹脂。   When the total of all repeating units constituting the radiation-sensitive acid generating group-containing resin is 100 mol%, the total content of the repeating units represented by the general formulas (1) and (2) is 10 The radiation-sensitive acid generating group-containing resin according to claim 2 or 3, which is -100 mol%. 請求項１に記載のパターン形成方法に使用される感放射線性樹脂組成物であって、樹脂成分として、請求項２乃至４のうちのいずれかに記載の感放射線性酸発生基含有樹脂のみを含有することを特徴とする感放射線性樹脂組成物。   It is a radiation sensitive resin composition used for the pattern formation method of Claim 1, Comprising: Only the radiation sensitive acid generating group containing resin in any one of Claims 2 thru | or 4 is used as a resin component. A radiation-sensitive resin composition characterized by containing.
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