JP5578994B2 - Actinic ray-sensitive or radiation-sensitive resin composition, and resist film and pattern forming method using the same - Google Patents

Description

  The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition suitably used in a lithography process performed in a manufacturing process such as a VLSI, a high-capacity microchip, an imprint mold structure, and other photofabrication processes. And a resist film and a pattern forming method using the same. More specifically, the present invention relates to a positive resist composition for electron beam, X-ray or EUV light preferably applied to the above process, and a resist film and a pattern forming method using the same.

  In recent years, microfabrication by lithography has been demanded to form ultrafine patterns on the order of several tens of nanometers as integrated circuits are highly integrated. Along with this requirement, there is a tendency to shorten the exposure wavelength from g-line to i-line and further to KrF excimer laser light. Furthermore, at present, in addition to excimer laser light, lithography using electron beam, X-ray, or EUV light is being developed.

  In addition, microfabrication using a resist composition is not only directly used for the production of integrated circuits, but also recently applied to the production of so-called imprint mold structures (for example, Patent Documents 1 and 2; And non-patent document 1).

  In particular, electron beam lithography is positioned as a next-generation or next-generation pattern forming technology, and a high-sensitivity, high-resolution positive resist composition is desired. In particular, high sensitivity is a very important issue in order to shorten the wafer processing time, but in the positive resist composition for electron beams, when trying to increase sensitivity, not only the resolution is lowered, Since the line edge roughness deteriorates, it is strongly desired to develop a resist that satisfies these characteristics at the same time. Here, the line edge roughness means that when the pattern is viewed from directly above because the resist pattern and the edge of the substrate interface vary irregularly in the direction perpendicular to the line direction due to the characteristics of the resist. Say that the edge looks uneven. The unevenness is transferred by an etching process using a resist as a mask, and the electrical characteristics are deteriorated, so that the yield is lowered. Particularly in the ultrafine region of 0.25 μm or less, the line edge roughness is an extremely important improvement issue. High sensitivity, high resolution, good pattern shape, and good line edge roughness are in a trade-off relationship, and it is very important how to satisfy them simultaneously.

  Similarly, in lithography using X-rays or EUV light, it is also important to satisfy high sensitivity, high resolution, good pattern shape, and good line edge roughness at the same time. It is.

  As one method for solving these problems, use of a resin having a photoacid generator in a polymer main chain or a side chain has been studied (see, for example, Patent Documents 3 to 8 and Non-Patent Document 2). However, since the technique disclosed in Patent Document 3 is a mixed system of a resin having a photoacid generator and a dissolution inhibiting compound whose solubility in an alkaline developer is increased by acid decomposition, these materials are mixed unevenly. It was difficult to obtain a good pattern shape and line edge roughness due to the property.

  On the other hand, Patent Document 4 discloses a resin having a photoacid-generating group and a group whose solubility in an alkali developer is increased by acid decomposition in the same molecule, but assuming ArF and ArF immersion exposure. In order to maintain transparency with respect to 193 nm light, an aromatic ring group was not introduced into the resin other than the cation portion of the photoacid generating group. In lithography using an electron beam or EUV light, for example, an aromatic ring site such as polyhydroxystyrene generates secondary electrons by exposure to the electron beam or EUV light, and the photoacid generator is decomposed by the secondary electrons. It is generally thought that acid is generated. For this reason, it is difficult to say that the sensitivity to electron beam, X-ray or EUV light is sufficient.

Patent Document 5 and Non-Patent Document 2 describe ternary copolymers of hydroxystyrene, an adamantyl group-containing acrylate, and a photoacid generator-containing acrylate. Patent Document 6 discloses a resist containing a resin containing a repeating unit that is sensitive to high energy rays or heat and generates sulfonic acid at a fluorine-containing terminal of a side chain in order to improve high resolution, density dependency, and exposure margin. Disclosure. Patent Document 7 discloses a resist composition containing a resin containing a repeating unit composed of hydroxyphenyl (meth) acrylate and the like in addition to a repeating unit that generates sulfonic acid at the fluorine-containing terminal of the side chain. Patent Document 8 discloses a resist material containing a repeating unit having a side chain that generates a sulfonium cation.
However, in a resin having a photoacid-generating group and an acid-decomposable group in the side chain, the structure of the photoacid-generating group is important. In the above-described known technique, high sensitivity is obtained in lithography using X-rays or EUV light. It was difficult to satisfy high resolution, good pattern shape, and good line edge roughness at the same time.
Also, depending on the structure of the photoacid generating group, the dry etching resistance of the resist may be reduced.

  As described above, the combination of currently known techniques sufficiently simultaneously provides high sensitivity, high resolution, good pattern shape, good line edge roughness, dry etching resistance, etc. in electron beam, X-ray or EUV light lithography. It is the present condition that I cannot be satisfied with.

JP 2004-158287 A JP 2008-162101 A JP-A-9-325497 JP 2009-93137 A US Patent Application Publication No. 2007/117043 JP 2008-133448 A JP 2009-263487 A JP 2006-215526 A

Nanoimprint Basics and Technology Development / Application Development-Nanoimprint Substrate Technology and Latest Technology Deployment-Editing: Yoshihiko Hirai Frontier Publishing (issued in June 2006) Proc. of SPIE Vol. 6923, 692312, 2008

  In view of the above-mentioned background art, the present invention is particularly sensitive to a sensitive light beam that simultaneously satisfies sensitivity, high resolution, pattern shape, line edge roughness, and dry etching resistance, in lithography using electron beam, X-ray or EUV light as an exposure light source. It is an object to provide a photosensitive or radiation-sensitive resin composition, a resist film using the same, and a pattern forming method.

上記一般式（Ａ１）中、
Ｒ _１ は、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。
Ａは２価の連結基を表す。
Ｒ _ａ１ 、Ｒ _ａ２ 及びＲ _ａ３ は、各々独立に、１価の置換基を表す。Ｒ _ａ１ が複数ある場合には、同じであっても異なっていてもよく、複数のＲ _ａ１ が互いに結合して環を形成していてもよい。Ｒ _ａ２ が複数ある場合には、同じであっても異なっていてもよく、複数のＲ _ａ２ が互いに結合して環を形成していてもよい。Ｒ _ａ３ が複数ある場合には、同じであっても異なっていてもよく、複数のＲ _ａ３ が互いに結合して環を形成していてもよい。Ｒ _ａ１ 、Ｒ _ａ２ 及びＲ _ａ３ のうちの２つが共同して環を形成してもよい。
ｎ１は０〜４の整数を表す。
ｎ２及びｎ３は、各々独立に０〜５の整数を表す。
上記一般式（Ａ２）中、
Ｒ _１ ’は、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。
Ａ’は２価の連結基を表す。
Ｒ _ａ１ ’及びＲ _ａ２ ’は、各々独立に、１価の置換基を表す。Ｒ _ａ１ ’が複数ある場合には、同じであっても異なっていてもよく、複数のＲ _ａ１ ’が互いに結合して環を形成していてもよい。Ｒ _ａ２ ’が複数ある場合には、同じであっても異なっていてもよく、複数のＲ _ａ２ ’が互いに結合して環を形成していてもよい。Ｒ _ａ１ ’及びＲ _ａ２ ’が共同して環を形成してもよい。
ｎ１’は０〜４の整数を表す。
ｎ２’は０〜５の整数を表す。
〔４〕
カチオンを有するカチオン性繰り返し単位（Ａ）、
前記カチオンとイオン対を形成するアニオンを有し、かつ活性光線又は放射線の照射により前記カチオンから解離して酸を発生するアニオン性繰り返し単位（Ｂ）、及び
酸の作用により分解してアルカリ可溶性基を発生する繰り返し単位（Ｃ）を有する樹脂（Ｐ）を含有する感活性光線性又は感放射線性樹脂組成物であって、
前記カチオン性繰り返し単位（Ａ）が下記一般式（Ａ２）又は（Ａ３）で表されるカチオン性繰り返し単位である、感活性光線性又は感放射線性樹脂組成物。

上記一般式（Ａ２）中、
Ｒ _１ ’は、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。
Ａ’は２価の連結基を表す。
Ｒ _ａ１ ’及びＲ _ａ２ ’は、各々独立に、１価の置換基を表す。Ｒ _ａ１ ’が複数ある場合には、同じであっても異なっていてもよく、複数のＲ _ａ１ ’が互いに結合して環を形成していてもよい。Ｒ _ａ２ ’が複数ある場合には、同じであっても異なっていてもよく、複数のＲ _ａ２ ’が互いに結合して環を形成していてもよい。Ｒ _ａ１ ’及びＲ _ａ２ ’が共同して環を形成してもよい。
ｎ１’は０〜４の整数を表す。
ｎ２’は０〜５の整数を表す。
一般式（Ａ３）中、
Ｒ _１ａ 〜Ｒ _１２ａ は、各々独立に、水素原子又は１価の置換基を表し、互いに結合して環を形成していてもよい。
Ｚは、単結合又は２価の連結基である。
Ｒ _１ は、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。
Ａは２価の連結基を表す。
〔５〕
カチオンを有するカチオン性繰り返し単位（Ａ）、
前記カチオンとイオン対を形成するアニオンを有し、かつ活性光線又は放射線の照射により前記カチオンから解離して酸を発生するアニオン性繰り返し単位（Ｂ）、及び
酸の作用により分解してアルカリ可溶性基を発生する繰り返し単位（Ｃ）を有する樹脂（Ｐ）を含有する感活性光線性又は感放射線性樹脂組成物であって、
前記アニオン性繰り返し単位（Ｂ）が、下記一般式（Ｉ）又は（ＩＩ）で表されるアニオン性繰り返し単位である、感活性光線性又は感放射線性樹脂組成物。

一般式（Ｉ）中、
Ｒ _１１ 、Ｒ _１２ 及びＲ _１３ は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。
Ｘ _１１ 、Ｘ _１２ 及びＸ _１３ は、各々独立に、単結合、−Ｏ−、−Ｓ−、−ＣＯ−、−ＳＯ _２ −、−ＮＲ−、２価の窒素含有非芳香族複素環基、又は、これらのうち２つ以上を組み合わせた基を表す。Ｒは水素原子又はアルキル基を表す。
Ａｒ _１ は、２価の芳香環基又は２価の芳香環基とアルキレン基とを組み合わせた基を表す。Ｘ _１１ が単結合である場合、Ｒ _１２ はＡｒ _１ と環を形成していてもよい。
Ｌ _１１ 及びＬ _１２ は、各々独立に、単結合、アルキレン基、アルケニレン基、シクロアルキレン基、２価の芳香環基、又はこれらの２以上を組み合わせた基を表す。
Ｚ _１ は、前記カチオン性繰り返し単位（Ａ）のカチオンとイオン対を形成するアニオン部位であって、活性光線又は放射線の照射により前記カチオンから解離して、スルホン酸基、イミド酸基又はメチド酸基となる部位を表す。
一般式（ＩＩ）中、
Ｒ _２１ 、Ｒ _２２ 及びＲ _２３ は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。
Ｘ _２１ は、−Ｏ−、−Ｓ−、−ＣＯ−、−ＳＯ _２ −、−ＮＲ−、２価の窒素含有非芳香族複素環基、又はこれらのうち２つ以上を組み合わせた基を表す。Ｒは水素原子又はアルキル基を表す。
Ｌ _２１ は、アルキレン基、アルケニレン基、シクロアルキレン基又はこれらの２以上を組み合わせた基を表す。
Ａｒ _２ は、２価の芳香環基又は２価の芳香環基とアルキレン基とを組み合わせた基を表す。
Ｘ _２２ 及びＸ _２３ は、各々独立に、単結合、−Ｏ−、−Ｓ−、−ＣＯ−、−ＳＯ _２ −、−ＮＲ−、２価の窒素含有非芳香族複素環基、又はこれらのうち２つ以上を組み合わせた基を表す。Ｒは水素原子又はアルキル基を表す。
Ｌ _２２ は、アルキレン基、アルケニレン基、シクロアルキレン基、２価の芳香環基、又はこれらの２以上を組み合わせた基を表す。
Ｚ _２ は、前記カチオン性繰り返し単位（Ａ）のカチオンとイオン対を形成するアニオン部位であり、活性光線又は放射線の照射により前記カチオンから解離して、スルホン酸基、イミド酸基又はメチド酸基となる部位を表す。
〔６〕
前記樹脂（Ｐ）が、下記一般式（ＶＩＤ）で表される繰り返し単位を更に含有する〔１〕〜〔５〕のいずれか１項に記載の感活性光線性又は感放射線性組成物。

上記一般式中、Ｒ _０１ 、Ｒ _０２ 及びＲ _０３ は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。
Ｒ _０３ が、アルキレン基を表し、Ｘ又はＡｒ _０１ と結合して主鎖の−Ｃ−Ｃ−鎖と共に５員若しくは６員環を形成していても良い。
Ａｒ _０１ は、芳香環基を表す。
ｎ０１は、１〜４の整数を表す。
Ｘは、単結合又は２価の連結基を表す。
〔７〕
前記繰り返し単位（Ｃ）が、下記一般式（Ｖ）で表される繰り返し単位である、〔１〕〜〔６〕のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。

一般式（Ｖ）において、
Ｒ _５１ 、Ｒ _５２ 及びＲ _５３ は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。
Ｒ _５２ はＬ _５ と結合して環を形成していてもよく、その場合のＲ _５２ はアルキレン基を表わす。
Ｌ _５ は、単結合又は２価の連結基を表し、Ｒ _５２ と環を形成する場合には３価の連結基を表す。
Ｒ _５４ はアルキル基を表し、Ｒ _５５ 及びＲ _５６ は、各々独立に、水素原子、アルキル基、シクロアルキル基又は１価の芳香環基を表す。Ｒ _５５ 及びＲ _５６ は互いに結合して環を形成してもよい。但し、Ｒ _５５ とＲ _５６ とが同時に水素原子であることはない。
〔８〕
前記樹脂（Ｐ）が、ラクトン構造を有する繰り返し単位を更に含有する、〔１〕〜〔７〕のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。
〔９〕
電子線、Ｘ線又はＥＵＶ光により露光される〔１〕〜〔８〕のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。
〔１０〕
〔１〕〜〔９〕のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物を用いて形成されたレジスト膜。
〔１１〕
〔１〕〜〔９〕のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物を用いて、膜を形成し、露光、現像する工程を有するパターン形成方法。
本発明は、上記〔１〕〜〔１１〕に関するものであるが、その他の事項（たとえば下記（１）〜（１６）に記載した事項など）についても参考のために記載した。
（１） カチオンを有するカチオン性繰り返し単位（Ａ）、
前記カチオンとイオン対を形成するアニオンを有し、かつ活性光線又は放射線の照射により前記カチオンから解離して酸を発生するアニオン性繰り返し単位（Ｂ）、及び
酸の作用により分解してアルカリ可溶性基を発生する繰り返し単位（Ｃ）を有する樹脂（Ｐ）を含有する感活性光線性又は感放射線性樹脂組成物。
（２）前記カチオン性繰り返し単位（Ａ）が下記一般式（Ａ１）又は（Ａ２）で表されるカチオン性繰り返し単位である、（１）に記載の感活性光線性又は感放射線性樹脂組成物。 As a result of intensive studies to solve the above problems, the present inventors have completed the present invention shown below.
[1]
A cationic repeating unit (A) having a cation,
An anionic repeating unit (B) having an anion that forms an ion pair with the cation, and dissociating from the cation upon irradiation with actinic rays or radiation to generate an acid; and
A resin (P) having a repeating unit (C) that decomposes by the action of an acid to generate an alkali-soluble group;
An amine derivative having a group leaving on the nitrogen atom by the action of an acid;
An actinic ray-sensitive or radiation-sensitive resin composition containing
[2]
A cationic repeating unit (A) having a cation,
An anionic repeating unit (B) having an anion that forms an ion pair with the cation, and dissociating from the cation upon irradiation with actinic rays or radiation to generate an acid; and
A resin (P) having a repeating unit (C) that decomposes by the action of an acid to generate an alkali-soluble group;
An actinic ray-sensitive or radiation-sensitive resin composition containing a hydrophobic resin different from the resin (P),
The hydrophobic resin is a resin having a silicon atom, or a resin having 10 to 100 mol% of repeating units having a fluorine atom in all repeating units of the hydrophobic resin,
Furthermore, the hydrophobic resin is an actinic ray-sensitive or radiation-sensitive resin composition having at least one group selected from the following groups (x) to (z).
(X) Alkali-soluble group
(Y) A group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer.
(Z) a group that decomposes by the action of an acid
[3]
The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein the cationic repeating unit (A) is a cationic repeating unit represented by the following general formula (A1) or (A2): object.

In the general formula (A1),
R ₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
A represents a divalent linking group.
R _a1 , R _a2 and R _a3 each independently represent a monovalent substituent. When there are a plurality of R _{a1 s,} they may be the same or different, and a plurality of R _a1s may be bonded to each other to form a ring. When there are a plurality of R _{a2 s,} they may be the same or different, and a plurality of R _a2s may be bonded to each other to form a ring. When there are a plurality of R _{a3 s,} they may be the same or different, and a plurality of R _a3 may be bonded to each other to form a ring. Two of R _a1 , R _a2 and R _a3 may jointly form a ring.
n1 represents an integer of 0 to 4.
n2 and n3 each independently represents an integer of 0 to 5.
In the general formula (A2),
R ₁ ′ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
A ′ represents a divalent linking group.
R _a1 ′ and R _a2 ′ each independently represents a monovalent substituent. When there are a plurality of R _a1 ′ s, they may be the same or different, and a plurality of R _a1 ′ s may be bonded to each other to form a ring. When there are a plurality of R _a2 ′ s, they may be the same or different, and a plurality of R _a2 ′ s may be bonded to each other to form a ring. R _a1 ′ and R _a2 ′ may jointly form a ring.
n1 ′ represents an integer of 0 to 4.
n2 ′ represents an integer of 0 to 5.
[4]
A cationic repeating unit (A) having a cation,
An anionic repeating unit (B) having an anion that forms an ion pair with the cation, and dissociating from the cation upon irradiation with actinic rays or radiation to generate an acid; and
An actinic ray-sensitive or radiation-sensitive resin composition containing a resin (P) having a repeating unit (C) that decomposes by the action of an acid to generate an alkali-soluble group,
The actinic ray-sensitive or radiation-sensitive resin composition, wherein the cationic repeating unit (A) is a cationic repeating unit represented by the following general formula (A2) or (A3).

In the general formula (A2),
R ₁ ′ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
A ′ represents a divalent linking group.
R _a1 ′ and R _a2 ′ each independently represents a monovalent substituent. When there are a plurality of R _a1 ′ s, they may be the same or different, and a plurality of R _a1 ′ s may be bonded to each other to form a ring. When there are a plurality of R _a2 ′ s, they may be the same or different, and a plurality of R _a2 ′ s may be bonded to each other to form a ring. R _a1 ′ and R _a2 ′ may jointly form a ring.
n1 ′ represents an integer of 0 to 4.
n2 ′ represents an integer of 0 to 5.
In general formula (A3),
R _{1a to} R _12a each independently represents a hydrogen atom or a monovalent substituent, and may be bonded to each other to form a ring.
Z is a single bond or a divalent linking group.
R ₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
A represents a divalent linking group.
[5]
A cationic repeating unit (A) having a cation,
An anionic repeating unit (B) having an anion that forms an ion pair with the cation, and dissociating from the cation upon irradiation with actinic rays or radiation to generate an acid; and
An actinic ray-sensitive or radiation-sensitive resin composition containing a resin (P) having a repeating unit (C) that decomposes by the action of an acid to generate an alkali-soluble group,
The actinic ray-sensitive or radiation-sensitive resin composition, wherein the anionic repeating unit (B) is an anionic repeating unit represented by the following general formula (I) or (II).

In general formula (I),
R ₁₁ , R ₁₂ and R ₁₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
X ₁₁ , X ₁₂ and X ₁₃ are each independently a single bond, —O—, —S—, —CO—, —SO ₂ —, —NR— , a divalent nitrogen-containing non-aromatic heterocyclic group, Or the group which combined 2 or more of these is represented. R represents a hydrogen atom or an alkyl group.
Ar ₁ represents a divalent aromatic ring group or a combination of a divalent aromatic ring group and an alkylene group. When X ₁₁ is a single bond, R ₁₂ may form a ring with Ar ₁ .
L ₁₁ and L ₁₂ each independently represent a single bond, an alkylene group, an alkenylene group, a cycloalkylene group, a divalent aromatic ring group, or a group obtained by combining two or more thereof.
Z ₁ is an anion site that forms an ion pair with the cation of the cationic repeating unit (A), and is dissociated from the cation by irradiation with actinic rays or radiation to form a sulfonic acid group, an imido acid group, or a methide acid. Represents a base site.
In general formula (II),
R ₂₁ , R ₂₂ and R ₂₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
X ₂₁ represents —O—, —S—, —CO—, —SO ₂ — , —NR—, a divalent nitrogen-containing non-aromatic heterocyclic group, or a group obtained by combining two or more thereof. . R represents a hydrogen atom or an alkyl group.
L ₂₁ represents an alkylene group, an alkenylene group, a cycloalkylene group, or a group obtained by combining two or more thereof.
Ar ₂ represents a divalent aromatic ring group or a combination of a divalent aromatic ring group and an alkylene group.
X ₂₂ and X ₂₃ each independently represent a single bond, —O—, —S—, —CO—, —SO ₂ —, —NR— , a divalent nitrogen-containing non-aromatic heterocyclic group, or these The group which combined 2 or more of them is represented. R represents a hydrogen atom or an alkyl group.
L ₂₂ represents an alkylene group, an alkenylene group, a cycloalkylene group, a divalent aromatic ring group, or a group obtained by combining two or more thereof.
Z ₂ is an anion site that forms an ion pair with the cation of the cationic repeating unit (A), and is dissociated from the cation by irradiation with actinic rays or radiation to form a sulfonic acid group, an imido acid group, or a methido acid group. Represents the site.
[6]
The actinic ray-sensitive or radiation-sensitive composition according to any one of [1] to [5], wherein the resin (P) further contains a repeating unit represented by the following general formula (VID).

In the above general formula, R ₀₁ , R ₀₂ and R ₀₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
R ₀₃ represents an alkylene group and may combine with X or Ar ₀₁ to form a 5-membered or 6-membered ring together with the main chain —C—C— chain.
Ar ₀₁ represents an aromatic ring group.
n01 represents an integer of 1 to 4.
X represents a single bond or a divalent linking group.
[7]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein the repeating unit (C) is a repeating unit represented by the following general formula (V).

In general formula (V):
R ₅₁ , R ₅₂ and R ₅₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
R ₅₂ may be bonded to L ₅ to form a ring, in which case R ₅₂ represents an alkylene group.
L ₅ represents a single bond or a divalent linking group, and in the case of forming a ring with R ₅₂ , represents a trivalent linking group.
R ₅₄ represents an alkyl group, and R ₅₅ and R ₅₆ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or a monovalent aromatic ring group. R ₅₅ and R ₅₆ may combine with each other to form a ring. _However, no and _{R 55} and _{R 56} are hydrogen atoms at the same time.
[8]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7], wherein the resin (P) further contains a repeating unit having a lactone structure.
[9]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8], which is exposed to electron beam, X-ray, or EUV light.
[10]
A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [9].
[11]
The pattern formation method which has the process of forming a film | membrane using the actinic-ray-sensitive or radiation-sensitive resin composition of any one of [1]-[9], exposing and developing.
The present invention relates to the above [1] to [11], but other matters (for example, the matters described in the following (1) to (16)) are also described for reference.
(1) Cationic repeating unit (A) having a cation,
An anionic repeating unit (B) that has an anion that forms an ion pair with the cation, and dissociates from the cation upon irradiation with actinic rays or radiation, and an alkali-soluble group that decomposes by the action of the acid An actinic ray-sensitive or radiation-sensitive resin composition containing a resin (P) having a repeating unit (C) that generates benzene.
(2) The actinic ray-sensitive or radiation-sensitive resin composition according to (1), wherein the cationic repeating unit (A) is a cationic repeating unit represented by the following general formula (A1) or (A2): .

In the general formula (A1),
R ₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
A represents a divalent linking group.
R _a1 , R _a2 and R _a3 each independently represent a monovalent substituent. When there are a plurality of R _{a1 s,} they may be the same or different, and a plurality of R _a1s may be bonded to each other to form a ring. When there are a plurality of R _{a2 s,} they may be the same or different, and a plurality of R _a2s may be bonded to each other to form a ring. When there are a plurality of R _{a3 s,} they may be the same or different, and a plurality of R _a3 may be bonded to each other to form a ring. Two of R _a1 , R _a2 and R _a3 may jointly form a ring.
n1 represents an integer of 0 to 4.
n2 and n3 each independently represents an integer of 0 to 5.
In the general formula (A2),
R ₁ ′ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
A ′ represents a divalent linking group.
R _a1 ′ and R _a2 ′ each independently represents a monovalent substituent. When there are a plurality of R _a1 ′ s, they may be the same or different, and a plurality of R _a1 ′ s may be bonded to each other to form a ring. When there are a plurality of R _a2 ′ s, they may be the same or different, and a plurality of R _a2 ′ s may be bonded to each other to form a ring. R _a1 ′ and R _a2 ′ may jointly form a ring.
n1 ′ represents an integer of 0 to 4.
n2 ′ represents an integer of 0 to 5.
(3) The cationic repeating unit (A) is a cationic repeating unit represented by the general formula (A1), and the cationic repeating unit represented by the general formula (A1) is represented by the following general formula (A3). The actinic ray-sensitive or radiation-sensitive resin composition according to (2), which is a cationic repeating unit represented by:

In general formula (A3),
R _{1a to} R _12a each independently represents a hydrogen atom or a monovalent substituent, and may be bonded to each other to form a ring.
Z is a single bond or a divalent linking group. R ₁ and A have the same meanings as R ₁ and A in formula (A1), respectively.
(4) The feeling according to any one of (1) to (3), wherein the anionic repeating unit (B) is an anionic repeating unit represented by the following general formula (I) or (II): Actinic ray-sensitive or radiation-sensitive resin composition.

In general formula (I),
R ₁₁ , R ₁₂ and R ₁₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
X ₁₁ , X ₁₂ and X ₁₃ are each independently a single bond, —O—, —S—, —CO—, —SO ₂ —, —NR—, a divalent nitrogen-containing non-aromatic heterocyclic group, Or the group which combined 2 or more of these is represented. R represents a hydrogen atom or an alkyl group.
Ar ₁ represents a divalent aromatic ring group or a combination of a divalent aromatic ring group and an alkylene group. When X ₁₁ is a single bond, R ₁₂ may form a ring with Ar ₁ .
L ₁₁ and L ₁₂ each independently represent a single bond, an alkylene group, an alkenylene group, a cycloalkylene group, a divalent aromatic ring group, or a group obtained by combining two or more thereof.
Z ₁ is an anion site that forms an ion pair with the cation of the cationic repeating unit (A), and is dissociated from the cation by irradiation with actinic rays or radiation to form a sulfonic acid group, an imido acid group, or a methide acid. Represents a base site.
In general formula (II),
R ₂₁ , R ₂₂ and R ₂₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
X ₂₁ represents —O—, —S—, —CO—, —SO ₂ —, —NR—, a divalent nitrogen-containing non-aromatic heterocyclic group, or a group obtained by combining two or more thereof. . R represents a hydrogen atom or an alkyl group.
L ₂₁ represents an alkylene group, an alkenylene group, a cycloalkylene group, or a group obtained by combining two or more thereof.
Ar ₂ represents a divalent aromatic ring group or a combination of a divalent aromatic ring group and an alkylene group.
X ₂₂ and X ₂₃ each independently represent a single bond, —O—, —S—, —CO—, —SO ₂ —, —NR—, a divalent nitrogen-containing non-aromatic heterocyclic group, or these The group which combined 2 or more of them is represented. R represents a hydrogen atom or an alkyl group.
L ₂₂ represents an alkylene group, an alkenylene group, a cycloalkylene group, a divalent aromatic ring group, or a group obtained by combining two or more thereof.
Z ₂ is an anion site that forms an ion pair with the cation of the cationic repeating unit (A), and is dissociated from the cation by irradiation with actinic rays or radiation to form a sulfonic acid group, an imido acid group, or a methido acid group. Represents the site.
(5) The actinic ray-sensitive or radiation-sensitive composition according to any one of (1) to (4), wherein the resin (P) further contains a repeating unit represented by the following general formula (VID). object.

In the above general formula, R ₀₁ , R ₀₂ and R ₀₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
R ₀₃ represents an alkylene group and may combine with X or Ar ₀₁ to form a 5-membered or 6-membered ring together with the main chain —C—C— chain.
Ar ₀₁ represents an aromatic ring group.
n01 represents an integer of 1 to 4.
X represents a single bond or a divalent linking group.
(6) The actinic ray-sensitive or radiation-sensitive resin according to any one of (1) to (5), wherein the repeating unit (C) is a repeating unit represented by the following general formula (V): Composition.

In general formula (V):
R ₅₁ , R ₅₂ and R ₅₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
R ₅₂ may be bonded to L ₅ to form a ring, in which case R ₅₂ represents an alkylene group.
L ₅ represents a single bond or a divalent linking group, and in the case of forming a ring with R ₅₂ , represents a trivalent linking group.
R ₅₄ represents an alkyl group, and R ₅₅ and R ₅₆ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or a monovalent aromatic ring group. R ₅₅ and R ₅₆ may combine with each other to form a ring. _However, no and _{R 55} and _{R 56} are hydrogen atoms at the same time.
(7) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (6), wherein the resin (P) further contains a repeating unit having a lactone structure.
(8) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (7), which is exposed to electron beam, X-ray or EUV light.
(9) A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (8).
(10) A pattern forming method comprising the steps of forming a film, exposing and developing using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (8).

The present invention preferably further has the following configuration.
(11) In the general formulas (I) and (II), Ar ₁ and Ar ₂ are each independently an arylene group or an aralkylene group, and L ₁₂ and L ₂₂ are each independently the following structures or structures: The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (4) to (8), which is represented by any one of a combination of the above.

In the above structure, in the general formula (I), * represents a bond with X ₁₃ (L ₁₁ when X ₁₃ is a single bond) or Z ₁ . In the general formula (II), * represents a bond with X ₂₃ (Ar ₂ when X ₂₃ is a single bond) or Z ₂ .
(12) In the general formula (VID), the divalent linking group for X is an alkylene group, a cycloalkylene group, an arylene group, —COO—, —OCO—, —CO—, —O—, —S—. , —S (═O) —, —S (═O) ₂ —, —OS (═O) ₂ —, and —NH—, or a combination of two or more thereof The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (5) to (8) or (11).
(13) The repeating unit (C) is a repeating unit represented by the following general formula (VI): (1) to (5), (7), (8), (11) or (12) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of the above.

In general formula (VI), R ₆₁ , R ₆₂ and R ₆₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₆₂ may be bonded to Ar ₆ to form a ring, in which case R ₆₂ represents an alkylene group. X ₆ represents a single bond, —COO— or —CONR ₆₄ —. R ₆₄ represents a hydrogen atom or an alkyl group.
Ar ₆ represents an (n + 1) -valent aromatic ring group, and when forming a ring with R ₆₂ , represents an (n + 2) -valent aromatic ring group. Y each independently represents a hydrogen atom or a group capable of leaving by the action of an acid. When n is an integer of 2 or more, a plurality of Y may be the same as or different from each other. However, at least one of Y represents a group capable of leaving by the action of an acid. n represents an integer of 1 to 4.
(14) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (7) and (11) to (13), which is for immersion exposure.
(15) The pattern forming method according to (10), wherein an electron beam, an X-ray or EUV light is used as the exposure light source.
(16) The pattern forming method according to (10), wherein the exposure is immersion exposure.

  According to the present invention, an actinic ray-sensitive or radiation-sensitive resin composition excellent in sensitivity, high resolution, pattern shape, line edge roughness, and dry etching resistance, and a resist film and a pattern forming method using the same are provided. In particular, in lithography using an electron beam, X-rays or EUV light as an exposure light source, it is excellent in sensitivity, high resolution, pattern shape, line edge roughness, and dry etching resistance.

Hereinafter, the present invention will be described in detail.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. . For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, “active light” or “radiation” means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams (EB), etc. To do. In the present invention, light means actinic rays or radiation.
In addition, “exposure” in the present specification is not limited to exposure to far ultraviolet rays, extreme ultraviolet rays, X-rays, EUV light and the like represented by mercury lamps and excimer lasers, but also electron beams, ion beams, and the like, unless otherwise specified. The exposure with the particle beam is also included in the exposure.

<Resin (P)>
The resin (P) contained in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is:
A cationic repeating unit (A) having a cation,
An anionic repeating unit (B) that has an anion that forms an ion pair with the cation, and dissociates from the cation upon irradiation with actinic rays or radiation, and an alkali-soluble group that decomposes by the action of the acid The repeating unit (C) which generate | occur | produces is contained. In the present invention, the ion pair formation between the cation of the cationic repeating unit (A) and the anion of the anionic repeating unit (B) is not limited to the ion pair formation in a single molecule of the polymer in the resin (P). , Is also meant to encompass ion pairing between multiple polymer molecules.
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably a positive resist composition.
The reason why the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is excellent in sensitivity, resolution, pattern shape, line edge roughness, and dry etching resistance is not clear, but is estimated as follows.
In the present invention, the cation of the cationic repeating unit (A) and the anion of the anionic repeating unit (B) form an ion pair, so that a three-dimensional network (network) between multiple molecules of the polymer molecule is formed. It is presumed that the dry etching resistance can be enhanced.
Moreover, the glass transition point (Tg) of the resist film is increased by the pseudo-crosslinking due to the ion pair formation, and the acid diffusibility can be greatly suppressed, so that the resolution and the line edge roughness are improved. It is estimated to be.
Further, since the pseudo-crosslinking due to the ion pair formation is released at the time of exposure, it is estimated that the dissolution contrast increases, contributing to higher sensitivity and pattern shape.
As described above, it is presumed that the actinic ray-sensitive or radiation-sensitive resin composition of the present invention imparts characteristics excellent in sensitivity, resolution, pattern shape, line edge roughness, and dry etching resistance.
[Cationic repeating unit (A)]
The resin (P) contained in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention has a cation that forms an ion pair with an anion of an anionic repeating unit (B) described later, and an actinic ray or radiation. The cationic repeating unit (A) dissociated from the anion by irradiation of
In the present invention, the cation of the cationic repeating unit (A) and the anion of the anionic repeating unit (B) can form an ion pair. For convenience, in the present specification and claims, a resin ( P) describes that it contains a cationic repeating unit (A) and an anionic repeating unit (B).
The cationic repeating unit (A) may be a repeating unit that dissociates from an anion of the anionic repeating unit (B) described later upon irradiation with actinic rays or radiation and generates a cation in the side chain of the resin.
The cationic repeating unit (A) having a cation that forms an ion pair with the anion of the anionic repeating unit (B) described below and dissociating from the anion upon irradiation with actinic rays or radiation includes a sulfonium cation and an iodonium cation. Or it is preferable that it is a cationic repeating unit which has a pyridinium cation.
Among these, a cationic repeating unit represented by the general formula (A1) or (A2) is more preferable.

In the general formula (A1),
R ₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
A represents a divalent linking group.
R _a1 , R _a2 and R _a3 each independently represent a monovalent substituent. When there are a plurality of R _{a1 s,} they may be the same or different, and a plurality of R _a1s are bonded to each other to form a ring (for example, an aromatic or non-aromatic hydrocarbon ring or a heterocyclic ring). You may do it. When there are a plurality of R _{a2 s,} they may be the same or different, and a plurality of R _a2s are bonded to each other to form a ring (for example, an aromatic or non-aromatic hydrocarbon ring or a heterocyclic ring). You may do it. When there are a plurality of R _{a3 s,} they may be the same or different, and a plurality of R _a3s are bonded to each other to form a ring (for example, an aromatic or non-aromatic hydrocarbon ring or a heterocycle). You may do it. Two of R _a1 , R _a2 and R _a3 may jointly form a ring (for example, an aromatic or non-aromatic hydrocarbon ring or a heterocyclic ring).
n1 represents an integer of 0 to 4.
n2 and n3 each independently represents an integer of 0 to 5.
In the general formula (A2),
R ₁ ′ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
A ′ represents a divalent linking group.
R _a1 ′ and R _a2 ′ each independently represents a monovalent substituent. When there are a plurality of R _a1 ′ s, they may be the same or different, and a plurality of R _a1 ′ s are bonded to each other to form a ring (for example, an aromatic or non-aromatic hydrocarbon ring or a heterocycle) May be formed. When there are a plurality of R _a2 ′ s, they may be the same or different, and a plurality of R _a2 ′ s are bonded to each other to form a ring (for example, an aromatic or non-aromatic hydrocarbon ring or a heterocycle) May be formed. R _a1 ′ and R _a2 ′ may jointly form a ring (for example, an aromatic or non-aromatic hydrocarbon ring or a heterocyclic ring).
n1 ′ represents an integer of 0 to 4.
n2 ′ represents an integer of 0 to 5.

Specific examples and preferred examples of the alkyl group, cycloalkyl group, halogen atom and alkoxycarbonyl group for R ₁ include R ₁₁ , R ₁₂ and R _{13 in} the general formula (I) of the anionic repeating unit (B). The thing similar to the specific example and preferable example which were made is mentioned.
The divalent linking group for A includes an alkylene group, a cycloalkylene group, an arylene group, -COO-, -OCO-, -CO-, -O-, -S-, -S (= O)-,- Examples thereof include a group selected from S (═O) ₂ —, —OS (═O) ₂ —, and —NH—, or a combination of two or more thereof.

The alkylene for A is preferably a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and examples thereof include a methylene group, an ethylene group, and a propylene group.
The cycloalkylene group for A preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and examples thereof include a 1,4-cyclohexylene group.
In the alkylene group and cycloalkylene group for A, some or all of the hydrogen atoms bonded to carbon may be substituted with a substituent.
The arylene group for A is preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 10 carbon atoms (for example, phenylene or naphthylene), and part or all of hydrogen atoms bonded to carbon. May be substituted with a substituent.

Examples of the substituent which the alkylene group, cycloalkylene group and arylene group for A may have include, for example, a halogen group such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a methoxy group, an ethoxy group, a tert- Alkoxy groups such as butoxy group; aryloxy groups such as phenoxy group and p-tolyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group and butoxycarbonyl group; aryloxycarbonyl groups such as phenoxycarbonyl group and p-tolyloxycarbonyl group; Acyloxy groups such as acetoxy group, propionyloxy group, benzoyloxy group; acyl groups such as acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, methoxalyl group; methylsulfanyl group, tert-butylsulfanyl group Kirsulfanyl group; arylsulfanyl group such as phenylsulfanyl group and p-tolylsulfanyl group; alkyl such as methylamino group and cyclohexylamino group or cycloalkylamino group, dialkyl such as dimethylamino group, diethylamino group, morpholino group and piperidino group Aryl group such as amino group, phenylamino group, p-tolylamino group, alkyl group such as methyl group, ethyl group, tert-butyl group, dodecyl group, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl Group, anthryl group, aryl group such as phenanthryl group, etc., hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, perfluoro Alkyl group, trialkyl Lil group, and the like.
The divalent linking group for A is preferably —COO— or —CONH—, more preferably —COO—.

Specific examples and preferred examples of monovalent substituents for R _a1 , R _a2 and R _a3 include specific examples and preferred examples of monovalent substituents described later for R _{1a to} R _{12a in} formula (A3). The same thing is mentioned.
n1 is preferably an integer of 0 to 2. n2 and n3 are preferably integers of 0 to 4.
R ₁ ′, A ′, R _a1 ′, R _a2 ′, n1 ′, and n2 ′ are respectively synonymous with R ₁ , A, R _a1 , R _a2 , n1, and n2, and specific examples and preferred examples are also included. The same thing is mentioned.

  A more preferable structure of the cationic repeating unit (A) is an outgas problem (when irradiated with high energy rays such as EUV light, the compound in the resist film is destroyed by fragmentation and volatilized as a low molecular component during exposure. And the general formula (A3) is preferable from the viewpoint of suppressing the problem of contaminating the environment in the exposure apparatus.

In General Formula (A3), R _{1a to} R _12a each independently represent a hydrogen atom or a monovalent substituent, and may be bonded to each other to form a ring. Z is a single bond or a divalent linking group. R ₁ and A are respectively synonymous with R ₁ and A in General Formula (A1), and the same examples can be given for specific examples and preferred examples.

R _{1a to} R _12a are each independently a hydrogen atom or a monovalent substituent, and the monovalent substituent is not particularly limited. For example, a halogen atom, an alkyl group (a cycloalkyl group, a bicycloalkyl group) , Including tricycloalkyl groups), alkenyl groups (including cycloalkenyl groups and bicycloalkenyl groups), alkynyl groups, aryl groups, heterocyclic groups (also referred to as heterocyclic groups), cyano groups, hydroxyl groups, nitro groups Group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, Acylamino group, aminocarbonylamino group, alkoxycarbonyl group Group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkylsulfinyl group, arylsulfinyl group, Alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, arylazo group, heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, a phosphono group, a silyl group, a hydrazino group, a ureido group, a boronic acid group (-B _(OH) 2), phosphato group (-OPO _(OH) 2), a sulfato group (-OSO ₃ H), the other known Examples of substituents That.

R _{1a to} R _12a are preferably a hydrogen atom or a halogen atom, an alkyl group (including a cycloalkyl group), an alkenyl group (including a cycloalkenyl group or a bicycloalkenyl group), an alkynyl group, an aryl group, a cyano group, or a carboxyl group. Alkoxy group, aryloxy group, acyloxy group, carbamoyloxy group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, alkylthio group, An arylthio group, a sulfamoyl group, an alkyl and arylsulfonyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an imide group, a silyl group, and a ureido group.

R _{1a to} R _12a are more preferably a hydrogen atom or a halogen atom, an alkyl group (including a cycloalkyl group), a cyano group, an alkoxy group, an acyloxy group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an alkyl, and An arylsulfonylamino group, an alkylthio group, a sulfamoyl group, an alkyl and arylsulfonyl group, an alkoxycarbonyl group, and a carbamoyl group.

R _{1a to} R _12a are particularly preferably a hydrogen atom, an alkyl group (including a cycloalkyl group), a halogen atom, or an alkoxy group.

Two of R _{1a to} R _12a may jointly form a ring (for example, an aromatic or non-aromatic hydrocarbon ring or a heterocyclic ring). Examples of the combination of two or more of R _{1a to} R _{12a that} form a ring include R _2a and R _3a , and R _6a and R _7a .
The ring to be formed may be a polycyclic fused ring. Specific examples of the ring include, for example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, Pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring Carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, phenothiazine ring, and phenazine ring.

The monovalent substituent as R _{1a to} R _12a and the ring that two of R _{1a to} R _12a may form may further have a substituent. Specific examples of the substituent are the same as the specific examples of the monovalent substituent.

The monovalent substituent as R _{1a to} R _12a preferably has 20 or less carbon atoms, and more preferably 15 or less carbon atoms.

Z represents a single bond or a divalent linking group. Examples of the divalent linking group include an ether group, a thioether group, an alkylene group, an arylene group, a carbonyl group, a sulfonyl group, a carbonyloxy group, a carbonylamino group, and a sulfonylamide. Group, amino group, disulfide group, acyl group, alkylsulfonyl group, —CH═CH—, —C≡C—, aminocarbonylamino group, aminosulfonylamino group and the like, which may have a substituent. These substituents are the same as the substituents shown for R _{1a to} R _12a above. Z preferably has a single bond, an ether group, a thioether group, an alkylene group, an arylene group, an amino group, —CH═CH—, —C≡C—, an aminocarbonylamino group, an aminosulfonylamino group, or the like. More preferably a single bond, an ether group or a thioether group, and particularly preferably a single bond.
Specific examples of the cationic repeating unit (A) having a cation that forms an ion pair with the anion of the anionic repeating unit (B) described below and dissociating from the anion upon irradiation with actinic rays or radiation are listed below. However, the present invention is not limited to this.

The polymerizable precursor corresponding to the cationic repeating unit (A) can be synthesized by using general esterification, etherification, and sulfonylation reactions. For example, a method in which a hydroxyl group-containing onium salt is reacted with (methyl) acrylic anhydride or (methyl) acrylic acid halide to esterify, a hydroxyl group-containing onium salt and a polymerizable group-containing halide compound are reacted with ether. The hydroxide, bromide, chloride, and the like of the onium salt of the polymerizable precursor corresponding to the cationic repeating unit (A) can be obtained by the method of converting to cation.
[Anionic repeating unit (B)]
The resin (P) contained in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention has an anion that forms an ion pair with the cation of the cationic repeating unit (A), and has an actinic ray or radiation. It contains an anionic repeating unit (B) that dissociates from the cation upon irradiation to generate an acid.
In the present invention, the resin (P) contains an anionic repeating unit (B) that generates an acid by being dissociated from the cation of the cationic repeating unit (A) by irradiation with actinic rays or radiation. It is possible to improve the resolution or pattern shape by suppressing the diffusion of the generated acid to the non-exposed portion.
The anionic repeating unit (B) is a repeating unit that dissociates from the cation of the cationic repeating unit (A) by irradiation with actinic rays or radiation to generate an acid anion in the side chain of the resin. An anionic repeating unit containing an aromatic ring in the side chain is preferred.
More specifically, the repeating unit (B) is preferably an anionic repeating unit represented by the following general formula (I) or (II).

In the general formula (I), R ₁₁ , R ₁₂ and R ₁₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
The alkyl group is a linear or branched alkyl group which may have a substituent, preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, or n-butyl which may have a substituent. Group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, dodecyl group and the like, and an alkyl group having 20 or less carbon atoms, more preferably an alkyl group having 8 or less carbon atoms, particularly preferably 3 or less carbon atoms. Of the alkyl group.
As the alkyl group contained in the alkoxycarbonyl group, the same alkyl groups as those described above for R ₁₁ , R ₁₂ and R ₁₃ are preferable.

Examples of the cycloalkyl group include monocyclic or polycyclic cycloalkyl groups which may have a substituent. Preferable examples include a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group which may have a substituent.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.

Preferred substituents in each of the above groups are a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, an amide group, a sulfonamide group, an alkyl group exemplified in R _{11 to} R ₁₃ , or a methoxy group. , Alkoxy groups such as ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group and butoxy group, alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, acyl groups such as formyl group, acetyl group and benzoyl group, acetoxy group , Acyloxy groups such as butyryloxy groups, and carboxy groups. In particular, a hydroxyl group and a halogen atom are preferable.

R ₁₁ , R ₁₂ and R ₁₃ in the formula (I) are more preferably a hydrogen atom, an alkyl group or a halogen atom, a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (—CF ₃ ) or a hydroxymethyl group. (—CH ₂ —OH), a chloromethyl group (—CH ₂ —Cl), and a fluorine atom (—F) are particularly preferred.

X ₁₁ , X ₁₂ , and X ₁₃ are each independently a single bond, —O—, —S—, —CO—, —SO ₂ —, —NR— (R is a hydrogen atom or an alkyl group), divalent It represents a nitrogen-containing non-aromatic heterocyclic group or a group obtained by combining two or more of these.
In —NR—, the alkyl group represented by R is a linear or branched alkyl group which may have a substituent, and is the same as the alkyl group in R ₁₁ , R ₁₂ and R ₁₃ above. An example is given. R is particularly preferably a hydrogen atom, a methyl group or an ethyl group. In addition, the divalent nitrogen-containing non-aromatic heterocyclic group means a non-aromatic heterocyclic group having at least one nitrogen atom, preferably 3 to 8 members, specifically, for example, Examples thereof include a divalent linking group having a structure.

When X ₁₁ is a single bond, R ₁₂ may form a ring with Ar _1, and R ₁₂ in this case represents an alkylene group. X ₁₁ is more preferably a single bond, —COO—, or —CONR— (where R is a hydrogen atom or an alkyl group), and particularly preferably a single bond or —COO—.
X ₁₂ is more preferably a single bond, —O—, —CO—, —SO ₂ —, —NR— (wherein R is a hydrogen atom or an alkyl group), and a group obtained by combining two or more thereof. A bond, —OCO—, and —OSO ₂ — are particularly preferable.
X ₁₃ is more preferably a single bond, —O—, —CO—, —SO ₂ —, —NR— (R is a hydrogen atom or an alkyl group), and a group obtained by combining two or more of these, A single bond, —OCO—, and —OSO ₂ — are particularly preferable.

L ₁₁ represents a single bond, an alkylene group, an alkenylene group, a cycloalkylene group, a divalent aromatic ring group, or a group obtained by combining two or more thereof. In the combined group, the 2 or more groups combined may be different even in the same, also, -O as a linking group -, - S -, - CO -, - SO 2 -, - NR- (R Is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, or a group obtained by combining two or more thereof.

The alkylene group for L ₁₁ may be linear or branched, and examples thereof include 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. The alkylene group is a preferred example. An alkylene group having 1 to 6 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is particularly preferable.

As the alkenylene group in any position of the alkylene group described above L _11, includes a group having a double bond.
The cycloalkylene group may be monocyclic or polycyclic, for example, a carbon such as a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a norbornanylene group, an adamantylene group, or a diamantylene group. A cycloalkylene group having a number of 3 to 17 is a preferred example. A cycloalkylene group having 5 to 12 carbon atoms is more preferable, and a cycloalkylene group having 6 to 10 carbon atoms is particularly preferable.

  Examples of the divalent aromatic ring group include an arylene group optionally having a substituent having 6 to 14 carbon atoms such as a phenylene group, a tolylene group, and a naphthylene group, or, for example, thiophene, furan, pyrrole, benzo Mention may be made of divalent aromatic ring groups containing heterocycles such as thiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole and the like.

Specific examples of —NR— and the divalent nitrogen-containing non-aromatic heterocyclic group include the same specific examples as those described above for X ₁₁ , and preferred examples are also the same.
L ₁₁ is more preferably a single bond, an alkylene group or a cycloalkylene group, and particularly preferably a single bond or an alkylene group.

L ₁₂ represents a single bond, an alkylene group, an alkenylene group, a cycloalkylene group, a divalent aromatic ring group, or a group in which two or more of these are combined, and these groups include a part or all of hydrogen atoms, It is preferably substituted with a substituent selected from a fluorine atom, a fluorinated alkyl group, a nitro group, or a cyano group. In the combined group, the 2 or more groups combined may be different even in the same, also, -O as a linking group -, - S -, - CO -, - SO 2 -, - NR- (R Is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, or a group obtained by combining two or more thereof.

L ₁₂ includes an alkylene group, a divalent aromatic ring group, or two of them, in which part or all of the hydrogen atoms are substituted with a fluorine atom or a fluorinated alkyl group (more preferably a perfluoroalkyl group). A group obtained by combining the above is more preferable, and an alkylene group in which at least a part or all of the group is substituted with a fluorine atom is particularly preferable. L ₁₂ is most preferably an alkylene group in which 30 to 100% of the number of hydrogen atoms are substituted with fluorine atoms.

The alkylene group for L ₁₂ may be linear or branched, and examples thereof include 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. The alkylene group is a preferred example. An alkylene group having 1 to 6 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is particularly preferable.
The alkenylene group includes a group having a double bond at an arbitrary position of the alkylene group.

  The cycloalkylene group may be monocyclic or polycyclic, for example, a carbon such as a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a norbornanylene group, an adamantylene group, or a diamantylene group. A cycloalkylene group having a number of 3 to 17 is a preferred example.

Examples of the divalent aromatic ring group include the same groups as the specific examples given for the divalent aromatic ring group as the linking group in L ₁₁ described above.
Specific examples of the linking group —NR— and the divalent nitrogen-containing non-aromatic heterocyclic group in L ₁₂ include the same specific examples as in X ₁₁ described above, and preferred examples are also the same.
Below, while indicating preferred embodiments of L _12, not particularly limited thereto. In specific examples, * represents a bond with X ₁₃ (L ₁₁ when X ₁₃ is a single bond) or Z ₁ .

Ar ₁ represents a divalent aromatic ring group or a combination of a divalent aromatic ring group and an alkylene group.
The divalent aromatic ring group may have a substituent, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, a naphthylene group, or a thiophene, furan, pyrrole, benzo Preferred examples include divalent aromatic ring groups containing a heterocycle such as thiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole.

Preferred substituents in each of the above groups are alkyl groups, methoxy groups, ethoxy groups, hydroxyethoxy groups, propoxy groups, hydroxypropoxy groups, butoxy groups and other aryl groups such as phenyl groups, and phenyl groups such as R _{11 to} R _13. Is mentioned.

  Examples of the combination of a divalent aromatic ring group and an alkylene group include the above-described divalent aromatic ring group and carbon numbers such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. Preferred examples include an aralkylene group in which 1 to 8 alkylene groups (which may be linear or branched) are combined.

As Ar ₁ , an arylene group having 6 to 18 carbon atoms which may have a substituent is more preferable, and a phenylene group substituted with a phenylene group, a naphthylene group, a biphenylene group, or a phenyl group is particularly preferable.

Z ₁ is an anion site that forms an ion pair with the cation of the cationic repeating unit (A), which is dissociated from the cation by irradiation with an actinic ray or radiation to form a sulfonic acid group, an imido acid group, or a methide acid group Represents the site. The site represented by Z ₁ is preferably a structure represented by the following general formulas (ZI) to (ZIII).

In the general formulas (ZII) and (ZIII), Z ₁ , Z ₂ , Z ₃ , Z ₄ , and Z ₅ each independently represent —CO— or —SO ₂ — to further reduce the pKa of the generated acid. and more preferably - -SO ₂ from the viewpoint of.
Rz ₁ , Rz ₂ and Rz ₃ each independently represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. In these groups, an embodiment in which part or all of hydrogen atoms are substituted with fluorine atoms or fluoroalkyl groups (more preferably perfluoroalkyl groups) is more preferable, and 30 to 100% of the number of hydrogen atoms is substituted with fluorine atoms. In particular, an alkyl group in which 30 to 100% of the number of hydrogen atoms is substituted with a fluorine atom is most preferable.

The alkyl group may be linear or branched. For example, an alkyl having 1 to 8 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and an octyl group. A group is mentioned as a preferred example. An alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.
As the cycloalkyl group, for example, a cycloalkyl group having 3 to 10 carbon atoms such as a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group is preferable, and a cycloalkyl group having 3 to 6 carbon atoms is more preferable.

As the aryl group, an aryl group having 6 to 18 carbon atoms is preferable, an aryl group having 6 to 10 carbon atoms is more preferable, and a phenyl group is particularly preferable.
Preferred examples of the aralkyl group include an aralkyl group in which an alkylene group having 1 to 8 carbon atoms and the aryl group are bonded. An aralkyl group in which an alkylene group having 1 to 6 carbon atoms and the aryl group are bonded is more preferable, and an aralkyl group in which an alkylene group having 1 to 4 carbon atoms and the aryl group are bonded is particularly preferable.
Rz ₁ , Rz ₂ and Rz _{3 in the} general formula (ZII) or (ZIII) are each independently more preferably an alkyl group, and a part or all of the hydrogen atoms are fluorine atoms or fluoroalkyl groups (more Alkyl groups substituted with perfluoroalkyl groups) are particularly preferred.

Rz ₁ , Rz ₂ , and Rz ₃ are more preferably alkyl groups in which some or all of the hydrogen atoms are substituted with fluorine atoms or fluoroalkyl groups (more preferably perfluoroalkyl groups), and 30 to 100 hydrogen atoms. Alkyl groups in which% is substituted with fluorine atoms are particularly preferred.
As the polymerizable monomer unit corresponding to the repeating unit of the general formula (I), as a sulfonic acid, imidic acid, or methide acid unit generated by leaving the cation of the cationic repeating unit (A) by irradiation with actinic rays or radiation, Examples are given below.

Next, general formula (II) will be described.
In the general formula (II), R ₂₁ , R ₂₂ and R ₂₃ have the same meanings as R ₁₁ , R ₁₂ and R ₁₃ in the general formula (I). Specific examples and preferred examples of each group include R ₁₁ , Examples thereof include the same groups as those described above for R ₁₂ and R ₁₃ .

X ₂₁ is —O—, —S—, —CO—, —SO ₂ —, —NR— (R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, or of these The group which combined 2 or more is represented.

In —NR—, the alkyl group represented by R is a linear or branched alkyl group which may have a substituent, and is the same as the alkyl group in R ₂₁ , R ₂₂ and R ₂₃ above. An example is given. R is particularly preferably a hydrogen atom, a methyl group or an ethyl group.

In addition, the divalent nitrogen-containing non-aromatic heterocyclic group means a non-aromatic heterocyclic group having at least one nitrogen atom, preferably 3 to 8 members. illustrated structure recited in _X 11 _{to X 13} in formula (I).

X ₂₁ is more preferably —O—, —CO—, —NR— (wherein R is a hydrogen atom or an alkyl group), or a combination of two or more of these, —COO—, —CONR— (R Is particularly preferably a hydrogen atom or an alkyl group.

L ₂₁ represents an alkylene group, an alkenylene group, a cycloalkylene group, or a group obtained by combining two or more thereof. In the combined group, the 2 or more groups combined may be different even in the same, also, -O as a linking group -, - S -, - CO -, - SO 2 -, - NR- (R Is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, a divalent aromatic ring group, or a combination of two or more thereof.

The alkylene group for L ₂₁ may be linear or branched, and examples thereof include 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. Is a preferred example. An alkylene group having 1 to 6 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is particularly preferable.
As the alkenylene group in any position of the alkylene group described above L _21, includes a group having a double bond.

  The cycloalkylene group may be monocyclic or polycyclic, for example, a carbon such as a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a norbornanylene group, an adamantylene group, or a diamantylene group. A cycloalkylene group having a number of 3 to 17 is a preferred example. A cycloalkylene group having 5 to 12 carbon atoms is more preferable, and a cycloalkylene group having 6 to 10 carbon atoms is particularly preferable.

Examples of the divalent aromatic ring group as the linking group include an arylene group optionally having a substituent having 6 to 14 carbon atoms such as a phenylene group, a tolylene group, and a naphthylene group, or a thiophene group, a furan group, and the like. , Pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole.
Specific examples of —NR— and the divalent nitrogen-containing non-aromatic heterocyclic group include the same specific examples as those described above for X ₂₁ , and preferred examples are also the same.

L ₂₁ is an alkylene group, a cycloalkylene group, or a group in which an alkylene group or a cycloalkylene group is combined through —OCO—, —O—, or —CONH— (for example, an -alkylene group-O-alkylene group, -Alkylene group-OCO-alkylene group-, -cycloalkylene group-O-alkylene group-, -alkylene group-CONH-alkylene group- and the like are particularly preferable.

X ₂₂ and X ₂₃ are each independently a single bond, —O—, —S—, —CO—, —SO ₂ —, —NR— (R is a hydrogen atom or an alkyl group), divalent nitrogen-containing non- It represents an aromatic heterocyclic group or a group obtained by combining two or more of these.
Specific examples of —NR— and divalent nitrogen-containing non-aromatic heterocyclic group in X ₂₂ and X ₂₃ are the same as those in X ₂₁ described above, and preferred examples are also the same.
X ₂₂ is more preferably a single bond, —S—, —O—, —CO—, —SO ₂ —, or a combination of two or more of these, a single bond, —S—, —OCO— , -OSO ₂ - are particularly preferred.
X ₂₃ is more preferably —O—, —CO—, —SO ₂ —, or a group obtained by combining two or more of these, and —OSO ₂ — is particularly preferred.

Ar ₂ represents a divalent aromatic ring group or a combination of a divalent aromatic ring group and an alkylene group.
The divalent aromatic ring group may have a substituent, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, a naphthylene group, or a thiophene, furan, pyrrole, benzo Preferred examples include divalent aromatic ring groups containing a heterocycle such as thiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole.

Preferred substituents in each of the above groups are alkyl groups, methoxy groups, ethoxy groups, hydroxyethoxy groups, propoxy groups, hydroxypropoxy groups, butoxy groups, etc., aryl groups such as phenyl groups, and the like mentioned for R _{21 to} R _23. Is mentioned.

  Examples of the group in which the divalent aromatic ring group and the alkylene group are combined include the above-described divalent aromatic ring group and, for example, 1 carbon atom such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. Preferred examples include aralkylene groups in which ˜8 alkylene groups (which may be linear or branched) are combined.

Ar ₂ is preferably an arylene group having 6 to 18 carbon atoms which may have a substituent, an aralkylene group in which an arylene group having 6 to 18 carbon atoms and an alkylene having 1 to 4 carbon atoms are combined, and a phenylene group A phenylene group substituted with a naphthylene group, a biphenylene group or a phenyl group is particularly preferred.

L ₂₂ represents an alkylene group, an alkenylene group, a cycloalkylene group, a divalent aromatic ring group, or a group in which two or more of these are combined, and these groups have a part or all of the hydrogen atoms being a fluorine atom, Substitution with a substituent selected from a fluorinated alkyl group, a nitro group, or a cyano group. In the combined group, the 2 or more groups combined may be different even in the same, also, -O as a linking group -, - S -, - CO -, - SO 2 -, - NR- (R Is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, or a group obtained by combining two or more thereof.

L ₂₂ includes an alkylene group, a divalent aromatic ring group, or two of them, in which part or all of the hydrogen atoms are substituted with a fluorine atom or a fluorinated alkyl group (more preferably a perfluoroalkyl group). A group obtained by combining the above is more preferable, and an alkylene group or a divalent aromatic ring group in which at least a part or all of the groups are substituted with a fluorine atom is particularly preferable. L ₂₂ is most preferably an alkylene group or a divalent aromatic ring group in which 30 to 100% of the number of hydrogen atoms are substituted with fluorine atoms.

The alkylene group for L ₂₂ may be linear or branched, and examples thereof include 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. The alkylene group is a preferred example. An alkylene group having 1 to 6 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is particularly preferable.
The alkenylene group includes a group having a double bond at an arbitrary position of the alkylene group.

The cycloalkylene group may be monocyclic or polycyclic, for example, a carbon such as a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a norbornanylene group, an adamantylene group, or a diamantylene group. A cycloalkylene group having a number of 3 to 17 is a preferred example.
Examples of the divalent aromatic ring group include the same groups as the specific examples given for the divalent aromatic ring group as the linking group in L ₂₁ described above.

Specific examples of the linking group —NR— and the divalent nitrogen-containing non-aromatic heterocyclic group in L ₂₂ include the same specific examples as in X ₂₁ described above, and preferred examples are also the same. Preferable specific examples of L ₂₂ include the structures exemplified for L ₁₂ in the general formula (I) described above.

Z ₂ is an anion site that forms an ion pair with the cation of the cationic repeating unit (A), and is dissociated from the cation by irradiation with an actinic ray or radiation to form a sulfonic acid group, an imido acid group, or a methido acid group. Represents the site. Z ₂ has the same meaning as _{Z 1} in the general formula (I), the above description of _{Z 1} is true for _{Z 2.}
As for the polymerizable monomer unit corresponding to the repeating unit of the general formula (II), as a sulfonic acid, imidic acid, or methide acid unit generated by leaving the cation of the cationic repeating unit (A) by irradiation with actinic rays or radiation, Examples are given below.

In addition, in another embodiment, the repeating unit (B) may be a repeating unit containing an aromatic ring in the side chain represented by other than the general formula (I) or (II).
As for the polymerizable monomer unit corresponding to such a repeating unit (B), as a sulfonic acid, an imidic acid, and a methide acid unit that are generated by detachment from the cation of the cationic repeating unit (A) by irradiation with actinic rays or radiation, Examples are given below.

  The anionic repeating unit (B) is also preferably represented by the general formula (III).

In the general formula (III), R ₃₁ , R ₃₂ and R ₃₃ have the same meaning as R ₁₁ , R ₁₂ and R ₁₃ in the general formula (I). Specific examples and preferred examples of each group include R ₁₁ , Examples thereof include the same groups as those described above for R ₁₂ and R ₁₃ .
The alkyl group is a linear or branched alkyl group which may have a substituent, preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, or n-butyl which may have a substituent. Group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, dodecyl group and the like, and an alkyl group having 20 or less carbon atoms, more preferably an alkyl group having 8 or less carbon atoms, particularly preferably 3 or less carbon atoms. Of the alkyl group.

As the alkyl group contained in the alkoxycarbonyl group, the same alkyl groups as those described above for R ₃₁ , R ₃₂ and R ₃₃ are preferable.

  Examples of the cycloalkyl group include monocyclic or polycyclic cycloalkyl groups which may have a substituent. Preferable examples include a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group which may have a substituent.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.

Preferred substituents that each of the above groups may have include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, an amide group, a sulfonamide group, and R _{21 to} R ₂₃ . Alkoxy groups, methoxy groups, ethoxy groups, hydroxyethoxy groups, propoxy groups, hydroxypropoxy groups, butoxy groups and other alkoxy groups, methoxycarbonyl groups, alkoxycarbonyl groups such as ethoxycarbonyl groups, formyl groups, acetyl groups, benzoyl groups, etc. An acyloxy group such as an acyl group, an acetoxy group, and a butyryloxy group, and a carboxy group. In particular, a hydroxyl group and a halogen atom are preferable.

R ₃₁ , R ₃₂ and R ₃₃ in the formula (III) are more preferably a hydrogen atom, an alkyl group or a halogen atom, a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (—CF ₃ ), a hydroxymethyl group. (—CH ₂ —OH), a chloromethyl group (—CH ₂ —Cl), and a fluorine atom (—F) are particularly preferred.

X ₃₁ and X ₃₂ each independently represent a single bond, —O—, —S—, —CO—, —SO ₂ —, —NR— (wherein R is a hydrogen atom or an alkyl group), divalent nitrogen-containing non- It represents an aromatic heterocyclic group or a group obtained by combining two or more of these.

In —NR—, the alkyl group represented by R is a linear or branched alkyl group which may have a substituent, and is the same as the alkyl group in R ₃₁ , R ₃₂ and R ₃₃ above. An example is given. R is particularly preferably a hydrogen atom, a methyl group or an ethyl group. In addition, the divalent nitrogen-containing non-aromatic heterocyclic group means a non-aromatic heterocyclic group having at least one nitrogen atom, preferably 3 to 8 members. illustrated structure recited in _X 11 _{to X 13} in formula (I).

X ₃₁ is more preferably a single bond, —O—, —CO—, —NR— (wherein R is a hydrogen atom or an alkyl group), or a group obtained by combining two or more of these, —COO—, —CONR -(R is a hydrogen atom or an alkyl group) is particularly preferable.

X ₃₂ is more preferably a single bond, —O—, —CO—, —SO ₂ —, a divalent nitrogen-containing non-aromatic heterocyclic group, or a group obtained by combining two or more thereof. , —OCO—, —OSO ₂ —, a combination of a divalent nitrogen-containing non-aromatic heterocyclic group and —SO ₂ — is particularly preferable.
L ₃₁ represents a single bond, an alkylene group, an alkenylene group, a cycloalkylene group, or a group obtained by combining two or more thereof. In the combined group, the 2 or more groups combined may be different even in the same, also, -O as a linking group -, - S -, - CO -, - SO 2 -, - NR- (R Is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, or a group obtained by combining two or more thereof.

The alkylene group for L ₃₁ may be linear or branched, and examples thereof include 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. Is a preferred example. An alkylene group having 1 to 6 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is particularly preferable.
As the alkenylene group in any position of the alkylene group described above L _31, includes a group having a double bond.

  The cycloalkylene group may be monocyclic or polycyclic, for example, a carbon such as a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a norbornanylene group, an adamantylene group, or a diamantylene group. A cycloalkylene group having a number of 3 to 17 is a preferred example. A cycloalkylene group having 5 to 12 carbon atoms is more preferable, and a cycloalkylene group having 6 to 10 carbon atoms is particularly preferable.

Specific examples of —NR— and the divalent nitrogen-containing non-aromatic heterocyclic group include the same specific examples as those described above for X ₃₁ , and preferred examples are also the same.

L ₃₁ represents a single bond, an alkylene group, a cycloalkylene group, or a group in which an alkylene group or a cycloalkylene group is combined through —OCO—, —O—, or —CONH— (for example, an —alkylene group —O-alkylene). Group-, -alkylene group-OCO-alkylene group-, -cycloalkylene group-O-alkylene group-, -alkylene group-CONH-alkylene group- and the like are particularly preferable.

L ₃₂ represents an alkylene group, an alkenylene group, a cycloalkylene group, or a group in which two or more of these are combined, and these groups are such that a part or all of the hydrogen atoms are fluorine atoms, fluorinated alkyl groups, nitro groups. Or a substituent selected from a cyano group. In the combined group, the 2 or more groups combined may be different even in the same, also, -O as a linking group -, - S -, - CO -, - SO 2 -, - NR- (R Is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, or a group obtained by combining two or more thereof.

L ₃₂ is more preferably an alkylene group in which part or all of the hydrogen atoms are substituted with a fluorine atom or a fluorinated alkyl group (more preferably a perfluoroalkyl group), and part or all of the hydrogen atoms are fluorine atoms. An alkylene group substituted with is particularly preferred. L ₃₂ is most preferably an alkylene group in which 30 to 100% of the number of hydrogen atoms are substituted with fluorine atoms.

The alkylene group for L ₃₂ may be linear or branched, and examples thereof include 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. The alkylene group is a preferred example. An alkylene group having 1 to 6 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is particularly preferable.
The alkenylene group includes a group having a double bond at an arbitrary position of the alkylene group.

The cycloalkylene group may be monocyclic or polycyclic, for example, a carbon such as a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a norbornanylene group, an adamantylene group, or a diamantylene group. A cycloalkylene group having a number of 3 to 17 is a preferred example.
Specific examples of the —NR— linking group and divalent nitrogen-containing non-aromatic heterocyclic group in L ₃₂ include the same specific examples as in X ₃₁ described above, and preferred examples are also the same.
Preferable specific examples of L ₃₂ include the structures exemplified for L ₁₂ in the general formula (I) described above.

Z ₃ is an anion site that forms an ion pair with the cation of the cationic repeating unit (A), and is dissociated from the cation by irradiation with an actinic ray or radiation to form a sulfonic acid group, an imido acid group, or a methido acid group. Represents the site. Z ₃ has the same meaning as _{Z 1} in the general formula (I), the above description of _{Z 1} is true for _{Z 3.}
About the polymerizable monomer unit corresponding to the anionic repeating unit represented by the general formula (III), a sulfonic acid, an imidic acid, which is generated by leaving from the cation of the cationic repeating unit (A) by irradiation with actinic rays or radiation, Examples of the methide acid unit are shown below.

  The polymerizable precursor corresponding to the anionic repeating unit (B) can be synthesized by using a general sulfonic acid esterification reaction or sulfonamidation reaction. For example, a method of selectively reacting one sulfonyl halide part of a bissulfonyl halide compound with an amine, alcohol, etc. to form a sulfonamide bond or a sulfonate ester bond, and then hydrolyzing the other sulfonyl halide part, Alternatively, lithium, sodium, potassium, and ammonium salts of organic acids, which are polymerizable precursors corresponding to the anionic repeating unit (B), can be obtained by a method of opening a cyclic sulfonic anhydride with an amine or alcohol. Also, US Pat. Fluorine Chem. 105 (2000) 129-136; Fluorine Chem. 116 (2002) 45-48 can also be easily synthesized.

Formation of an ion pair between the cation of the polymerizable precursor corresponding to the cationic repeating unit (A) and the anion of the polymerizable precursor corresponding to the anionic repeating unit (B) is performed by the anionic repeating unit synthesized above ( From the lithium, sodium and potassium salts of organic acids corresponding to B) and the precursors hydroxide, bromide, chloride and the like corresponding to the cationic repeating unit (A) synthesized above, Ions easily by using the salt exchange method described in JP-A No. 501909 or JP-A No. 2003-246786, or the salt exchange method described in JP-A No. 10-232490 or Japanese Patent No. 4025039. Pairs can be formed.
As described above, the monomer pair of the monomer corresponding to the cationic repeating unit (A) formed by ion pairing and the monomer corresponding to the anionic repeating unit (B) can be subjected to a polymerization reaction described later to form a resin (P ).

The content of the repeating units (A) and (B) in the resin (P) in the present invention is the resin monomer charge amount corresponding to the repeating units (A) and (B) during the synthesis of the resin (P). (P) The range of 0.5-50 mol% is preferable with respect to all polymerizable compounds at the time of synthesis, more preferably 1-40 mol%, and more preferably 2-30 mol%. Is more preferable.
In the resin (P) in the present invention, the content molar ratio or charging ratio of the repeating units (A) and (B) is preferably 20:80 to 80:20, and 30:70 to 70:30. It is more preferable that the ratio is 40:60 to 60:40.

[Repeating unit (C)]
In addition to the repeating units (A) and (B), the resin (P) is a repeating unit (C) that is decomposed by the action of an acid to generate an alkali-soluble group (hereinafter referred to as “a repeating unit having an acid-decomposable group”). ”).

  Alkali-soluble groups include phenolic hydroxyl groups, carboxyl groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (alkylsulfonyl) (alkylcarbonyl) imides. Group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group, etc. Is mentioned.

  Preferred alkali-soluble groups include phenolic hydroxyl groups, carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol), and sulfonic acid groups.

  A preferable group as the acid-decomposable group is a group obtained by substituting the hydrogen atom of these alkali-soluble groups with a group capable of leaving with an acid.

As the acid eliminable group, there can be, for _{example, -C (R 36) (R} 37) (R 38), - C (R 36) (R 37) (OR 39), - C (R 01) (R 02 ) (OR ₃₉ ) and the like.

In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, a monovalent aromatic ring group, a group in which an alkylene group and a monovalent aromatic ring group are combined, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.

R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a monovalent aromatic ring group, a group in which an alkylene group and a monovalent aromatic ring group are combined, or an alkenyl group.

The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. More preferably, it is a tertiary alkyl ester group.
As the repeating unit (C), a repeating unit represented by the following general formula (V) is more preferable.

In the general formula (V), R ₅₁ , R ₅₂ and R ₅₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₅₂ may be bonded to L ₅ to form a ring (preferably a 5-membered or 6-membered ring), in which case R ₅₂ represents an alkylene group.
L ₅ represents a single bond or a divalent linking group, and in the case of forming a ring with R ₅₂ , represents a trivalent linking group.
R ₅₄ represents an alkyl group, and R ₅₅ and R ₅₆ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or a monovalent aromatic ring group. R ₅₅ and R ₅₆ may combine with each other to form a ring. _However, no and _{R 55} and _{R 56} are hydrogen atoms at the same time.

The general formula (V) will be described in more detail.
As the alkyl group of R _{51 to} R ₅₃ in the general formula (V), a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, which may preferably have a substituent, Examples thereof include alkyl groups having 20 or less carbon atoms such as hexyl group, 2-ethylhexyl group, octyl group and dodecyl group, more preferably alkyl groups having 8 or less carbon atoms, and particularly preferably alkyl groups having 3 or less carbon atoms.

The alkyl group contained in the alkoxycarbonyl group is preferably the same as the alkyl group in the above R _{51 to} R ₅₃ .

The cycloalkyl group may be monocyclic or polycyclic. Preferable examples include a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group which may have a substituent.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.

  Preferred substituents in each of the above groups include, for example, alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, acyls. Group, acyloxy group, alkoxycarbonyl group, cyano group, nitro group and the like, and the substituent preferably has 8 or less carbon atoms.

When R ₅₂ is an alkylene group and forms a ring with L ₅ , the alkylene group is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, or an octylene group. Groups. An alkylene group having 1 to 4 carbon atoms is more preferable, and an alkylene group having 1 to 2 carbon atoms is particularly preferable.

R ₅₁ and R ₅₃ in Formula (V) are more preferably a hydrogen atom, an alkyl group, or a halogen atom, and a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (—CF ₃ ), a hydroxymethyl group (—CH ₃ ). _2- OH), a chloromethyl group (—CH ₂ —Cl), and a fluorine atom (—F) are particularly preferable. R ₅₂ is more preferably a hydrogen atom, an alkyl group, a halogen atom, or an alkylene group (forming a ring with L ₅ ), a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (—CF ₃ ), a hydroxymethyl group Particularly preferred are (—CH ₂ —OH), a chloromethyl group (—CH ₂ —Cl), a fluorine atom (—F), a methylene group (forms a ring with L ₅ ), and an ethylene group (forms a ring with L ₅ ). .

Examples of the divalent linking group represented by L _5, an alkylene group, a divalent aromatic ring _{group, -COO-L 1 -, -} O-L 1 -, a group formed by combining two or more of these Etc. Here, L ₁ represents an alkylene group, a cycloalkylene group, a divalent aromatic ring group, or a group in which an alkylene group and a divalent aromatic ring group are combined.
Examples of the trivalent linking group as L ₅ in the case of forming a ring with R ₅₂ include a group formed by removing any one hydrogen atom from the above examples of the above divalent linking group.

L ₅ is preferably a single bond, a group represented by —COO—L ₁ —, or a divalent aromatic ring group.

The alkyl group for R _{54 to} R ₅₆ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Particularly preferred are those having 1 to 4 carbon atoms such as a group, an isobutyl group and a t-butyl group.

The cycloalkyl group represented by R ₅₅ and R _56, preferably one having 3 to 20 carbon atoms, cyclopentyl, may be of monocyclic and cyclohexyl group, norbornyl group, adamantyl group, Polycyclic ones such as a tetracyclodecanyl group and a tetracyclododecanyl group may be used.

The ring formed by combining R ₅₅ and R ₅₆ with each other preferably has 3 to 20 carbon atoms, and may be monocyclic such as a cyclopentyl group or a cyclohexyl group, or a norbornyl group. A polycyclic group such as an adamantyl group, a tetracyclodecanyl group, or a tetracyclododecanyl group. When R ₅₅ and R ₅₆ are bonded to each other to form a ring, R ₅₄ is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group.

The monovalent aromatic ring groups represented by R ₅₅ and _{R 56,} preferably has 6 to 20 carbon atoms, for example, a phenyl group, a naphthyl group, and the like. When one of R ₅₅ and R ₅₆ is a hydrogen atom, the other is preferably a monovalent aromatic ring group.

R ₅₅ and R ₅₆ in general formula (V) are each independently more preferably a hydrogen atom, an alkyl group, or a cycloalkyl group.

As a method for synthesizing a monomer corresponding to the repeating unit represented by the general formula (V), a general method for synthesizing a polymerizable group-containing ester can be applied and is not particularly limited.
Specific examples of the repeating unit (C) are shown below, but the present invention is not limited thereto. In specific examples, Rx and Xa ₁ represent a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Rxa and Rxb each represents an alkyl group having 1 to 4 carbon atoms. Z represents a substituent containing a polar group, and when there are a plurality of them, each is independent. Specifically, a polar group itself such as a hydroxyl group, a cyano group, an amino group, an alkylamide group or a sulfonamide group, or It represents a linear or branched alkyl group or cycloalkyl group. p represents 0 or a positive integer.

  The repeating unit (C) may be a repeating unit represented by the following general formula (VI).

In general formula (VI), R ₆₁ , R ₆₂ and R ₆₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₆₂ may be bonded to Ar ₆ to form a ring (preferably a 5-membered or 6-membered ring), in which case R ₆₂ represents an alkylene group.
X ₆ represents a single bond, —COO—, —CONR ₆₄ — (R ₆₄ represents a hydrogen atom or an alkyl group).
Ar ₆ represents an (n + 1) -valent aromatic ring group, and when forming a ring with R ₆₂ , represents an (n + 2) -valent aromatic ring group. Y each independently represents a hydrogen atom or a group capable of leaving by the action of an acid. When n is an integer of 2 or more, a plurality of Y may be the same as or different from each other. However, at least one of Y represents a group capable of leaving by the action of an acid. n represents an integer of 1 to 4.

General formula (VI) will be described in more detail.
As the alkyl group of R _{61 to} R ₆₃ in the general formula (VI), a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, which may preferably have a substituent, Examples thereof include alkyl groups having 20 or less carbon atoms such as hexyl group, 2-ethylhexyl group, octyl group, and dodecyl group, and more preferable examples include alkyl groups having 8 or less carbon atoms.

As the alkyl group contained in the alkoxycarbonyl group, the same alkyl groups as those described above for R _{61 to} R ₆₃ are preferable.

The cycloalkyl group may be monocyclic or polycyclic, and is preferably a monocyclic type having 3 to 8 carbon atoms such as a cyclopropyl group, cyclopentyl group or cyclohexyl group which may have a substituent. A cycloalkyl group is mentioned.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is more preferable.

If R ₆₂ represents an alkylene group, the alkylene group, preferably a methylene group which may have a substituent group, an ethylene group, a propylene group, butylene group, hexylene group, 1 to 8 carbon atoms such as octylene Can be mentioned.
X ₆ represents a single bond, —COO—, —CONR ₆₄ — (R ₆₄ represents a hydrogen atom or an alkyl group). _Examples of the alkyl group for R ₆₄ include the same as the alkyl groups for R _{61 to} R ₆₃ .
X ₆ is preferably a single bond, —COO—, or —CONH—, and more preferably a single bond or —COO—.

The (n + 1) -valent or (n + 2) -valent aromatic ring group for Ar ₆ may have a substituent, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, a naphthylene group, Or, for example, an arbitrary hydrogen atom is removed from a divalent aromatic ring group containing a heterocycle such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole, etc. As a preferred example,

Examples of the substituent that the above-described alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group and divalent aromatic ring group may have include the groups represented by R _{51 to} R ₅₃ in the above general formula (V). Specific examples similar to the substituents that may be included are listed.

n is preferably 1 or 2, and more preferably 1.
n Y's each independently represent a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one of n represents a group capable of leaving by the action of an acid.
Examples of the group Y leaving by the action of an acid include —C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —C (═O) —O—C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ). _{), - C (R 01)} (R 02) (OR 39), - C (R 01) (R 02) -C (= O) -O-C (R 36) (R 37) (R 38), —CH (R ₃₆ ) (Ar) and the like can be mentioned.

In the formula, R _{36 to} R ₃₉ each independently represent an alkyl group, a cycloalkyl group, a monovalent aromatic ring group, a group in which an alkylene group and a monovalent aromatic ring group are combined, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.

R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a monovalent aromatic ring group, a group in which an alkylene group and a monovalent aromatic ring group are combined, or an alkenyl group. Ar represents a monovalent aromatic ring group.

The alkyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkyl group having 1 to 8 carbon atoms, such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl. Group, octyl group and the like.

The cycloalkyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ may be monocyclic or polycyclic. The monocyclic type is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. As the polycyclic type, a cycloalkyl group having 6 to 20 carbon atoms is preferable. For example, an adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group, tetracyclododecyl group. Group, androstanyl group and the like. A part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

The monovalent aromatic ring group of R _{36 to} R ₃₉ , R ₀₁ , R ₀₂ and Ar is preferably a monovalent aromatic ring group having 6 to 10 carbon atoms, for example, an aryl such as a phenyl group, a naphthyl group or an anthryl group. And a divalent aromatic ring group containing a heterocyclic ring such as a group, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole.

The group in which the alkylene group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ and the monovalent aromatic ring group are combined is preferably an aralkyl group having 7 to 12 carbon atoms, such as benzyl group, phenethyl group, naphthylmethyl. Groups and the like.

The alkenyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.

The ring formed by combining R ₃₆ and R ₃₇ with each other may be monocyclic or polycyclic. The monocyclic type is preferably a cycloalkyl structure having 3 to 8 carbon atoms, and examples thereof include a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, a cyclohexane structure, a cycloheptane structure, and a cyclooctane structure. As the polycyclic type, a cycloalkyl structure having 6 to 20 carbon atoms is preferable, and examples thereof include an adamantane structure, a norbornane structure, a dicyclopentane structure, a tricyclodecane structure, and a tetracyclododecane structure. A part of carbon atoms in the cycloalkyl structure may be substituted with a hetero atom such as an oxygen atom.

Each of the groups as R _{36 to} R ₃₉ , R ₀₁ , R ₀₂ and Ar may have a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, and an amino group. Amide group, ureido group, urethane group, hydroxyl group, carboxyl group, halogen atom, alkoxy group, thioether group, acyl group, acyloxy group, alkoxycarbonyl group, cyano group, nitro group, etc. The number of carbon atoms is preferably 8 or less.
As the group Y leaving by the action of an acid, a structure represented by the following general formula (VI-A) is more preferable.

Here, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a monovalent aromatic ring group, or a group in which an alkylene group and a monovalent aromatic ring group are combined.
M represents a single bond or a divalent linking group.
Q represents an alkyl group, a cycloalkyl group which may contain a hetero atom, a monovalent aromatic ring group which may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group or an aldehyde group.
At least two of Q, M, and L ₁ may combine to form a ring (preferably a 5-membered or 6-membered ring).

The alkyl group as L ₁ and L ₂ is, for example, an alkyl group having 1 to 8 carbon atoms, specifically, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl. Preferred examples include a group and an octyl group.

The cycloalkyl group as L ₁ and L ₂ is, for example, a cycloalkyl group having 3 to 15 carbon atoms. Specifically, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and the like are preferable examples. Can do.

The monovalent aromatic ring group as L ₁ and L ₂ is, for example, an aryl group having 6 to 15 carbon atoms. Specifically, a phenyl group, a tolyl group, a naphthyl group, an anthryl group and the like are preferable examples. Can be mentioned.

Group formed by combining an alkylene group and a monovalent aromatic ring group represented by L ₁ and L ₂ are, for example, a 7 to 20 carbon atoms, a benzyl group, an aralkyl group such as a phenethyl group.

The divalent linking group as M is, for example, an alkylene group (for example, methylene group, ethylene group, propylene group, butylene group, hexylene group, octylene group, etc.), cycloalkylene group (for example, cyclopentylene group, cyclohexylene group). Group, adamantylene group, etc.), alkenylene group (for example, vinylene group, propenylene group, butenylene group, etc.), divalent aromatic ring group (for example, phenylene group, tolylene group, naphthylene group, etc.), -S-, -O _{-, - CO -, - SO} 2 -, - N (R 0) -, and a divalent linking group formed by combining a plurality of these. R ₀ is a hydrogen atom or an alkyl group (for example, an alkyl group having 1 to 8 carbon atoms, specifically, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group). Octyl group, etc.).

The alkyl group as Q is the same as each group as L ₁ and L ₂ described above.
In the cycloalkyl group which may contain a hetero atom as Q and the monovalent aromatic ring group which may contain a hetero atom, an aliphatic hydrocarbon ring group which does not contain a hetero atom and a hetero atom Examples of the monovalent aromatic ring group that does not include the above-described cycloalkyl groups as L ₁ and L ₂ , and monovalent aromatic ring groups, preferably 3 to 15 carbon atoms.

  Examples of the cycloalkyl group containing a hetero atom and the monovalent aromatic ring group containing a hetero atom include thiirane, cyclothiolane, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, Groups having a heterocyclic structure such as thiadiazole, thiazole, pyrrolidone and the like can be mentioned, but if they are structures generally called heterocycles (rings formed from carbon and heteroatoms, or rings formed from heteroatoms), these It is not limited to.

Q, M, as a ring which may be formed by combining at least two L _1, Q, M, by combining at least two L _1, for example, a propylene group, to form a butylene group, an oxygen atom The case where a 5-membered or 6-membered ring containing is formed is mentioned.

Each group represented by L ₁ , L ₂ , M, and Q in the general formula (VI-A) may have a substituent, for example, R _{36 to} R ₃₉ , R ₀₁ , R ₀₂ described above. And those described as the substituent that Ar may have, and the carbon number of the substituent is preferably 8 or less.

  The group represented by -MQ is preferably a group composed of 1 to 30 carbon atoms, more preferably a group composed of 5 to 20 carbon atoms.

  Specific examples of the repeating unit represented by formula (VI) are shown below as preferred specific examples of the repeating unit (C), but the present invention is not limited thereto.

In the resin (P) of the present invention, the repeating unit (C) is more preferably a repeating unit represented by the general formula (V) or (VI), but is a repeating unit represented by the general formula (V). It is particularly preferred.
The content of the repeating unit (C) in the resin (P) of the present invention is the total polymerization at the time of resin (P) synthesis as the charged amount of the polymerizable compound corresponding to the repeating unit (C) at the time of resin (P) synthesis. Preferably it is in the range of 3 to 90 mol%, more preferably in the range of 5 to 80 mol%, particularly preferably in the range of 7 to 70 mol% with respect to the active compound.

[Repeating unit (D)]
When the composition of the present invention is irradiated with KrF excimer laser light, electron beam, X-ray or high-energy light beam (for example, EUV) having a wavelength of 50 nm or less, this resin is represented by the general formula (VID). It preferably has a repeating unit (D). Since the repeating unit represented by the general formula (VID) has an alkali-soluble group, the alkali-solubility of the resin can be assisted. Further, the pattern strength can be improved, and further, a function of controlling the Tg of a film formed using the composition of the present invention can be imparted.

In the above general formula, R ₀₁ , R ₀₂ and R ₀₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
R ₀₃ represents an alkylene group and may be bonded to X or Ar ₀₁ to form a 5-membered or 6-membered ring together with the main chain —C—C— chain.
Ar ₀₁ represents an aromatic ring group.
n01 represents an integer of 1 to 4. n01 is preferably 1 or 2, and more preferably 1.
X represents a single bond or a divalent linking group.
Examples of the divalent linking group for X include an alkylene group, a cycloalkylene group, an arylene group, —COO—, —OCO—, —CO—, —O—, —S—, —S (═O) —, — Examples thereof include a group selected from any one selected from the group consisting of S (═O) ₂ —, —OS (═O) ₂ —, and —NH—, or a combination of two or more thereof.

The alkylene for X is preferably a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and examples thereof include a methylene group, an ethylene group, and a propylene group.
As a cycloalkylene group about X, Preferably it is C3-C20, More preferably, it is C3-C10, for example, a 1, 4- cyclohexylene group etc. are mentioned.
In the alkylene group and cycloalkylene group for X, part or all of the hydrogen atoms bonded to carbon may be substituted with a substituent.
The arylene group for X is preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 10 carbon atoms (for example, phenylene or naphthylene), and part or all of hydrogen atoms bonded to carbon. May be substituted with a substituent.

  Examples of the substituent that the alkylene group, cycloalkylene group, and arylene group for X may have include, for example, a halogen group such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a methoxy group, an ethoxy group, and a tert- Alkoxy groups such as butoxy group; aryloxy groups such as phenoxy group and p-tolyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group and butoxycarbonyl group; aryloxycarbonyl groups such as phenoxycarbonyl group and p-tolyloxycarbonyl group; Acyloxy groups such as acetoxy group, propionyloxy group, benzoyloxy group; acyl groups such as acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, methoxalyl group; methylsulfanyl group, tert-butylsulfanyl group, etc. Kirsulfanyl group; arylsulfanyl group such as phenylsulfanyl group and p-tolylsulfanyl group; alkyl such as methylamino group and cyclohexylamino group or cycloalkylamino group, dialkyl such as dimethylamino group, diethylamino group, morpholino group and piperidino group Aryl group such as amino group, phenylamino group, p-tolylamino group, alkyl group such as methyl group, ethyl group, tert-butyl group, dodecyl group, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl Group, anthryl group, aryl group such as phenanthryl group, etc., hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, perfluoro Alkyl group, trialkyl Lil group, and the like.

The alkyl group as R _{01 to} R ₀₃ is, for example, an alkyl group having 20 or less carbon atoms, and preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a hexyl group. , 2-ethylhexyl group, octyl group or dodecyl group. More preferably, these alkyl groups are alkyl groups having 8 or less carbon atoms. In addition, these alkyl groups may have a substituent.

The alkyl group contained in the alkoxycarbonyl group is preferably the same as the alkyl group in R _{01 to} R ₀₃ described above.
The cycloalkyl group may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. Preferably, a C3-C8 monocyclic cycloalkyl group, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, is mentioned. In addition, these cycloalkyl groups may have a substituent.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is more preferable.
When R ₀₃ represents an alkylene group, the alkylene group is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and an octylene group.
The aromatic ring group as Ar ₀₁ preferably has 6 to 14 carbon atoms, and examples thereof include a benzene ring, a toluene ring and a naphthalene ring. In addition, these aromatic ring groups may have a substituent.
Specific examples of the repeating unit represented by the general formula (VI) are shown below. However, it is not limited to these.

  When the resin (P) contains the repeating unit (D), the charge amount of the polymerizable compound corresponding to the repeating unit (D) represented by the general formula (VID) during the synthesis of the resin (P) is P) It is preferably in the range of 20 to 90 mol%, more preferably in the range of 30 to 80 mol%, based on the total polymerizable compound at the time of synthesis.

[Repeating unit (E)]
The resin (P) preferably further has a repeating unit (E) having a group that decomposes under the action of an alkali developer and increases the dissolution rate in the alkali developer.
Examples of the group that decomposes by the action of an alkali developer and increases the dissolution rate in the alkali developer include a lactone structure and a phenyl ester structure.
As the repeating unit (E), a repeating unit represented by the following general formula (AII) is more preferable.

In general formula (AII),
Rb ₀ represents a hydrogen atom, a halogen atom or an optionally substituted alkyl group (preferably having 1 to 4 carbon atoms).
Preferable substituents that the alkyl group of Rb ₀ may have include a hydroxyl group and a halogen atom. Examples of the halogen atom for Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb ₀ is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic cycloalkylene group, an ether group, an ester group, a carbonyl group, or a divalent linking group obtained by combining these. Ab is preferably a single bond or a divalent linking group represented by —Ab ₁ —CO ₂ —.
Ab ₁ is a linear or branched alkylene group, a monocyclic or polycyclic cycloalkylene group, and preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group.

  V represents a group that decomposes under the action of an alkali developer and increases the dissolution rate in the alkali developer. A group having an ester bond is preferable, and a group having a lactone structure is more preferable.

  As the group having a lactone structure, any group having a lactone structure can be used, but a 5- to 7-membered ring lactone structure is preferable, and a bicyclo structure or a spiro structure is added to the 5- to 7-membered ring lactone structure. Those in which other ring structures are condensed in the form to be formed are preferred. It is more preferable to have a repeating unit having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-17). The lactone structure may be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), and (LC1-14).

The lactone structure portion may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, and a carboxyl group. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. More preferably, they are a C1-C4 alkyl group, a cyano group, and an acid-decomposable group. n ₂ represents an integer of 0-4. When n ₂ is 2 or more, a plurality of substituents (Rb ₂ ) may be the same or different, and a plurality of substituents (Rb ₂ ) may be bonded to form a ring. .

  The repeating unit having a lactone group usually has an optical isomer, but any optical isomer may be used. One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, the optical purity (ee) thereof is preferably 90% or more, more preferably 95% or more.

When the resin (P) contains the repeating unit (E), the amount of the polymerizable compound corresponding to the repeating unit (E) at the time of synthesizing the resin (P) is the total polymerizable compound at the time of synthesizing the resin (P). In contrast, the range of 1 to 60 mol% is preferable, the range of 2 to 50 mol% is more preferable, and the range of 5 to 40 mol% is more preferable. One type of repeating unit (E) may be used, or two or more types may be used in combination. By using a specific lactone structure, line edge roughness and development defects are improved.
Although the specific example of the repeating unit (E) in resin (P) is shown below, this invention is not limited to this. In the formula, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

[Repeating unit (F)]
The resin (P) of the present invention may have a repeating unit (F) having an alkali-soluble group in addition to the repeating unit (D). Examples of the alkali-soluble group include a phenolic hydroxyl group, a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol (for example, hexafluoroisopropanol group) substituted at the α-position with an electron-withdrawing group. .
Specific examples of the repeating unit having an alkali-soluble group other than the repeating unit (D) are shown below, but the present invention is not limited thereto.
In specific examples, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

  When the resin (P) in the present invention has a repeating unit (F), the charge amount of the polymerizable compound corresponding to the repeating unit (F) during the synthesis of the resin (P) is the resin (P) synthesis. 1-50 mol% is preferable with respect to all the polymeric compounds at the time, More preferably, it is 3-40 mol%, More preferably, it is 5-35 mol%.

[Other repeat units]
Resin (P) is a repeating unit other than the repeating units described above, and may further have a repeating unit having a hydroxyl group or a cyano group. As a result, substrate adhesion and developer compatibility can be improved. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, and preferably has no acid-decomposable group. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is preferably an adamantyl group, a diamantyl group, or a norbornyl group. As the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, partial structures represented by the following general formulas (VIIa) to (VIId) are preferable.

In the general formulas (VIIa) to (VIIc), R ₂ c to R ₄ c each independently represents a hydrogen atom, a hydroxyl group, or a cyano group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group or a cyano group. Preferably, one or two of R ₂ c to R ₄ c are a hydroxyl group and the rest are hydrogen atoms. In general formula (VIIa), more preferably, _two of R ₂ c to R ₄ c are a hydroxyl group and the rest are hydrogen atoms.

  Examples of the repeating unit having a partial structure represented by the general formulas (VIIa) to (VIId) include the repeating units represented by the following general formulas (AIIa) to (AIId).

In the general formulas (AIIa) to (AIId), R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
R ₂ c to R ₄ c are in the general formula (VIIa) ~ _(VIIc), same meanings as R 2 c~R ₄ c.

When the resin (P) has a repeating unit having a hydroxyl group or a cyano group, the charge amount of the polymerizable compound corresponding to the repeating unit having a hydroxyl group or a cyano group at the time of synthesis of the resin (P) is the resin (P) synthesis. 5-40 mol% is preferable with respect to all the polymeric compounds at the time, More preferably, it is 5-30 mol%.
Specific examples of the repeating unit having a hydroxyl group or a cyano group are given below, but the present invention is not limited thereto.

  The resin (P) of the present invention can further have a repeating unit that has an alicyclic hydrocarbon structure having no polar group and does not exhibit acid decomposability. An example of such a repeating unit is a repeating unit represented by the general formula (VII).

In general formula (VII), R ₅ represents a hydrocarbon group having at least one hydrocarbon structure and having no polar group (hydroxyl group, cyano group, etc.).
Ra represents a hydrogen atom, an alkyl group, or a —CH ₂ —O—Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group, or an acyl group. Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.

The hydrocarbon group for R ₅ preferably has a cyclic structure therein. Specific examples of the cyclic structure include monocyclic or polycyclic cycloalkyl groups (preferably having 3 to 12 carbon atoms, more preferably 3 to 7 carbon atoms), monocyclic or polycyclic cycloalkenyl groups (having 3 to 12 carbon atoms). ), An aryl group (preferably having 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms), an aralkyl group (preferably having 7 to 20 carbon atoms, more preferably 7 to 12 carbon atoms), and the like.
Examples of the monocyclic cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like. Examples of the cycloalkyl group having 3 to 12 carbon atoms and the monocyclic cycloalkenyl group include a cyclohexenyl group. Especially, it is a C3-C7 monocyclic cycloalkyl group, More preferably, a cyclopentyl group and a cyclohexyl group are mentioned.

The polycyclic hydrocarbon group includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group, and examples of the ring assembly hydrocarbon group include a bicyclohexyl group and a perhydronaphthalenyl group. As the bridged cyclic hydrocarbon ring, for example, bicyclic such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) Hydrocarbon rings and tricyclic hydrocarbon rings such as homobredan, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [4.3.1.1 ^2,5 ] undecane ring, tetracyclo [ 4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring. The bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, perhydroindene. A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings such as a phenalene ring are condensed is also included.

Preferred examples of the bridged cyclic hydrocarbon ring include a norbornyl group, an adamantyl group, a bicyclooctanyl group, a tricyclo [5,2,1,0 ^2,6 ] decanyl group, and the like. More preferable examples of the bridged cyclic hydrocarbon ring include a norbornyl group and an adamantyl group.

  These hydrocarbon groups may have a substituent, and preferred substituents include a halogen atom, an alkyl group, a hydroxyl group protected with a protecting group, an amino group protected with a protecting group, and the like. Preferred halogen atoms include bromine, chlorine and fluorine atoms, and preferred alkyl groups include methyl, ethyl, butyl and t-butyl groups. The above alkyl group may further have a substituent, and examples of the substituent that may further have a halogen atom, an alkyl group, a hydroxyl group protected with a protective group, and an amino group protected with a protective group Can be mentioned.

  Examples of the protecting group include an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkyloxycarbonyl group. Preferred alkyl groups include alkyl groups having 1 to 4 carbon atoms, preferred substituted methyl groups include methoxymethyl, methoxythiomethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl groups, and preferred substituted ethyl groups. 1-ethoxyethyl, 1-methyl-1-methoxyethyl, preferred acyl groups include formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, pivaloyl groups, etc., aliphatic acyl groups having 1 to 6 carbon atoms, alkoxycarbonyl Examples of the group include an alkoxycarbonyl group having 1 to 4 carbon atoms.

  Resin (P) has a hydrocarbon structure having no polar group and may or may not contain a repeating unit that does not exhibit acid decomposability, but has a hydrocarbon structure having no polar group, When a repeating unit that does not exhibit acid-decomposability is contained, the amount of the polymerizable compound that corresponds to the repeating unit that has a hydrocarbon structure having no polar group and does not exhibit acid-decomposability during the synthesis of the resin (P) Is preferably from 1 to 40 mol%, more preferably from 1 to 20 mol%, based on the total polymerizable compound during the synthesis of the resin (P).

Specific examples of the repeating unit having a hydrocarbon structure not having a polar group and not exhibiting acid decomposability are listed below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

  The resin (P) of the present invention has, in addition to the above repeating structural units, dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general required properties of resist, resolving power, heat resistance, sensitivity. Various repeating structural units can be included for the purpose of adjusting the etc.

Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to the following monomers.
Thereby, performance required for the resin used in the composition of the present invention, in particular,
(1) Solubility in coating solvent,
(2) Film formability (glass transition point),
(3) Alkali developability,
(4) Membrane slip (hydrophobic, alkali-soluble group selection),
(5) Adhesion of unexposed part to substrate,
(6) Dry etching resistance,
Etc. can be finely adjusted.

As such a monomer, for example, addition polymerization selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonic acid esters, etc. Examples include compounds having one unsaturated bond.
In addition, any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating structural units may be copolymerized.

  In the resin (P) used in the composition of the present invention, the molar ratio of each repeating structural unit is the resist dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general resist performance required. It is appropriately set to adjust the resolving power, heat resistance, sensitivity and the like.

The form of the resin (P) of the present invention may be any of random type, block type, comb type, and star type.
The resin (P) can be synthesized, for example, by radical, cation, or anionic polymerization of an unsaturated monomer corresponding to each structure. It is also possible to obtain the desired resin by conducting a polymer reaction after polymerization using an unsaturated monomer corresponding to the precursor of each structure.
In particular, the above-described monomer pair of the monomer corresponding to the cationic repeating unit (A) formed with an ion pair and the monomer corresponding to the anionic repeating unit (B) can be used as the unsaturated monomer. .

  For example, as a general synthesis method, an unsaturated monomer and a polymerization initiator are dissolved in a solvent, and a batch polymerization method in which polymerization is performed by heating, a solution of an unsaturated monomer and a polymerization initiator in a heating solvent for 1 to 10 hours. The dropping polymerization method etc. which are dropped and added over are mentioned, and the dropping polymerization method is preferable.

  Examples of the solvent used for the polymerization include a solvent that can be used in preparing the actinic ray-sensitive or radiation-sensitive resin composition described below, and more preferably the composition of the present invention. Polymerization is preferably carried out using the same solvent as used in the above. Thereby, generation | occurrence | production of the particle at the time of a preservation | save can be suppressed.

  The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis (2-methylpropionate) and the like. If necessary, the polymerization may be performed in the presence of a chain transfer agent (for example, alkyl mercaptan).

The reaction concentration is 5 to 70% by mass, preferably 10 to 50% by mass. The reaction temperature is usually from 10 ° C to 150 ° C, preferably from 30 ° C to 120 ° C, more preferably from 40 ° C to 100 ° C.
The reaction time is usually 1 to 48 hours, preferably 1 to 24 hours, more preferably 1 to 12 hours.

  After completion of the reaction, the mixture is allowed to cool to room temperature and purified. Purification can be accomplished by a liquid-liquid extraction method that removes residual monomers and oligomer components by combining water and an appropriate solvent, and a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less. , Reprecipitation method that removes residual monomer by coagulating resin in poor solvent by dripping resin solution into poor solvent and purification in solid state such as washing filtered resin slurry with poor solvent A normal method such as a method can be applied. For example, the resin is precipitated as a solid by contacting a solvent (poor solvent) in which the resin is hardly soluble or insoluble in a volume amount of 10 times or less, preferably 10 to 5 times that of the reaction solution.

  The solvent (precipitation or reprecipitation solvent) used in the precipitation or reprecipitation operation from the polymer solution may be a poor solvent for the polymer, and may be a hydrocarbon, halogenated hydrocarbon, nitro, depending on the type of polymer. A compound, ether, ketone, ester, carbonate, alcohol, carboxylic acid, water, a mixed solvent containing these solvents, and the like can be appropriately selected for use. Among these, as a precipitation or reprecipitation solvent, a solvent containing at least an alcohol (particularly methanol or the like) or water is preferable.

  The amount of the precipitation or reprecipitation solvent used can be appropriately selected in consideration of efficiency, yield, and the like, but generally 100 to 10000 parts by mass, preferably 200 to 2000 parts by mass with respect to 100 parts by mass of the polymer solution, More preferably, it is 300-1000 mass parts.

  The temperature for precipitation or reprecipitation can be appropriately selected in consideration of efficiency and operability, but is usually about 0 to 50 ° C., preferably around room temperature (for example, about 20 to 35 ° C.). The precipitation or reprecipitation operation can be performed by a known method such as a batch method or a continuous method using a conventional mixing vessel such as a stirring tank.

  The precipitated or re-precipitated polymer is usually subjected to conventional solid-liquid separation such as filtration and centrifugation, and dried before use. Filtration is performed using a solvent-resistant filter medium, preferably under pressure. Drying is performed at a temperature of about 30 to 100 ° C., preferably about 30 to 50 ° C. under normal pressure or reduced pressure (preferably under reduced pressure).

  In addition, after depositing and separating the resin once, it may be dissolved again in a solvent, and the resin may be brought into contact with a hardly soluble or insoluble solvent. That is, after completion of the radical polymerization reaction, a solvent in which the polymer is hardly soluble or insoluble is brought into contact, the resin is precipitated (step a), the resin is separated from the solution (step b), and the resin solution A is dissolved again in the solvent. (Step c), and then, the resin solution A is brought into contact with a solvent in which the resin is hardly soluble or insoluble in a volume amount that is less than 10 times that of the resin solution A (preferably 5 times or less). This may be a method including precipitating a resin solid (step d) and separating the precipitated resin (step e).

  The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like. If desired, an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is 5 to 50% by mass, preferably 10 to 30% by mass. The reaction temperature is usually from 10 ° C to 150 ° C, preferably from 30 ° C to 120 ° C, more preferably from 60 ° C to 100 ° C.

  The molecular weight of the resin (P) according to the present invention is not particularly limited, but the weight average molecular weight is preferably in the range of 1000 to 100,000, more preferably in the range of 1500 to 60000, and in the range of 2000 to 45000. It is particularly preferred. By setting the weight average molecular weight in the range of 1000 to 100,000, it is possible to prevent heat resistance and dry etching resistance from being deteriorated, and also to prevent developability from being deteriorated and the film forming property from being deteriorated due to increased viscosity. be able to. Here, the weight average molecular weight of the resin indicates a molecular weight in terms of polystyrene measured by GPC (carrier: THF or N-methyl-2-pyrrolidone (NMP)).

  The dispersity (Mw / Mn) is preferably 1.00 to 5.00, more preferably 1.03 to 3.50, and still more preferably 1.05 to 2.50. The smaller the molecular weight distribution, the better the resolution and the resist shape, and the smoother the side wall of the resist pattern, the better the roughness.

Resin (P) of this invention can be used individually by 1 type or in combination of 2 or more types. The content of the resin (P) is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, based on the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. 70-100 mass% is especially preferable.
Although the more preferable specific example of resin (P) is shown below, this invention is not limited to these. In addition, P-1 to P-43 described later are also given as specific examples.

  The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may further include a basic compound, a resin that decomposes by the action of an acid to increase the dissolution rate in an aqueous alkaline solution, and a conventional photoacid generator. An agent, a surfactant, an acid-decomposable dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a dissolution promoting compound for a developer, a compound having a proton acceptor functional group, and the like can be contained.

<Basic compound>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a basic compound.
The basic compound is preferably a nitrogen-containing organic basic compound.

Although the basic compound which can be used is not specifically limited, For example, the compound classified into the following (1)-(4) is used preferably.
(1) Compound represented by the following general formula (BS-1)

In general formula (BS-1),
Each R is independently a hydrogen atom, an alkyl group (straight or branched), a cycloalkyl group (monocyclic or polycyclic), a monovalent aromatic ring group, an alkylene group and a monovalent aromatic ring group Represents any of the groups. However, not all three Rs are hydrogen atoms.

  Although carbon number of the alkyl group as R is not specifically limited, Usually, 1-20, Preferably it is 1-12.

  Although carbon number of the cycloalkyl group as R is not specifically limited, Usually, 3-20, Preferably it is 5-15.

  Although carbon number of the monovalent | monohydric aromatic ring group as R is not specifically limited, Usually, 6-20, Preferably it is 6-10. Specifically, aryl groups, such as a phenyl group and a naphthyl group, are mentioned.

  Although carbon number of the group which combined the alkylene group and monovalent | monohydric aromatic ring group as R is not specifically limited, Usually, 7-20, Preferably it is 7-11. Specific examples include aralkyl groups such as a benzyl group.

  In the alkyl group, cycloalkyl group, monovalent aromatic ring group, or group in which the alkylene group and the monovalent aromatic ring group are combined as R, a hydrogen atom may be substituted with a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, a monovalent aromatic ring group, a group in which an alkylene group and a monovalent aromatic ring group are combined, a hydroxyl group, a carboxyl group, an alkoxy group, an aryloxy group, Examples thereof include an alkylcarbonyloxy group and an alkyloxycarbonyl group.

  In the compound represented by the general formula (BS-1), it is preferable that only one of three Rs is a hydrogen atom, or all Rs are not hydrogen atoms.

  Specific examples of the compound of the general formula (BS-1) include tri-n-butylamine, tri-n-pentylamine, tri-n-octylamine, tri-n-decylamine, triisodecylamine, dicyclohexylmethylamine, Tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, didecylamine, methyloctadecylamine, dimethylundecylamine, N, N-dimethyldodecylamine, methyldioctadecylamine, N, N-dibutylaniline, N, N- Examples include dihexylaniline, 2,6-diisopropylaniline, 2,4,6-tri (t-butyl) aniline.

  In addition, a compound in which at least one R in the general formula (BS-1) is an alkyl group substituted with a hydroxyl group can be mentioned as one of preferable embodiments. Specific examples of the compound include triethanolamine and N, N-dihydroxyethylaniline.

The alkyl group as R may have an oxygen atom in the alkyl chain, and an oxyalkylene chain may be formed. As the oxyalkylene chain, —CH ₂ CH ₂ O— is preferable. Specific examples include tris (methoxyethoxyethyl) amine and compounds exemplified in column 3, line 60 and thereafter of US Pat. No. 6,040,112.

(2) Compound having a nitrogen-containing heterocyclic structure The heterocyclic structure may or may not have aromaticity. Moreover, you may have two or more nitrogen atoms, Furthermore, you may contain hetero atoms other than nitrogen. Specifically, compounds having an imidazole structure (2-phenylbenzimidazole, 2,4,5-triphenylimidazole, etc.), compounds having a piperidine structure (N-hydroxyethylpiperidine, bis (1,2,2,6) , 6-pentamethyl-4-piperidyl) sebacate), compounds having a pyridine structure (such as 4-dimethylaminopyridine), and compounds having an antipyrine structure (such as antipyrine and hydroxyantipyrine).

  A compound having two or more ring structures is also preferably used. Specific examples include 1,5-diazabicyclo [4.3.0] non-5-ene and 1,8-diazabicyclo [5.4.0] -undec-7-ene.

(3) Amine compound having a phenoxy group An amine compound having a phenoxy group has a phenoxy group at the terminal opposite to the nitrogen atom of the alkyl group of the amine compound. The phenoxy group is, for example, a substituent such as an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryloxy group. You may have.

More preferably, it is a compound having at least one oxyalkylene chain between the phenoxy group and the nitrogen atom. The number of oxyalkylene chains in one molecule is preferably 3-9, more preferably 4-6. Among the oxyalkylene chains, —CH ₂ CH ₂ O— is preferable.

  Specific examples include 2- [2- {2- (2,2-dimethoxy-phenoxyethoxy) ethyl} -bis- (2-methoxyethyl)]-amine and US Patent Application Publication No. 2007/0224539. The compounds (C1-1) to (C3-3) exemplified in paragraph [0066] of the above.

(4) Ammonium salt An ammonium salt is also used as appropriate. Preferred is hydroxide or carboxylate. More specifically, tetraalkylammonium hydroxide represented by tetrabutylammonium hydroxide is preferable.

  In addition, compounds synthesized in Examples of JP-A No. 2002-363146, compounds described in paragraph 0108 of JP-A No. 2007-298869, and the like can also be used.

A basic compound is used individually or in combination of 2 or more types.
The usage-amount of a basic compound is 0.001-10 mass% normally on the basis of the total solid of actinic-ray-sensitive or radiation-sensitive resin composition, Preferably it is 0.01-5 mass%.

  The molar ratio of acid generator / basic compound is preferably 2.5 to 300. That is, the molar ratio is preferably 2.5 or more from the viewpoints of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to pattern thickening over time until post-exposure heat treatment. This molar ratio is more preferably 5.0 to 200, and still more preferably 7.0 to 150.

  The acid generator in the above molar ratio is the total amount of the repeating units (A) and (B) contained in the resin (P) and the acid generator other than the resin (P) described later.

<Resin that decomposes by the action of an acid and increases the dissolution rate in an aqueous alkali solution>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may contain, in addition to the resin (P), a resin that decomposes by the action of an acid and increases the dissolution rate in an alkaline aqueous solution.

  Resins that decompose due to the action of an acid and increase the dissolution rate in an alkaline aqueous solution (hereinafter also referred to as “acid-decomposable resins”) are not included in the main chain or side chain of the resin, or both of the main chain and side chain. It is a resin having a group (acid-decomposable group) that decomposes by the action of and produces an alkali-soluble group. Among these, a resin having an acid-decomposable group in the side chain is more preferable.

  The acid-decomposable resin is decomposed with an acid into an alkali-soluble resin as disclosed in European Patent No. 254853, JP-A-2-25850, JP-A-3-223860, JP-A-4-251259, and the like. It can be obtained by reacting a precursor of a group capable of being reacted or copolymerizing an alkali-soluble resin monomer having an acid-decomposable group bonded thereto with various monomers.

  As the acid-decomposable group, for example, in a resin having an alkali-soluble group such as —COOH group and —OH group, a group in which the hydrogen atom of the alkali-soluble group shown on the left is substituted with a group capable of leaving by the action of an acid is preferable.

  Specifically, the acid-decomposable group is preferably the same group as the acid-decomposable group described in the above-described resin of the present invention (for example, the acid-decomposable group described as the repeating unit (C) in the resin (P)). As an example.

  The resin having an alkali-soluble group is not particularly limited. For example, poly (o-hydroxystyrene), poly (m-hydroxystyrene), poly (p-hydroxystyrene) and copolymers thereof, hydrogenated poly (Hydroxystyrene), poly (hydroxystyrene) s having a substituent represented by the following structure, and resins having phenolic hydroxyl groups, styrene-hydroxystyrene copolymers, α-methylstyrene-hydroxystyrene copolymers, hydrogen An alkali-soluble resin having a hydroxystyrene structural unit such as a modified novolak resin, and an alkali-soluble resin containing a repeating unit having a carboxyl group such as (meth) acrylic acid or norbornenecarboxylic acid.

  The alkali dissolution rate of these alkali-soluble resins is preferably at least 170 kg / second as measured with 2.38 mass% tetramethylammonium hydroxide (TMAH) (23 ° C.). Particularly preferably, it is 330 Å / second or more.

  The content of the group capable of decomposing with an acid is the number of repeating units (X) having a group decomposable with an acid in the resin and the number of repeating units having an alkali-soluble group not protected with a group capable of leaving with an acid. With (Y), it is represented by X / (X + Y). The content is preferably 0.01 to 0.7, more preferably 0.05 to 0.50, and still more preferably 0.05 to 0.40.

  The weight average molecular weight of the acid-decomposable resin is preferably 50,000 or less, more preferably 1,000 to 20,000, and particularly preferably 1,000 to 10,000 as a polystyrene conversion value by the GPC method.

  The dispersity (Mw / Mn) of the acid-decomposable resin is preferably 1.0 to 3.0, more preferably 1.05 to 2.0, and still more preferably 1.1 to 1.7.

  Two or more acid-decomposable resins may be used in combination.

  In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the compounding amount in the composition of the acid-decomposable resin excluding the resin (P) is preferably 0 to 70% by mass in the total solid content of the composition, More preferably, it is 0-50 mass%, More preferably, it is 0-30 mass%.

<Acid generator>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a resin (P) having a photoacid-generating structure. In addition to the resin (P), from the viewpoint of improving sensitivity, A low molecular weight compound that generates an acid upon irradiation with radiation (hereinafter, also referred to as “acid generator”) may be contained.

  Examples of such an acid generator include a photoinitiator for photocationic polymerization, a photoinitiator for radical photopolymerization, a photodecolorant for dyes, a photochromic agent, or an actinic ray or radiation used for a microresist. A known compound that generates an acid by irradiation and a mixture thereof can be appropriately selected and used.

  Examples thereof include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates. Specific examples thereof include those described in [0164] to [0248] of US Patent Application Publication No. 2008 / 0241737A1.

  In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, when an acid generator is used in addition to the resin (P) having a photoacid generating structure, the acid generator is used alone or in combination of two. The above can be used in combination. The content of the acid generator in the composition is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, and still more preferably 0 to 7% by mass, based on the total solid content of the composition of the present invention. is there. The acid generator is not an essential component in the present invention, but is usually used in an amount of 0.01% by mass or more in order to obtain the effect of addition.

<Low molecular compound (D) having a group capable of leaving by the action of an acid>
As the low molecular compound (D) having a group capable of leaving by the action of an acid, a commercially available product or a compound synthesized by a known method may be used.
Moreover, the low molecular weight compound (D) is preferably an amine derivative having a group on the nitrogen atom that is eliminated by the action of an acid.

  The low molecular compound (D) may have a carbamate group having a protective group on the nitrogen atom. The protecting group constituting the carbamate group can be represented by the following general formula (d-1).

In general formula (d-1),
R ′ each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, an aryl group, an aralkyl group, or an alkoxyalkyl group. R ′ may be bonded to each other to form a ring.
R ′ is preferably a linear or branched alkyl group, cycloalkyl group, or aryl group. More preferably, it is a linear or branched alkyl group or cycloalkyl group.

A low molecular compound (D) can also be comprised by combining arbitrarily the structure represented by the said basic compound and general formula (d-1).
It is particularly preferable that the low molecular compound (D) has a structure represented by the following general formula (A).
The low molecular compound (D) may correspond to the above basic compound as long as it is a low molecular compound having a group capable of leaving by the action of an acid.

In the general formula (A), Ra independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When n = 2, the two Ras may be the same or different, and the two Ras are bonded to each other to form a divalent heterocyclic hydrocarbon group (preferably having 20 or less carbon atoms) or a derivative thereof. May be formed.
Rb independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. However, in -C (Rb) (Rb) (Rb), when one or more Rb is a hydrogen atom, at least one of the remaining Rb is a cyclopropyl group or a 1-alkoxyalkyl group.
At least two Rb's may combine to form an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group or a derivative thereof.
n represents an integer of 0 to 2, m represents an integer of 1 to 3, and n + m = 3.

In general formula (A), the alkyl group, cycloalkyl group, aryl group and aralkyl group represented by Ra and Rb are functional groups such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group and an oxo group, It may be substituted with an alkoxy group or a halogen atom.
The alkyl group, cycloalkyl group, aryl group or aralkyl group of Ra and Rb (these alkyl group, cycloalkyl group, aryl group and aralkyl group may be substituted with the above functional group, alkoxy group or halogen atom). )as,
For example, a group derived from a linear or branched alkane such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, etc., a group derived from these alkanes, for example, A group substituted with one or more cycloalkyl groups such as a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group,
Groups derived from cycloalkanes such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornane, adamantane, noradamantane, groups derived from these cycloalkanes, for example, methyl group, ethyl group, n-propyl group, a group substituted with one or more linear or branched alkyl groups such as i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like,
Groups derived from aromatic compounds such as benzene, naphthalene, anthracene, etc., and groups derived from these aromatic compounds are, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2 A group substituted with one or more linear or branched alkyl groups such as -methylpropyl group, 1-methylpropyl group, t-butyl group, and the like;
Groups derived from heterocyclic compounds such as pyrrolidine, piperidine, morpholine, tetrahydrofuran, tetrahydropyran, indole, indoline, quinoline, perhydroquinoline, indazole, benzimidazole, and groups derived from these heterocyclic compounds are linear or branched A group substituted with one or more groups derived from an alkyl group or aromatic compound, a group derived from a linear or branched alkane, a group derived from a cycloalkane, a phenyl group, a naphthyl group A group substituted with one or more groups derived from an aromatic compound such as an anthracenyl group or the like, or the above substituent is a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, an oxo group And a group substituted with a functional group such as.

Examples of the divalent heterocyclic hydrocarbon group (preferably having 1 to 20 carbon atoms) or a derivative thereof formed by bonding of Ra to each other include, for example, pyrrolidine, piperidine, morpholine, 1, 4, 5 , 6-tetrahydropyrimidine, 1,2,3,4-tetrahydroquinoline, 1,2,3,6-tetrahydropyridine, homopiperazine, 4-azabenzimidazole, benzotriazole, 5-azabenzotriazole, 1H-1, 2,3-triazole, 1,4,7-triazacyclononane, tetrazole, 7-azaindole, indazole, benzimidazole, imidazo [1,2-a] pyridine, (1S, 4S)-(+)-2 , 5-diazabicyclo [2.2.1] heptane, 1,5,7-triazabicyclo [4.4.0] dec-5-ene Groups derived from heterocyclic compounds such as indole, indoline, 1,2,3,4-tetrahydroquinoxaline, perhydroquinoline, 1,5,9-triazacyclododecane, groups derived from these heterocyclic compounds A group derived from a linear or branched alkane, a group derived from a cycloalkane, a group derived from an aromatic compound, a group derived from a heterocyclic compound, a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group And a group substituted with one or more functional groups such as a morpholino group and an oxo group.
Although the particularly preferable low molecular compound (D) in the present invention is specifically shown, the present invention is not limited thereto.

  The compound represented by the general formula (A) can be easily synthesized from a commercially available amine by a method described in Protective Groups in Organic Synthesis Fourth Edition. As the most general method, there is a method obtained by reacting a dicarbonate or haloformate with a commercially available amine. In the formula, X represents a halogen atom. Ra and Rb are synonymous with Ra and Rb in the general formula (A), respectively.

  In the present invention, the low molecular compound (D) having a group capable of leaving by the action of an acid can be used singly or in combination of two or more.

  In the present invention, the amount of the low molecular compound (D) having a group capable of leaving by the action of an acid is usually 0.001 to 20 mass based on the total solid content of the composition combined with the basic compound. %, Preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass.

  The use ratio in the composition of the low molecular compound (D) having a group capable of leaving by the action of an acid and an acid is as follows: acid generator / [low molecular compound having a group capable of leaving by the action of an acid (D) + Basic compound] (molar ratio) = 2.5 to 300 is preferable. In other words, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to the thickening of the resist pattern over time until post-exposure heat treatment. The acid generator / [low molecular compound (D) having a group capable of leaving by the action of an acid + the basic compound] (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150. It is.

<Hydrophobic resin>
When the film comprising the composition according to the present invention is exposed through an immersion medium, a hydrophobic resin can be further added to the actinic ray-sensitive or radiation-sensitive resin composition as necessary. . As a result, when the hydrophobic resin is unevenly distributed on the surface layer of the film and the immersion medium is water, the receding contact angle of the resist film surface with respect to the water when the film is formed can be improved, and the immersion liquid followability can be improved. . As the hydrophobic resin, any resin can be used as long as the receding contact angle on the surface can be improved by addition, but a resin having at least one of a fluorine atom and a silicon atom is preferable. The receding contact angle of the film is preferably 60 ° to 90 °, more preferably 70 ° or more. The hydrophobic resin is unevenly distributed at the interface as described above, but unlike the surfactant, it does not necessarily have a hydrophilic group in the molecule and contributes to uniform mixing of polar / nonpolar substances. It is not necessary.

The receding contact angle is a contact angle measured when the contact line at the droplet-substrate interface recedes, and is useful for simulating the ease of movement of the droplet in a dynamic state. It is generally known. In simple terms, it can be defined as the contact angle when the droplet interface recedes when the droplet discharged from the needle tip is deposited on the substrate and then sucked into the needle again. It can be measured by using a contact angle measuring method generally called an expansion / contraction method.
In the immersion exposure process, the immersion head needs to move on the wafer following the movement of the exposure head to scan the wafer at high speed to form the exposure pattern. In this case, the contact angle of the immersion liquid with respect to the resist film is important, and the resist is required to follow the high-speed scanning of the exposure head without remaining droplets.

  The fluorine atom or silicon atom in the hydrophobic resin may be present in the main chain of the resin or may be substituted with a side chain.

The hydrophobic resin is preferably a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom.
The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and further a fluorine atom It may have a substituent other than.
The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom.
Examples of the aryl group having a fluorine atom include those in which at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom. .

  Preferred examples of the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, and the aryl group having a fluorine atom include groups represented by the following general formulas (F2) to (F4). The present invention is not limited to this.

In general formulas (F2) to (F4),
R _{57 to} R ₆₈ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group (straight or branched). Provided that at least one of R _{57 to} R ₆₁ , at least one of R _{62 to} R ₆₄ , and at least one of R _{65 to} R ₆₈ are each independently a fluorine atom or at least one hydrogen atom is a fluorine atom. It represents a substituted alkyl group (preferably having 1 to 4 carbon atoms). R _{57 to} R ₆₁ and R _{65 to} R ₆₇ are preferably all fluorine atoms. R ₆₂ , R ₆₃ and R ₆₈ are preferably an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Further preferred. R ₆₂ and R ₆₃ may be connected to each other to form a ring.

Specific examples of the group represented by the general formula (F2) include a p-fluorophenyl group, a pentafluorophenyl group, and a 3,5-di (trifluoromethyl) phenyl group.
Specific examples of the group represented by the general formula (F3) include trifluoromethyl group, pentafluoropropyl group, pentafluoroethyl group, heptafluorobutyl group, hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2 -Methyl) isopropyl group, nonafluorobutyl group, octafluoroisobutyl group, nonafluorohexyl group, nonafluoro-t-butyl group, perfluoroisopentyl group, perfluorooctyl group, perfluoro (trimethyl) hexyl group, 2,2 , 3,3-tetrafluorocyclobutyl group, perfluorocyclohexyl group and the like. Hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2-methyl) isopropyl group, octafluoroisobutyl group, nonafluoro-t-butyl group and perfluoroisopentyl group are preferable, and hexafluoroisopropyl group and heptafluoroisopropyl group are preferable. Further preferred.
Specific examples of the group represented by the general formula (F4) include, for example, —C (CF ₃ ) ₂ OH, —C (C ₂ F ₅ ) ₂ OH, —C (CF ₃ ) (CH ₃ ) OH, -CH _(CF 3) OH and the like, -C _{(CF 3)} 2 OH is preferred.

Furthermore, the hydrophobic resin may have at least one group selected from the following groups (x) to (z).
(X) an alkali-soluble group (y) a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer (z) a group that decomposes by the action of an acid

  Examples of the alkali-soluble group (x) include phenolic hydroxyl group, carboxylic acid group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) ( Alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) ) And a methylene group. Preferred alkali-soluble groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and bis (alkylcarbonyl) methylene groups.

The repeating unit having an alkali-soluble group (x) includes a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or a main group of the resin via a linking group. Examples include a repeating unit in which an alkali-soluble group is bonded to the chain. Furthermore, a polymerization initiator or a chain transfer agent having an alkali-soluble group can be introduced at the end of the polymer chain at the time of polymerization. Is also preferable.
The content of the repeating unit having an alkali-soluble group (x) is preferably from 1 to 50 mol%, more preferably from 3 to 35 mol%, still more preferably from 5 to 20 mol%, based on all repeating units in the hydrophobic resin. .

Examples of the group (y) that decomposes by the action of an alkali developer and increases the solubility in the alkali developer include a group having a lactone structure, an acid anhydride group, an acid imide group, and the like, and preferably a lactone A group having a structure.
As the repeating unit having a group (y) that is decomposed by the action of an alkali developer and increases the solubility in the alkali developer, an alkali is added to the main chain of the resin, such as a repeating unit of an acrylate ester or a methacrylate ester. A polymerization initiator having a repeating unit to which a group (y) that is decomposed by the action of the developer and increases the solubility in an alkali developer is bonded, or a group (y) that increases the solubility in an alkali developer And a chain transfer agent used at the time of polymerization are preferably introduced at the end of the polymer chain.
The content of the repeating unit having a group (y) that increases the solubility in an alkali developer is preferably 1 to 40 mol%, more preferably 3 to 30 mol%, based on all repeating units in the hydrophobic resin. Preferably it is 5-15 mol%.

  Specific examples of the repeating unit having a group (y) whose solubility in an alkali developer increases can be the same as the repeating unit having a lactone structure described for the resin (P).

  Examples of the repeating unit having a group (z) capable of decomposing by the action of an acid in the hydrophobic resin include the same repeating units having an acid-decomposable group as described for the resin (P). In the hydrophobic resin, the content of the repeating unit having a group (z) that decomposes by the action of an acid is preferably from 1 to 80 mol%, more preferably from 10 to 80 mol, based on all repeating units in the hydrophobic resin. %, More preferably 20 to 60 mol%.

  The hydrophobic resin may further have a repeating unit represented by the following general formula (IIIc).

In general formula (IIIc):
R _c31 represents a hydrogen atom, an alkyl group, or an alkyl group _optionally substituted with fluorine, a cyano group, or a —CH ₂ —O—Rac ₂ group. In the formula, Rac ₂ represents a hydrogen atom, an alkyl group or an acyl group. R _c31 is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.
R _c32 represents a group having an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group or an aryl group. These groups may be substituted with a group containing a silicon atom or a fluorine atom.
L _c3 represents a single bond or a divalent linking group.

In general formula (IIIc), the alkyl group represented by R _c32 is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.
The cycloalkyl group for R _c32 is preferably a cycloalkyl group having 3 to 20 carbon atoms.
The alkenyl group for R _c32 is preferably an alkenyl group having 3 to 20 carbon atoms.
The cycloalkenyl group for R _c32 is preferably a cycloalkenyl group having 3 to 20 carbon atoms.
The aryl group for R _c32 is preferably an aryl group having 6 to 20 carbon atoms, and particularly preferably a phenyl group.
R _c32 is preferably an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom.
The divalent linking group of L _c3 is preferably an ester bond, an alkylene group (preferably having a carbon number of 1 to 5), an ether bond, a phenylene group, or a divalent linking group in which two or more of these are combined.
It is also preferable that the hydrophobic resin further has a repeating unit represented by the following general formula (CII-AB).

In the formula (CII-AB),
R _c11 ′ and R _c12 ′ each independently represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group.
Z′c represents an atomic group for forming an alicyclic structure containing two bonded carbon atoms (C—C).

  When the hydrophobic resin has a fluorine atom, the content of the fluorine atom is preferably 5 to 80% by mass and more preferably 10 to 80% by mass with respect to the weight average molecular weight of the hydrophobic resin. Moreover, it is preferable that the repeating unit containing a fluorine atom is 10-100 mol% in all the repeating units of hydrophobic resin, and it is more preferable that it is 30-100 mol%.

The weight average molecular weight in terms of standard polystyrene of the hydrophobic resin is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 15,000.
Moreover, the hydrophobic resin may be used alone or in combination.
The content of the hydrophobic resin in the composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass with respect to the total solid content in the composition of the present invention. 5 mass% is still more preferable.

  The hydrophobic resin, like the above-mentioned acid-decomposable resin, naturally has few impurities such as metals, and it is preferable that the residual monomer and oligomer components are as close to zero as possible. Specifically, it is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and even more preferably 0 to 1% by mass. Thereby, a resist composition having no change over time such as foreign matter in liquid or sensitivity can be obtained. The molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 5, more preferably 1 to 3, and still more preferably from the viewpoints of resolution, resist shape, resist pattern sidewall, roughness, and the like. It is the range of 1-2.

  As the hydrophobic resin, various commercially available products can be used, and synthesis and purification can be performed according to a conventional method (for example, radical polymerization). For details of the synthesis and purification method, refer to the description in Chapter 2 “Polymer Synthesis” of “5th edition Experimental Chemistry Course 26 Polymer Chemistry” published by Maruzen Co., Ltd.

  Specific examples of the hydrophobic resin include a resin having a silicon atom described in paragraphs 0172 to 0253 of US2008 / 030543A1, and a resin having a fluorine atom shown below.

<Organic solvent>
Solvents that can be used when preparing the actinic ray-sensitive or radiation-sensitive resin composition by dissolving the above components include, for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate Esters, alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 10 carbon atoms), monoketone compounds which may contain rings (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates, alkyl pyruvates, etc. Mention may be made of organic solvents.

  Examples of the alkylene glycol monoalkyl ether carboxylate include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl Preferred examples include ether propionate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate.

  Preferred examples of the alkylene glycol monoalkyl ether include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether.

  Preferred examples of the alkyl lactate include methyl lactate, ethyl lactate, propyl lactate and butyl lactate.

  Preferable examples of the alkyl alkoxypropionate include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-methoxypropionate.

  Examples of cyclic lactones include β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone, γ-caprolactone, and γ-octano. Preferred are iclactone and α-hydroxy-γ-butyrolactone.

  Examples of the monoketone compound which may contain a ring include 2-butanone, 3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 2 -Methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2-hexanone, 3-hexanone, 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5-hexen-2-one, -Penten-2-one, cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone, cyclohexanone, 3-methyl Cyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone, 3-methylcyclo A preferred example is heptanone.

Preferred examples of the alkylene carbonate include propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate.
Examples of the alkyl alkoxyacetate include 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, 3-methoxy-3-methylbutyl acetate, and 1-methoxy-acetate. 2-propyl is preferred.
Preferred examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.

Preferred solvents that can be used include 2-heptanone, cyclopentanone, γ-butyrolactone, cyclohexanone, butyl acetate, ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 3-ethoxypropionic acid Examples include ethyl, ethyl pyruvate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, and propylene carbonate. Particularly preferred solvents include propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether.
In the present invention, the above solvents may be used alone or in combination of two or more.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a solvent having a normal pressure (760 mmHg) and a boiling point of 150 ° C. or lower.
The said solvent may be used independently and may use 2 or more types together. Moreover, you may use together the solvent whose boiling point exceeds 150 degreeC at a normal pressure. In the composition of the present invention, the content of the solvent having a boiling point of 150 ° C. or less is preferably 50% by mass or more, and more preferably 65% by mass or more based on the total amount of the solvent. Most preferably, it is 70 mass%-100 mass%.
The solvent having a boiling point of 150 ° C. or lower preferably has a boiling point of 50 to 150 ° C., more preferably 80 to 150 ° C.

The solvent having a boiling point of 150 ° C. or lower is preferably an organic solvent, and may contain, for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, alkyl alkoxypropionate, cyclic lactone, or ring. It can be selected from organic solvents such as good monoketone compounds, alkylene carbonates, alkyl alkoxyacetates and alkyl pyruvates.
For example, a solvent having a boiling point of 150 ° C. or lower at normal pressure is selected from the solvents shown below, and used alone or in combination of two or more, and further, a solvent having a boiling point of higher than 150 ° C. at normal pressure. be able to.

Examples of the alkylene glycol monoalkyl ether carboxylate include propylene glycol monomethyl ether acetate (PGMEA; 1-methoxy-2-acetoxypropane) (bp = 146 ° C.), propylene glycol monoethyl ether acetate (bp). = 164-165 ° C.), propylene glycol monopropyl ether acetate (bp = 173-174 ° C./740 mmHg), ethylene glycol monomethyl ether acetate (bp = 143 ° C.), ethylene glycol monoethyl ether acetate (b P. = 156 ° C.).
Examples of the alkylene glycol monoalkyl ether include propylene glycol monomethyl ether (PGME; 1-methoxy-2-propanol) (bp = 119 ° C.), propylene glycol monoethyl ether (bp = 130-131 ° C.). ), Propylene glycol monopropyl ether (bp = 148 ° C.), propylene glycol monobutyl ether (bp = 169-170 ° C.), ethylene glycol monomethyl ether (bp = 124-125 ° C.), ethylene Preferred examples include glycol monoethyl ether (bp = 134-135 ° C.).

  Examples of the alkyl lactate ester include methyl lactate (bp = 145 ° C.), ethyl lactate (bp = 154 ° C.), propyl lactate (bp = 169-172 ° C.), butyl lactate (b (P. = 185-187 ° C.).

  Examples of the alkyl alkoxypropionate include, for example, ethyl 3-ethoxypropionate (bp = 169-170 ° C.), methyl 3-ethoxypropionate (bp = 138-141 ° C.), 3-methoxypropionic acid Preferred is ethyl (bp = 156-158 ° C.).

  Examples of the cyclic lactone include β-propiolactone (bp = 162 ° C.), β-butyrolactone (bp = 71-73 ° C./29 mmHg), and γ-butyrolactone (bp = 204−). 205 ° C.), α-methyl-γ-butyrolactone (bp = 78-81 ° C./10 mmHg), β-methyl-γ-butyrolactone (bp = 87-88 ° C./10 mmHg), γ-valerolactone (Bp = 82-85 ° C./10 mmHg), γ-caprolactone (bp = 219 ° C.), γ-octanoic lactone (bp = 234 ° C.), α-hydroxy-γ-butyrolactone (Bp = 133 ° C./10 mmHg) is preferable.

  Examples of the monoketone compound that may contain a ring include 2-butanone (bp = 80 ° C.), 3-methylbutanone (bp = 94-95 ° C.), pinacolone (bp == 106 ° C), 2-pentanone (bp = 101-105 ° C), 3-pentanone (bp = 102 ° C), 3-methyl-2-pentanone (bp = 118 ° C), 4 -Methyl-2-pentanone (bp = 117-118 ° C.), 2-methyl-3-pentanone (bp = 113 ° C.), 4,4-dimethyl-2-pentanone (bp == 125-130 ° C.), 2,4-dimethyl-3-pentanone (bp = 124 ° C.), 2,2,4,4-tetramethyl-3-pentanone (bp = 152-153 ° C.) 2-hexanone (bp = 127 ° C.), 3-hexanone (bp) 123 ° C.), 5-methyl-2-hexanone (bp = 145 ° C.), 2-heptanone (bp = 149-150 ° C.), 3-heptanone (bp = 146-148 ° C.) 4-heptanone (bp = 145 ° C.), 2-methyl-3-heptanone (bp = 158-160 ° C.), 5-methyl-3-heptanone (bp = 161-162 ° C.) ), 2,6-dimethyl-4-heptanone (bp = 165-170 ° C.), 2-octanone (bp = 173 ° C.), 3-octanone (bp = 167-168 ° C.) 2-nonanone (bp = 192 ° C./743 mmHg), 3-nonanone (bp = 187-188 ° C.), 5-nonanone (bp = 186-187 ° C.), 2-decanone ( bp = 211 ° C.), 3-decanone (bp = 204−). 05 ° C.), 4-decanone (bp = 206-207 ° C.), 5-hexen-2-one (bp = 128-129 ° C.), 3-penten-2-one (bp) = 121-124 ° C), cyclopentanone (bp = 130-131 ° C), 2-methylcyclopentanone (bp = 139 ° C), 3-methylcyclopentanone (bp == 145 ° C.), 2,2-dimethylcyclopentanone (bp = 143-145 ° C.), 2,4,4-trimethylcyclopentanone (bp = 160 ° C.), cyclohexanone (bp). = 157 ° C.), 3-methylcyclohexanone (bp = 169-170 ° C.), 4-methylcyclohexanone (bp = 169-171 ° C.), 4-ethylcyclohexanone (bp = 192-194). ° C), 2,2-dimethyl Cyclohexanone (b. p. = 169-170 ° C), 2,6-dimethylcyclohexanone (bp = 174-176 ° C), 2,2,6-trimethylcyclohexanone (bp = 178-179 ° C), cycloheptanone (b Preferred examples include 2-methylcycloheptanone (bp = 182-185 ° C.) and 3-methylcycloheptanone (bp = 100 ° C./40 mmHg).

  Examples of the alkylene carbonate include propylene carbonate (bp = 240 ° C.), vinylene carbonate (bp = 162 ° C.), ethylene carbonate (bp = 243-244 ° C./740 mmHg), butylene carbonate ( (b.p. = 88 / 0.8 mmHg.degree. C.)).

  Examples of the alkyl alkoxyacetate include, for example, 2-methoxyethyl acetate (bp = 145 ° C.), 2-ethoxyethyl acetate (bp = 155-156 ° C.), acetic acid-2- (2-ethoxy Preferred are ethoxy) ethyl (bp = 219 ° C.) and 1-methoxy-2-propyl acetate (bp = 145-146 ° C.).

  As the alkyl pyruvate, for example, methyl pyruvate (bp = 134-137 ° C.), ethyl pyruvate (bp = 144 ° C.), and propyl pyruvate (bp = 166 ° C.) are preferable. Can be mentioned.

  Preferred solvents that can be used include 2-heptanone, cyclopentanone, γ-butyrolactone, cyclohexanone, butyl acetate, ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 3-ethoxypropionic acid Examples include ethyl, ethyl pyruvate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, and propylene carbonate. From the viewpoint of reducing outgas, 2-heptanone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl A solvent having a boiling point at atmospheric pressure of 150 ° C. or lower, such as ether, is particularly preferable.

  The amount of the solvent used in the total amount of the composition of the present invention (including those having a boiling point of 150 ° C. or higher) can be appropriately adjusted according to the desired film thickness, etc. The total solid content concentration of the composition is 0.5-30% by mass, preferably 1.0-20% by mass, more preferably 1.5-10% by mass.

<Surfactant>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may or may not further contain a surfactant. As the surfactant, fluorine-based and / or silicon-based surfactants are preferable.

  Surfactants corresponding to these include Megafac F176, Megafac R08 manufactured by Dainippon Ink and Chemicals, PF656, PF6320 manufactured by OMNOVA, Troisol S-366 manufactured by Troy Chemical, Sumitomo 3M Examples include Fluorad FC430 manufactured by Co., Ltd., polysiloxane polymer KP-341 manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

  Further, other surfactants other than fluorine-based and / or silicon-based surfactants can also be used. More specific examples include polyoxyethylene alkyl ethers and polyoxyethylene alkyl aryl ethers.

  In addition, known surfactants can be used as appropriate. Examples of the surfactant that can be used include those described in [0273] et seq. Of US Patent Application Publication No. 2008/0248425.

Surfactants may be used alone or in combination of two or more.
When a surfactant is contained in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the surfactant content is preferably relative to the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. Is 0.0001 to 2% by mass, more preferably 0.001 to 1% by mass.

<Acid-decomposable dissolution inhibiting compound>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is a dissolution inhibiting compound having a molecular weight of 3000 or less (hereinafter referred to as “dissolution inhibiting compound”) that decomposes by the action of an acid and increases the dissolution rate in an alkali developer. May also be included).

  The dissolution inhibiting compound is preferably an alicyclic or aliphatic compound containing an acid-decomposable group, such as a cholic acid derivative containing an acid-decomposable group described in Proceeding of SPIE, 2724, 355 (1996). . Examples of the acid-decomposable group and alicyclic structure are the same as those described for the acid-decomposable resin.

When the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is irradiated with an electron beam or EUV light, it preferably contains a structure in which the phenolic hydroxyl group of the phenol compound is substituted with an acid-decomposable group. The phenol compound preferably contains 1 to 9 phenol skeletons, more preferably 2 to 6 phenol skeletons.
The molecular weight of the dissolution inhibiting compound in the present invention is 3000 or less, preferably 300 to 3000, and more preferably 500 to 2500.
<Dye>
Suitable dyes include oily dyes and basic dyes.

  In order to improve the acid generation efficiency by exposure, the following photosensitizers can be added.

  The dissolution accelerating compound for the developer that can be used in the present invention is a low molecular weight compound having a molecular weight of 1,000 or less and having two or more phenolic OH groups or one or more carboxy groups. When it has a carboxy group, an alicyclic or aliphatic compound is preferable. Examples of such a phenol compound having a molecular weight of 1000 or less include those described in JP-A-4-1222938, JP-A-2-28531, US Pat. No. 4,916,210, and European Patent 219294.

  In addition, compounds having a proton acceptor functional group described in JP-A No. 2006-208781 and JP-A No. 2007-286574 can be suitably used for the composition of the present application.

<Pattern formation method>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention can be applied on a support such as a substrate to form a resist film. The thickness of this resist film is preferably 0.02 to 0.1 μm.
As a method of coating on the substrate, spin coating is preferable, and the rotation speed is preferably 1000 to 3000 rpm.

  For example, an actinic ray-sensitive or radiation-sensitive resin composition is applied to a substrate (eg, silicon, silicon / silicon dioxide coating, silicon nitride) used in the manufacture of precision integrated circuit elements, photomasks, imprint molds, and the like. , A quartz substrate having a Cr layer, etc.) by a suitable coating method such as a spinner or a coater and dried to form a resist film. In addition, a known antireflection film can be applied in advance.

The resist film is irradiated with actinic rays or radiation, preferably electron beam (EB), X-ray or EUV light (13 nm), preferably baked (heated) and developed. Thereby, a good pattern can be obtained.
It is also preferable to include a preheating step (PB; Prebake) after the film formation and before the exposure step.
It is also preferable to include a post-exposure heating step (PEB; Post Exposure Bake) after the exposure step and before the development step.
The heating temperature is preferably 70 to 140 ° C for both PB and PEB, and more preferably 80 to 135 ° C.
The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 100 seconds.
Heating can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.
The reaction of the exposed part is promoted by baking, and the sensitivity and pattern profile are improved.

Examples of actinic rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, X-rays, and electron beams. As these actinic rays or radiation, for example, those having a wavelength of 250 nm or less, particularly 220 nm or less are more preferable. Examples of such actinic rays or radiation include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, EUV (13 nm), and electron beam (electron beam). It is done. Preferred actinic rays or radiation include ArF excimer laser, F ₂ excimer laser, X-ray, EUV (13 nm) and electron beam, with X-ray, EUV (13 nm) and electron beam being particularly preferred.

  Note that exposure may be performed by filling a liquid (such as pure water) having a higher refractive index than air between the photosensitive film and the lens. That is, immersion exposure may be performed. Thereby, the resolution can be further increased. In this case, an immersion liquid sparingly soluble film (also referred to as “topcoat”) is provided on the resist film between the resist film and the immersion liquid in order to avoid contact between the resist film and the immersion liquid. May be. Further, as another means for avoiding contact between the resist film and the immersion liquid, the aforementioned hydrophobic resin may be added to the aforementioned composition in advance.

  In the development step, an alkali developer is usually used. Examples of the alkaline developer of the composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, and primary amines such as ethylamine and n-propylamine. , Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide (TMAH), tetraethyl Alkaline aqueous solutions such as quaternary ammonium salts such as ammonium hydroxide and cyclic amines such as pyrrole and pihelidine can be used.

Furthermore, alcohols and surfactants can be added in appropriate amounts to the alkaline developer.
The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
The pH of the alkali developer is usually from 10.0 to 15.0.

  For details on producing an imprint mold structure by applying the composition of the present invention, for example, the basics of nanoimprint and technological development / application development-Nanoimprint substrate technology and latest technological development-Editing : Yoshihiko Hirai Frontier Publishing (issued in June 2006), Japanese Patent No. 4109085, Japanese Unexamined Patent Application Publication No. 2008-162101, and the like.

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, the content of this invention is not limited by this.
Hereinafter, Examples 2A, 3A, 6C, 7C, 8D, 38D, 6E, and 7E shall be read as Reference Examples 2A, 3A, 6C, 7C, 8D, 38D, 6E, and 7E, respectively.
<Synthesis of monomer>
Synthesis Example 1 (Synthesis of B-1)
100.00 parts by mass of p-acetoxystyrene was dissolved in 400 parts by mass of ethyl acetate, cooled to 0 ° C., and 47.60 parts by mass of sodium methoxide (28 mass% methanol solution) was added dropwise over 30 minutes, Stir at room temperature for 5 hours. Ethyl acetate was added, and the organic layer was washed 3 times with distilled water, dried over anhydrous sodium sulfate, the solvent was distilled off, and 131.70 parts by mass of p-hydroxystyrene (54% by mass ethyl acetate solution) was added. Obtained.

18.52 parts by mass of p-hydroxystyrene (54% by mass ethyl acetate solution) is dissolved in 56.00 parts by mass of ethyl acetate, and 1,1,2,2,3,3-hexafluoropropane-1,3-di 31.58 parts by mass of sulfonyl difluoride was added and cooled to 0 ° C. A solution prepared by dissolving 12.63 parts by mass of triethylamine in 25.00 parts by mass of ethyl acetate was added dropwise over 30 minutes, and the mixture was stirred at 0 ° C. for 4 hours. Ethyl acetate was added and the organic layer was washed 3 times with saturated brine, and then the solvent was distilled off. 35.00 parts by mass of the obtained compound was dissolved in 315 parts by mass of methanol, cooled to 0 ° C., 245 parts by mass of 1N aqueous sodium hydroxide solution was added, and the mixture was stirred at room temperature for 2 hours. The solvent was distilled off, ethyl acetate was added, and the organic layer was washed 3 times with saturated brine, and then the solvent was distilled off to obtain 34.46 parts by mass of Compound A.
¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 7.42 (d, 2H), 7.22 (d, 2H), 6.68 (dd, 1H), 5.74 (d, 1H) , 5.32 (d, 1H)

40 parts by mass of 4-tert-butoxyphenyldiphenylsulfonium p-toluenesulfonate was dissolved in 200 parts by mass of dichloromethane, 1.2 parts by mass of 10-camphorsulfonic acid was added, and the mixture was heated and stirred at 40 ° C. for 4 hours. The reaction solution was ice-cooled, 8.3 parts by mass of methacryloyl chloride was added, and 8.1 parts by mass of triethylamine was added at a temperature not exceeding 10 ° C. To the reaction solution, 4.0 parts by mass of 10-camphorsulfonic acid and 100 parts by mass of water were added to separate the organic layer. Next, the organic layer was washed 5 times with 200 parts by mass of water. Dichloromethane was distilled off under reduced pressure using a rotary evaporator, and diethyl ether was added to the resulting residue for recrystallization. Filtration under reduced pressure and drying under reduced pressure were performed to obtain 35.0 parts by mass of the desired product as white crystals.
The obtained white solid was dissolved in 30.00 parts by mass of methanol, and 19.0 parts by mass of Compound B was obtained from the obtained solution using an ion exchange resin (Amberlite®; IRA410).
¹ H-NMR (CDCl ₃ : ppm) δ: 2.05 to 2.05 (3H, t), 5.84 to 5.85 (1H, m), 6.37 to 6.39 (1H, m) 7.48-7.51 (2H, d), 7.65-7.86 (12H, m)

  Compound A (20.00 parts by mass) was dissolved in methanol (100.00 parts by mass), compound B (17.55 parts by mass) was added, and the mixture was stirred at room temperature for 3 hours. The solvent was distilled off, distilled water was added, and the mixture was extracted 3 times with chloroform. The obtained organic layer was washed three times with distilled water, and then the solvent was distilled off to obtain 30.23 parts by mass of the target compound (B-1).

<Resin synthesis>
Synthesis Example 2 (Synthesis of P-1)
12.8 parts by mass of methyl ethyl ketone was heated to 85 ° C. under a nitrogen stream. While stirring this solution, 7.61 parts by mass of monomer (B-1) obtained in Synthesis Example 1 above, 7.69 parts by mass of monomer (M-1) having the following structure, 6.01 of 4-hydroxystyrene A mixed solution of 1 part by mass, 51.1 parts by mass of methyl ethyl ketone, dimethyl 2,2′-azobisisobutyrate [V-601, manufactured by Wako Pure Chemical Industries, Ltd.], 0.05 part by mass of triethylamine for 2 hours It was dripped over. After completion of dropping, the mixture was further stirred at 85 ° C. for 4 hours. The reaction solution is allowed to cool and then reprecipitated with a large amount of heptane / ethyl acetate. The obtained solid is dissolved again in acetone, reprecipitated with a large amount of water / methanol and vacuum-dried. 15.5 mass parts of resin (P-1) was obtained.

The weight average molecular weight (Mw: polystyrene conversion) calculated from GPC (carrier: N-methyl-2-pyrrolidone (NMP)) of the obtained resin was Mw = 30000.
Thereafter, Resins P-2 to P-43 and the following Comparative Compounds 1 to 6 were synthesized in the same manner. The following table shows the charge amount ratio (mol%; corresponding to each repeating unit in order from the left) and the weight average molecular weight (Mw). In addition, the molar ratio of the cationic repeating unit (A) to the anionic repeating unit (B) in the monomer pair (3) in the following table is 1: 1.

<Basic compound>
The following compounds C-1 to C-3 were used as basic compounds.
C-1: 2,4,5-triphenylimidazole C-2: Tetrabutylammonium hydroxide C-3: 1,5-diazabicyclo [4.3.0] non-5-ene

  <Low molecular compound (D) (compound (D)) having a group capable of leaving by the action of an acid>

<Surfactant>
The following W-1 to W-4 were used as the surfactant.
W-1: MegaFuck F176 (Dainippon Ink Chemical Co., Ltd .; fluorine-based)
W-2: Megafuck R08 (Dainippon Ink Chemical Co., Ltd .; fluorine and silicon)
W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd .; silicon-based)
W-4: PF6320 (manufactured by OMNOVA) (fluorine-based)
<PAG>

<Solvent>
As the solvent, the following A1 to A4 and B1 to B3 were used. In addition, these solvents were used by being appropriately mixed.
A1: Propylene glycol monomethyl ether acetate (PGMEA)
A2: 2-Heptanone A3: Cyclohexanone A4: γ-Butyrolactone B1: Propylene glycol monomethyl ether (PGME)
B2: Ethyl lactate B3: Propylene carbonate <Example A>
(Examples 1A to 15A and Comparative Examples 1A to 3A)
(Resist preparation)
The components shown in Table 9 below were dissolved in a solvent to prepare a solution having a solid concentration of 4.0% by mass. This solution was filtered through a polytetrafluoroethylene filter having a pore size of 0.1 μm to obtain a positive resist solution.

(Resist evaluation)
First, an antireflection film DUV-42 manufactured by Brewer Science Co., Ltd. is uniformly applied to a film thickness of 60 nm on a silicon substrate that has been subjected to hexamethyldisilazane treatment using a spin coater, and is heated on a hot plate at 100 ° C. for 90 seconds. After drying, heat drying was performed at 190 ° C. for 240 seconds. Thereafter, each positive resist solution was applied using a spin coater and dried at 120 ° C. for 90 seconds to form a resist film having a thickness of 0.12 μm.

  Using this ArF excimer laser exposure apparatus (trade name: NSR S306C, manufactured by Nikon Corporation) through a 6% half-tone mask of 1: 1 line and space pattern with a line width of 150 nm, NA: 0.78, Sigma : It exposed on condition of 0.93 / 0.69, and it heated on the hotplate for 90 second at 120 degreeC immediately after exposure. Furthermore, development was performed at 23 ° C. for 60 seconds using an aqueous 2.38 mass% tetramethylammonium hydroxide solution, rinsed with pure water for 30 seconds, and then dried to obtain a line pattern.

〔sensitivity〕
In the obtained resist film, the exposure amount (mJ / cm ² ) when forming a resist pattern having a line width of 150 nm and a distance between the lines of 150 nm (line and space is 1: 1). ) Was used as an optimum exposure amount and an index of sensitivity. The smaller this value, the higher the sensitivity.
[Resolution (unit: nm)]
Among the line widths of the line-and-space resist pattern formed by the sensitivity evaluation, the minimum line width (nm) of the lines was used as the resolution evaluation value (in Table 9, “resolution (nm)”). . The smaller the numerical value, the better the resolution.

[Line edge roughness (LER)]
A line pattern having a line width of 150 nm (L / S = 1/1) was formed at an irradiation dose showing the above sensitivity. And about arbitrary 30 points | pieces contained in the length direction 50 micrometers, the distance from the reference line which should have an edge was measured using the scanning electron microscope (S-9220 by Hitachi, Ltd.). And the standard deviation of this distance was calculated | required and 3 (sigma) was computed. A smaller value indicates better performance.

[Pattern shape]
The exposure amount for reproducing a mask pattern having a line width of 150 nm and a line and space (L / S = 1/1) was set as the optimum exposure amount, and the profile at the optimum exposure amount was observed with a scanning microscope (SEM).

<Dry etching resistance evaluation>
The unexposed resist film was dry-etched with HITACHI U-621 using Ar / C ₄ F ₆ / O ₂ gas for 30 seconds. Thereafter, the resist remaining film ratio was measured and used as an index of dry etching resistance.
Good: Remaining film ratio is 95% or more.
Defect: Less than 95%.

  The resin, photoacid generator, basic compound, surfactant and solvent were appropriately selected from those shown above.

As is clear from the results shown in Table 9, Comparative Examples 1A to 3A not containing the repeating unit (A) or (B) according to the present invention are inferior in sensitivity, resolution, LER, pattern shape, and dry etching resistance. I understand that.
On the other hand, it can be seen that Examples 1A to 15A according to the present invention are excellent in sensitivity, resolution, LER, and pattern shape in ArF exposure. Moreover, it turns out that it is excellent also about dry etching tolerance. That is, it can be seen that the composition of the present invention has excellent performance as a positive resist composition in ArF excimer laser exposure.
Moreover, it turns out that Example 4A, 5A, 7A-11A using resin containing the repeating unit which has a specific anion structure tends to be excellent in LER and resolving power.

<Example B1>
A resist solution was prepared and coated in the same manner as in Example A except that 0.06 g of the following polymer was added to the composition of Example 1A to obtain a resist film. The obtained resist film was subjected to pattern exposure through an immersion liquid (pure water) using an ArF excimer laser immersion scanner (XTML1250i; NA0.85 manufactured by ASML), and a pattern was formed in the same manner as in Example A. did. The obtained pattern was confirmed to have the same evaluation result in any of the pattern shape, sensitivity, resolution, LER, and dry etching resistance.

<Example B2>
A resist solution was prepared and coated in the same manner as in Example A except that 0.06 g of the following polymer was added to the composition of Example 1A to obtain a resist film. The obtained resist film was subjected to pattern exposure through an immersion liquid (pure water) using an ArF excimer laser immersion scanner (XTML1250i; NA0.85 manufactured by ASML), and a pattern was formed in the same manner as in Example A. did. And about the obtained pattern, it confirmed that the same evaluation result was obtained in any of a sensitivity, resolving power, LER, pattern shape, and dry etching tolerance.

<Example B3>
A resist solution was prepared and coated in the same manner as in Example A except that 0.06 g of the following polymer was added to the composition of Example 1A to obtain a resist film. The obtained resist film was subjected to pattern exposure through an immersion liquid (pure water) using an ArF excimer laser immersion scanner (XTML1250i; NA0.85 manufactured by ASML), and a pattern was formed in the same manner as in Example A. did. And about the obtained pattern, it confirmed that the same evaluation result was obtained in any of a sensitivity, resolving power, LER, pattern shape, and dry etching tolerance.

<Example C>
(Examples 1C to 11C and Comparative Examples 1C to 3C)
(Resist preparation)
The components shown in Table 10 below were dissolved in a solvent, and then filtered through a polytetrafluoroethylene filter having a pore size of 0.1 μm to prepare a positive resist solution having a solid content concentration of 4.5 mass%.

(Resist evaluation)
The prepared positive resist solution is uniformly applied on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater, and is heated and dried on a hot plate at 100 ° C. for 90 seconds to obtain a film thickness of 0.4 μm. The resist film was formed.
This resist film was subjected to pattern exposure using a KrF excimer laser stepper (NA = 0.63) and a 6% halftone mask of 1: 1 line and space pattern with a line width of 180 nm, and immediately after exposure, 110 ° C. For 90 seconds on a hot plate. Thereafter, development was performed at 23 ° C. for 60 seconds using an aqueous 2.38 mass% tetramethylammonium hydroxide solution, rinsed with pure water for 30 seconds, and then dried to form a line pattern.

〔sensitivity〕
In the obtained resist film, the exposure amount (mJ / cm ² ) when forming a resist pattern having a line width of 180 nm and a distance between the lines of 180 nm (line and space is 1: 1). ) Was used as an optimum exposure amount and an index of sensitivity. The smaller this value, the higher the sensitivity.
[Resolution (unit: nm)]
Of the line widths of the line-and-space resist pattern formed by the sensitivity evaluation, the minimum line width (nm) of the lines was used as the evaluation value of resolution (in Table 10, “resolution (nm)”). . The smaller the numerical value, the better the resolution.

[Line edge roughness (LER)]
A line pattern having a line width of 180 nm (L / S = 1/1) was formed at an irradiation dose showing the above sensitivity. And about arbitrary 30 points | pieces contained in the length direction 50 micrometers, the distance from the reference line which should have an edge was measured using the scanning electron microscope (S-9220 by Hitachi, Ltd.). And the standard deviation of this distance was calculated | required and 3 (sigma) was computed. A smaller value indicates better performance.

[Pattern shape]
The exposure amount for reproducing a line and space (L / S = 1/1) mask pattern having a line width of 180 nm was set as the optimal exposure amount, and the profile at the optimal exposure amount was observed with a scanning microscope (SEM).

<Dry etching resistance evaluation>
The dry etching resistance was evaluated in the same manner as described for Example A.

  The resin, photoacid generator, basic compound, surfactant and solvent were appropriately selected from those shown above.

As is apparent from the results shown in Table 10, Comparative Examples 1C to 3C not containing the repeating unit (A) or (B) according to the present invention are inferior in sensitivity, resolution, LER, pattern shape, and dry etching resistance. I understand that.
On the other hand, it can be seen that the composition according to the present invention is excellent in sensitivity, LER, and pattern shape in KrF exposure. It can also be seen that the dry etching resistance is excellent. That is, it can be seen that the photosensitive composition of the present invention has excellent performance as a positive resist composition in KrF excimer laser exposure.
It can also be seen that Examples 1C, 5C, 9C, and 10C using a resin containing a repeating unit having a specific anion structure tend to be excellent in LER and resolution.
Moreover, it turns out that Example 1C-10C using resin containing the repeating unit which has a phenol structure tends to be excellent in a sensitivity, a resolution, and LER.

<Example D>
(Examples 1D to 38D and Comparative Examples 1D to 3D)
(Resist preparation)
The components shown in Tables 11 and 12 below were dissolved in a solvent, and then filtered through a polytetrafluoroethylene filter having a pore size of 0.1 μm to prepare a positive resist solution having a solid content concentration of 4.0% by mass. .

(Resist evaluation)
The prepared positive resist solution is uniformly coated on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater, and dried by heating on a hot plate at 100 ° C. for 60 seconds to obtain a film thickness of 100 nm. A resist film having was formed.
This resist film was irradiated with an electron beam projection lithography apparatus (acceleration voltage 100 keV) manufactured by Nikon Corporation, and immediately after the irradiation, it was heated on a hot plate at 110 ° C. for 90 seconds. Thereafter, development was performed at 23 ° C. for 60 seconds using a 2.38 mass% tetramethylammonium hydroxide aqueous solution, rinsed with pure water for 30 seconds, and then dried to form a line and space pattern.

(Sensitivity evaluation)
The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.). Sensitivity was defined as the minimum irradiation energy when resolving a line having a line width of 100 nm (line: space = 1: 1). The smaller this value, the higher the sensitivity.

(Resolution evaluation)
Of the line widths of the line-and-space resist pattern formed by the sensitivity evaluation, the limiting resolution (minimum width at which lines and spaces are separated and resolved) was defined as the resolution.

(Pattern shape evaluation)
The cross-sectional shape of the line pattern with a line width of 100 nm at the irradiation dose exhibiting the above sensitivity is observed using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.), and the rectangular shape, the T-top, the taper, and the inverse taper. A stage evaluation was performed.

[Line edge roughness (LER)]
About arbitrary 30 points in the length direction 50 μm of the line width 100 nm line pattern at the irradiation dose showing the above sensitivity, from the reference line that should have an edge using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.) The distance was measured, the standard deviation was obtained, and 3σ was calculated. A smaller value indicates better performance.

[Outgas (Evaluation of film thickness fluctuation rate after exposure)]
The irradiation dose twice as high as the above sensitivity was irradiated, the film thickness after exposure (before post-heating) was measured, and the variation rate from the unexposed film thickness was determined from the following equation.
Film thickness fluctuation rate = 100 × (film thickness at unexposed−film thickness after exposure) / film thickness at unexposed film The smaller the film thickness fluctuation rate, the better the outgassing.
<Dry etching resistance evaluation>
The dry etching resistance was evaluated in the same manner as described for Example A.

As is apparent from the results shown in Tables 11 and 12, Comparative Examples 1D to 3D that do not contain the repeating unit (A) or (B) according to the present invention have sensitivity, resolution, LER, pattern shape, outgas, and dry etching resistance. It turns out that both are inferior.
On the other hand, it can be seen that the composition according to the present invention is excellent in pattern shape in electron beam irradiation, and is excellent in sensitivity, LER, and resolving power. Moreover, it turns out that it is excellent also about dry etching tolerance. That is, it can be seen that the composition of the present invention has excellent performance as a positive resist composition by electron beam irradiation.
Moreover, it turns out that Example 1D, 4D, 7D, 13D, 17D-20D, and 23D-38D using the resin containing the repeating unit which has a specific anion tend to be excellent in LER and resolving power.
Moreover, it turns out that Examples 1D-15D, 21D-22D, and 27D-38D using the resin containing the repeating unit which has a phenol structure tend to be excellent in sensitivity.
Moreover, it turns out that Examples 2D-6D, 10D-15D, 18D-22D, 24D-25D, 28D, 30D-31D using the resin containing the repeating unit which has a specific cation tend to be excellent in outgas performance.

<Example E>
(Examples 1E to 15E and Comparative Examples 1E to 3E)
(Resist preparation)
The components shown in Table 13 below were dissolved in a solvent and filtered through a polytetrafluoroethylene filter having a pore size of 0.1 μm to prepare a positive resist solution having a solid content concentration of 8% by mass.

(Resist evaluation)
The prepared positive resist solution is uniformly coated on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater, and dried by heating on a hot plate at 100 ° C. for 60 seconds to obtain a film thickness of 100 nm. A resist film having was formed.

This resist film is irradiated with an EUV exposure apparatus (manufactured by RISOTEC JAPAN, wavelength 13 nm) using a 6% halftone mask of a 1: 1 line and space pattern with a line width of 100 nm, and immediately after irradiation at 130 ° C. for 90 seconds. Heated on a hot plate. Further, development was performed at 23 ° C. for 60 seconds using an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by mass, rinsed with pure water for 30 seconds, and then spin-dried to obtain a resist pattern.
(Sensitivity evaluation)
The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.). The minimum exposure energy when resolving a line having a line width of 100 nm (line: space = 1: 1) was defined as sensitivity.
(Resolution evaluation)
Of the line widths of the line-and-space resist pattern formed by the sensitivity evaluation, the limiting resolution (minimum width at which lines and spaces are separated and resolved) was defined as the resolution.

(Pattern shape evaluation)
The cross-sectional shape of a line pattern with a line width of 100 nm at the exposure amount exhibiting the above sensitivity is observed using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.), and the rectangular shape, T-top, taper, and inverse taper are 4 A stage evaluation was performed.

[Line edge roughness (LER)]
With respect to an arbitrary 30 points in the length direction 50 μm of the line pattern of 100 nm line pattern at the exposure amount showing the above sensitivity, from the reference line that should have an edge using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.) The distance was measured, the standard deviation was obtained, and 3σ was calculated.
[Outgas (Evaluation of film thickness fluctuation rate after exposure)]
Irradiation amount twice as much as the exposure amount indicating the above sensitivity was irradiated, the film thickness after exposure (before post-heating) was measured, and the variation rate from the unexposed film thickness was determined from the following formula.
Film thickness fluctuation rate = 100 × (film thickness at unexposed−film thickness after exposure) / film thickness at unexposed film The smaller the film thickness fluctuation rate, the better the outgassing.
<Dry etching resistance evaluation>
The dry etching resistance was evaluated in the same manner as described for Example A.

As is apparent from the results shown in Table 13, Comparative Examples 1E to 3E that do not contain the repeating unit (A) or (B) according to the present invention have any of sensitivity, resolution, LER, pattern shape, outgas, and dry etching resistance. It turns out that it is inferior.
On the other hand, it can be seen that the composition according to the present invention is excellent in sensitivity, LER, and resolution in EUV exposure. That is, it can be seen that the photosensitive composition of the present invention has excellent performance as a positive resist composition by EUV irradiation.
Moreover, it turns out that Example 1E, 5E, 9E, 11E-15E using resin containing the repeating unit which has a specific anion tends to be excellent in LER and resolving power.
Moreover, it turns out that Examples 1E-9E and 14E using the resin containing the repeating unit which has a phenol structure tend to be excellent in a sensitivity.
Moreover, it turns out that Example 2E-4E, 8E-11E, 13E-15E using resin containing the repeating unit which has a specific cation tends to be excellent in an outgas performance.

Claims (11)

A cationic repeating unit (A) having a cation,
An anionic repeating unit (B) that has an anion that forms an ion pair with the cation, and dissociates from the cation upon irradiation with actinic rays or radiation, and an alkali-soluble group that decomposes by the action of the acid and resin (P) having a repeating unit (C) for generating,
An actinic ray-sensitive or radiation-sensitive resin composition comprising an amine derivative having a group capable of leaving by the action of an acid on a nitrogen atom and an amine derivative .   A cationic repeating unit (A) having a cation,
  An anionic repeating unit (B) having an anion that forms an ion pair with the cation, and dissociating from the cation upon irradiation with actinic rays or radiation to generate an acid; and
  A resin (P) having a repeating unit (C) that decomposes by the action of an acid to generate an alkali-soluble group;
  An actinic ray-sensitive or radiation-sensitive resin composition containing a hydrophobic resin different from the resin (P),
  The hydrophobic resin is a resin having a silicon atom, or a resin having 10 to 100 mol% of repeating units having a fluorine atom in all repeating units of the hydrophobic resin,
  Furthermore, the hydrophobic resin is an actinic ray-sensitive or radiation-sensitive resin composition having at least one group selected from the following groups (x) to (z).
  (X) Alkali-soluble group
  (Y) A group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer.
  (Z) a group decomposable by the action of an acid The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2 , wherein the cationic repeating unit (A) is a cationic repeating unit represented by the following general formula (A1) or (A2).

In the general formula (A1),
R ₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
A represents a divalent linking group.
R _a1 , R _a2 and R _a3 each independently represent a monovalent substituent. When there are a plurality of R _{a1 s,} they may be the same or different, and a plurality of R _a1s may be bonded to each other to form a ring. When there are a plurality of R _{a2 s,} they may be the same or different, and a plurality of R _a2s may be bonded to each other to form a ring. When there are a plurality of R _{a3 s,} they may be the same or different, and a plurality of R _a3 may be bonded to each other to form a ring. Two of R _a1 , R _a2 and R _a3 may jointly form a ring.
n1 represents an integer of 0 to 4.
n2 and n3 each independently represents an integer of 0 to 5.
In the general formula (A2),
R ₁ ′ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
A ′ represents a divalent linking group.
R _a1 ′ and R _a2 ′ each independently represents a monovalent substituent. When there are a plurality of R _a1 ′ s, they may be the same or different, and a plurality of R _a1 ′ s may be bonded to each other to form a ring. When there are a plurality of R _a2 ′ s, they may be the same or different, and a plurality of R _a2 ′ s may be bonded to each other to form a ring. R _a1 ′ and R _a2 ′ may jointly form a ring.
n1 ′ represents an integer of 0 to 4.
n2 ′ represents an integer of 0 to 5. A cationic repeating unit (A) having a cation,
An anionic repeating unit (B) having an anion that forms an ion pair with the cation, and dissociating from the cation upon irradiation with actinic rays or radiation to generate an acid; and
An actinic ray-sensitive or radiation-sensitive resin composition containing a resin (P) having a repeating unit (C) that decomposes by the action of an acid to generate an alkali-soluble group,
The cationic repeat unit (A) is a cationic repeating units represented by the following general formula (A2) or (A3), actinic ray-sensitive or radiation-sensitive resin composition.

In the general formula (A2),
R ₁ ′ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
A ′ represents a divalent linking group.
R _a1 ′ and R _a2 ′ each independently represents a monovalent substituent. When there are a plurality of R _a1 ′ s, they may be the same or different, and a plurality of R _a1 ′ s may be bonded to each other to form a ring. When there are a plurality of R _a2 ′ s, they may be the same or different, and a plurality of R _a2 ′ s may be bonded to each other to form a ring. R _a1 ′ and R _a2 ′ may jointly form a ring.
n1 ′ represents an integer of 0 to 4.
n2 ′ represents an integer of 0 to 5.
In general formula (A3),
R _{1a to} R _12a each independently represents a hydrogen atom or a monovalent substituent, and may be bonded to each other to form a ring.
Z is a single bond or a divalent linking group.
R ₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
A represents a divalent linking group. A cationic repeating unit (A) having a cation,
An anionic repeating unit (B) having an anion that forms an ion pair with the cation, and dissociating from the cation upon irradiation with actinic rays or radiation to generate an acid; and
An actinic ray-sensitive or radiation-sensitive resin composition containing a resin (P) having a repeating unit (C) that decomposes by the action of an acid to generate an alkali-soluble group,
The anionic repeating units (B) is an anionic repeating unit represented by the following general formula (I) or (II), actinic ray-sensitive or radiation-sensitive resin composition.

In general formula (I),
R ₁₁ , R ₁₂ and R ₁₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
X ₁₁ , X ₁₂ and X ₁₃ are each independently a single bond, —O—, —S—, —CO—, —SO ₂ —, —NR—, a divalent nitrogen-containing non-aromatic heterocyclic group, Or the group which combined 2 or more of these is represented. R represents a hydrogen atom or an alkyl group.
Ar ₁ represents a divalent aromatic ring group or a combination of a divalent aromatic ring group and an alkylene group. When X ₁₁ is a single bond, R ₁₂ may form a ring with Ar ₁ .
L ₁₁ and L ₁₂ each independently represent a single bond, an alkylene group, an alkenylene group, a cycloalkylene group, a divalent aromatic ring group, or a group obtained by combining two or more thereof.
Z ₁ is an anion site that forms an ion pair with the cation of the cationic repeating unit (A), and is dissociated from the cation by irradiation with actinic rays or radiation to form a sulfonic acid group, an imido acid group, or a methide acid. Represents a base site.
In general formula (II),
R ₂₁ , R ₂₂ and R ₂₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
X ₂₁ represents —O—, —S—, —CO—, —SO ₂ —, —NR—, a divalent nitrogen-containing non-aromatic heterocyclic group, or a group obtained by combining two or more thereof. . R represents a hydrogen atom or an alkyl group.
L ₂₁ represents an alkylene group, an alkenylene group, a cycloalkylene group, or a group obtained by combining two or more thereof.
Ar ₂ represents a divalent aromatic ring group or a combination of a divalent aromatic ring group and an alkylene group.
X ₂₂ and X ₂₃ each independently represent a single bond, —O—, —S—, —CO—, —SO ₂ —, —NR—, a divalent nitrogen-containing non-aromatic heterocyclic group, or these The group which combined 2 or more of them is represented. R represents a hydrogen atom or an alkyl group.
L ₂₂ represents an alkylene group, an alkenylene group, a cycloalkylene group, a divalent aromatic ring group, or a group obtained by combining two or more thereof.
Z ₂ is an anion site that forms an ion pair with the cation of the cationic repeating unit (A), and is dissociated from the cation by irradiation with actinic rays or radiation to form a sulfonic acid group, an imido acid group, or a methido acid group. Represents the site. The resin (P) is sensitive or radiation-sensitive composition according to any one of claims 1 to 5, further containing a repeating unit represented by the following general formula (VID).

In the above general formula, R ₀₁ , R ₀₂ and R ₀₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
R ₀₃ represents an alkylene group and may combine with X or Ar ₀₁ to form a 5-membered or 6-membered ring together with the main chain —C—C— chain.
Ar ₀₁ represents an aromatic ring group.
n01 represents an integer of 1 to 4.
X represents a single bond or a divalent linking group. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 6 , wherein the repeating unit (C) is a repeating unit represented by the following general formula (V).

In general formula (V):
R ₅₁ , R ₅₂ and R ₅₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
R ₅₂ may be bonded to L ₅ to form a ring, in which case R ₅₂ represents an alkylene group.
L ₅ represents a single bond or a divalent linking group, and in the case of forming a ring with R ₅₂ , represents a trivalent linking group.
R ₅₄ represents an alkyl group, and R ₅₅ and R ₅₆ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or a monovalent aromatic ring group. R ₅₅ and R ₅₆ may combine with each other to form a ring. _However, no and _{R 55} and _{R 56} are hydrogen atoms at the same time. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 7 , wherein the resin (P) further contains a repeating unit having a lactone structure. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 8 , which is exposed to an electron beam, an X-ray or EUV light. Resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1-9. With claim 1 actinic ray-sensitive or radiation-sensitive resin composition according to any one of 9, film is formed, an exposure pattern forming method having the step of developing.