JP6252049B2 - Resist composition and method for producing resist pattern - Google Patents

Description

  The present invention relates to a resist composition and a method for producing a resist pattern.

また、レジスト組成物から、フォトリソグラフィによりレジストパターンを形成する際、アルカリ現像液で現像するとポジ型レジストパターンが得られ、有機溶剤で現像するとネガ型レジストパターンが得られることが知られている（非特許文献１）。 As a semiconductor microfabrication technique, photolithography using a resist composition has been studied. Patent Document 1 describes a resist composition containing only the following compound as an acid generator.

Further, it is known that when a resist pattern is formed from a resist composition by photolithography, a positive resist pattern is obtained when developed with an alkaline developer, and a negative resist pattern is obtained when developed with an organic solvent ( Non-patent document 1).

JP 2004-4669 A

Published by Techno Times Inc. Monthly Display '11 June p. 31

  In the conventional resist compositions described above, when a negative resist pattern is produced, there are cases where the development residue (scum) and pattern shape generated in the portion removed by development cannot always be sufficiently satisfied.

The present invention includes the following inventions.
[1] A resist composition comprising a resin comprising a structural unit having an acid labile group and a structural unit having a phenolic hydroxy group, a nonionic acid generator, an ionic acid generator, and a crosslinking agent.
[2] containing a resin comprising a structural unit having an acid labile group and a structural unit having a phenolic hydroxy group, a nonionic acid generator, an ionic acid generator and a crosslinking agent;
The resist composition whose content of a nonionic acid generator is 0.5 to 20 parts by mass with respect to 100 parts by mass of the resin.
[3] The resist composition according to [1], wherein the content ratio of the nonionic acid generator to the ionic acid generator is 40:60 to 95: 5 on a mass basis.
[4] (1) A step of applying the resist composition according to any one of [1] to [3] on a substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer;
(4) a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating,
A method for producing a resist pattern including:

  By using the resist composition of the present invention, it is possible to produce a negative resist pattern having a good pattern shape with little occurrence of scum in a portion removed by development.

It is a schematic sectional drawing for demonstrating the shape of the resist pattern produced using the resist composition of this invention.

The resist composition of the present invention contains a resin (A), an acid generator (B), and a crosslinking agent (E).
The acid generator (B) is a nonionic acid generator (hereinafter sometimes referred to as “acid generator (B1)”) and an ionic acid generator (hereinafter also referred to as “acid generator (B2)”). including.
Furthermore, the resist composition of the present invention preferably contains a quencher (C) and / or a solvent (D).
In this specification, unless otherwise indicated, the compound illustrated as each component can be used individually or in combination of multiple types.
In the present specification, “(meth) acrylate” means “at least one of acrylate and methacrylate”.

<Resin (A)>
The resin (A) may have a structural unit having an acid labile group (hereinafter sometimes referred to as “structural unit (a1)”) and a structural unit having a phenolic hydroxy group (hereinafter referred to as “structural unit (h)”). ).
In the present specification, the “acid labile group” is a group having a leaving group and forming a hydrophilic group (for example, a hydroxy group or a carboxy group) by leaving the leaving group by contact with an acid. Means.
The resin (A) may further contain a structural unit having no acid labile group (hereinafter sometimes referred to as “structural unit (s)”).

［式（１）中、Ｒ^a1〜Ｒ^a3は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数３〜２０の脂環式炭化水素基又はこれらを組み合わせた基を表すか、Ｒ^a1及びＲ^a2は互いに結合して炭素数２〜２０の２価の炭化水素基を形成する。＊は結合手を表す。］ <Structural unit (a1)>
The structural unit (a1) is derived from a monomer having an acid labile group (hereinafter sometimes referred to as “monomer (a1)”).
Examples of the acid labile group include a group represented by the formula (1) (hereinafter sometimes referred to as “group (1)”) and a group represented by the formula (2) (hereinafter referred to as “group (2)”). In some cases).

[In the formula (1), R ^{a1 to} R ^a3 each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a combination of these, or R ^a1 and R ^a2 are bonded to each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms. * Represents a bond. ]

［式（２）中、Ｒ^ａ１’及びＲ^ａ２’は、互いに独立に、水素原子又は炭素数１〜１２の炭化水素基を表し、Ｒ^ａ３’は、炭素数１〜２０の炭化水素基を表すか、Ｒ^ａ２’及びＲ^ａ３’は互いに結合して炭素数２〜２０の２価の炭化水素基を形成する。該炭化水素基及び該２価の炭化水素基を構成するメチレン基は、酸素原子、カルボニル基又は硫黄原子で置き換わってもよい。＊は結合手を表す。］

[In the formula (2), R ^{a1 ′} and R ^{a2 ′} each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ^{a3 ′} represents a hydrocarbon group having 1 to 20 carbon atoms. R ^{a2 ′} and R ^{a3 ′} are bonded to each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms. The hydrocarbon group and the methylene group constituting the divalent hydrocarbon group may be replaced with an oxygen atom, a carbonyl group or a sulfur atom. * Represents a bond. ]

アルキル基と脂環式炭化水素基とを組合わせた基としては、例えば、メチルシクロヘキシル基、ジメチルシクロへキシル基、メチルノルボルニル基等が挙げられる。 ^Examples of the alkyl group represented by R ^{a1 to} R ^a3 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.
The alicyclic hydrocarbon group for R ^{a1 to} R ^a3 may be monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group, and the following groups (* represents a bond). The alicyclic hydrocarbon group of R ^{a1 to} R ^a3 preferably has 3 to 16 carbon atoms.

Examples of the group obtained by combining an alkyl group and an alicyclic hydrocarbon group include a methylcyclohexyl group, a dimethylcyclohexyl group, and a methylnorbornyl group.

Examples of —C (R ^a1 ) (R ^a2 ) (R ^a3 ) in the case where R ^a1 and R ^a2 are bonded to each other to form a divalent hydrocarbon group include the following groups. The divalent hydrocarbon group preferably has 3 to 12 carbon atoms. * Represents a bond with -O-.

Examples of the group (1) include a 1,1-dialkylalkoxycarbonyl group (in the formula (1), R ^{a1 to} R ^a3 are alkyl groups, preferably a tert-butoxycarbonyl group), 2-alkyladamantane- 2-yloxycarbonyl group (in the formula (1), R ^a1 and R ^a2 are bonded to form an adamantyl group, and R ^a3 is an alkyl group) and 1- (adamantan-1-yl) -1- And an alkylalkoxycarbonyl group (in the formula (1), R ^a1 and R ^a2 are alkyl groups, and R ^a3 is an adamantyl group).

Examples of the hydrocarbon group of R ^{a1 ′ to} R ^{a3 ′} include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group obtained by combining these.
Examples of the aliphatic hydrocarbon group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, hexadecyl group, pentadecyl group, hexyl. Examples thereof include alkyl groups such as decyl group, heptadecyl group, octadecyl group and icosyl group.
Examples of the alicyclic hydrocarbon group are the same as those described above.
Aromatic hydrocarbon groups include phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl Groups, phenanthryl groups, 2,6-diethylphenyl groups, aryl groups such as 2-methyl-6-ethylphenyl, and the like.
Examples of the group obtained by combining an aliphatic hydrocarbon group and an alicyclic hydrocarbon group include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, and an isobornyl group.
Examples of the group obtained by combining an aliphatic hydrocarbon group and an aromatic hydrocarbon group include aralkyl groups such as a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, and a naphthylethyl group.
Examples of the divalent hydrocarbon group formed by combining R ^{a2 ′} and R ^{a3 ′} include groups in which one hydrogen atom has been removed from the hydrocarbon groups of R ^{a1 ′ to} R ^{a3 ′} .
At least one of R ^{a1 ′} and R ^{a2 ′} is preferably a hydrogen atom.

Specific examples of the group (2) include the following groups. * Represents a bond.

The monomer (a1) is preferably a monomer having an acid labile group and an ethylenically unsaturated bond, and more preferably a monomer having an acid labile group and a (meth) acryloyl group.
The acid labile group is preferably group (1) and / or group (2), more preferably a monomer having group (2).
The monomer (a1) is preferably a monomer having an aromatic hydrocarbon group.

［式（ａ１−４）中、Ｒ^ａ１’〜Ｒ^ａ３’は、上記と同じ意味を表す。
Ｒ^ａ５は、水素原子又はメチル基を表す。
Ａ^ａ１は、２価の炭素数６〜１４の芳香族炭化水素基を表す。］
Ｒ^ａ５は、好ましくは、水素原子である。
Ａ^ａ１の芳香族炭化水素基は、好ましくは、フェニレン基及びナフタレンジイル基であり、より好ましくは、フェニレン基である。 As the structural unit (a1), a structural unit represented by the formula (a1-4) (hereinafter sometimes referred to as “structural unit (a1-4)”) and a structural unit represented by the formula (a1-5) (Hereinafter, it is sometimes referred to as “structural unit (a1-5)”). More preferably, it is a structural unit (a1-4).

[In formula (a1-4), R ^{a1 ′ to} R ^{a3 ′} represent the same meaning as described above.
R ^a5 represents a hydrogen atom or a methyl group.
A ^a1 represents a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms. ]
R ^a5 is preferably a hydrogen atom.
The aromatic hydrocarbon group for A ^a1 is preferably a phenylene group or a naphthalenediyl group, and more preferably a phenylene group.

［式（ａ１−５）中、Ｒ^ａ１〜Ｒ^ａ３は、上記と同じ意味を表す。
Ｒ^ａ６は、水素原子又はメチル基を表す。
Ａ^ａ２は、２価の炭素数６〜１４の芳香族炭化水素基を表す。
Ａ^ａ３は、単結合及び酸素原子を表す。］
Ｒ^ａ６は、好ましくは、水素原子である。
Ａ^ａ２の芳香族炭化水素基は、好ましくは、フェニレン基及びナフタレンジイル基であり、より好ましくは、フェニレン基である。

[In the formula (a1-5), R ^{a1 to} R ^a3 represent the same meaning as described above.
R ^a6 represents a hydrogen atom or a methyl group.
A ^a2 represents a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms.
A ^a3 represents a single bond and an oxygen atom. ]
R ^a6 is preferably a hydrogen atom.
The aromatic hydrocarbon group for A ^a2 is preferably a phenylene group or a naphthalenediyl group, and more preferably a phenylene group.

As the structural unit (a1-4), for example, a structural unit represented by any of the formulas (a1-4-1) to (a1-4-16) can be given, and preferably the structural unit (a1-4) -1) to a structural unit represented by formula (a1-4-8), more preferably represented by any one of formula (a1-4-1) to formula (a1-4-3). Is a structural unit.

Examples of the structural unit (a1-5) include structural units represented by any of the formulas (a1-5-1) to (a1-5-7), and preferably the formula (a1-5-1) And a structural unit represented by any one of formulas (a1-5-2).

  In the resin (A), the content of the structural unit (a1) is preferably from 10 to 95 mol%, more preferably from 15 to 80 mol%, more preferably from 20 to 70 mol%, based on all structural units of the resin (A). Is more preferable.

［式（ａ２−１）中、
Ｒ^a30は、水素原子又はメチル基を表す。
Ｒ^a31は、ハロゲン原子、ヒドロキシ基、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、炭素数２〜４のアシル基、炭素数２〜４のアシルオキシ基、アクリロイル基又はメタクリロイル基を表す。
ｍａは０〜４の整数を表す。ｍａが２以上の整数である場合、複数のＲ^a31は互いに同一又は相異なる。］ <Structural unit (h)>
The structural unit (h) is derived from a monomer having a phenolic hydroxy group (hereinafter sometimes referred to as “monomer (h)”).
The monomer (h) is preferably a monomer having a phenolic hydroxy group and an ethylenically unsaturated bond, and may be referred to as a structural unit represented by the formula (a2-1) (hereinafter referred to as “structural unit (a2-1)”). ) Is more preferable.

[In the formula (a2-1),
R ^a30 represents a hydrogen atom or a methyl group.
R ^a31 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an acryloyl group, or methacryloyl. Represents a group.
ma represents an integer of 0 to 4. When ma is an integer of 2 or more, the plurality of R ^a31 are the same or different from each other. ]

R ^a30 is preferably a hydrogen atom.
Examples of the alkyl group for R ^a31 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, and a hexyl group. An alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is preferable. A group is more preferable, and a methyl group is more preferable.
Examples of the alkoxy group for R ^a31 include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group, and an alkoxy group having 1 to 4 carbon atoms is preferable and preferable. Is more preferably a methoxy group or an ethoxy group, and even more preferably a methoxy group.
ma is preferably 0, 1 or 2, more preferably 0 or 1, and still more preferably 0.

As a monomer which introduce | transduces a structural unit (a2-1), the monomer described in Unexamined-Japanese-Patent No. 2010-204634 is mentioned, for example.
Especially, as a structural unit (a2-1), what is each represented by a formula (a2-1-1)-a formula (a2-1-4) is preferable.

  The content of the structural unit (a2-1) is preferably 5 to 90 mol%, more preferably 15 to 85 mol%, and still more preferably 30 to 80 mol% with respect to all the structural units of the resin (A).

［式（ａ２−２）中、
Ｒ^a32は、水素原子又はメチル基を表す。
Ｒ^a33は、ハロゲン原子、ヒドロキシ基、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、炭素数２〜４のアシル基、炭素数２〜４のアシルオキシ基、アクリロイル基又はメタクリロイル基を表す。
ｍｂは０〜４の整数を表す。ｍａが２以上の整数である場合、複数のＲ^a33は互いに同一又は相異なる。
Ｒ^a34は、炭素数１〜８のアルキル基及び炭素数２〜８のアシル基を表す。］ <Structural unit (s)>
The structural unit (s) is derived from a monomer having no acid labile group (hereinafter sometimes referred to as “monomer (s)”).
Examples of the structural unit (s) include a structural unit represented by the formula (a2-2) (hereinafter may be referred to as “structural unit (a2-2)”).

[In the formula (a2-2),
R ^a32 represents a hydrogen atom or a methyl group.
R ^a33 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an acryloyl group, or methacryloyl. Represents a group.
mb represents the integer of 0-4. When ma is an integer of 2 or more, the plurality of R ^a33 are the same or different from each other.
R ^a34 represents an alkyl group having 1 to 8 carbon atoms and an acyl group having 2 to 8 carbon atoms. ]

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, and an octyl group.
As the acyl group, for example, an acetyl group, a propionyl group, a butyryl group, a valeryl group, a hexanoyl group, a heptanoyl group, an octanoyl group or the like in which an alkyl group and a carbonyl group are bonded, an aryl group such as a benzoyl group and a carbonyl group Are combined.
R ^a34 is preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
R ^a32 is preferably a hydrogen atom.
As R ^a33 , the same as R ^a31 in formula (a2-1) can be mentioned.
mb is preferably 0, 1 or 2, more preferably 0 or 1, and still more preferably 0.

As the structural unit (a2-2), structural units represented by formula (a2-2-1) to formula (a2-2-6) can be given.

  When the resin (A) has a structural unit (a2-2), the content is preferably 1 to 40 mol%, more preferably 3 to 30 mol%, based on all structural units of the resin (A). 5-20 mol% is more preferable.

  In the resin (A), the content ratio of the structural unit (a1) and the structural unit (h) [structural unit (a1): structural unit (h) (molar ratio)] is preferably 10:90 to 95: 5, 15 : 85 to 85:15 is more preferable, and 20:80 to 70:30 is more preferable.

Each structural unit constituting the resin (A) can be produced by a known polymerization method (for example, radical polymerization method) using a monomer that derives these structural units. The content rate of each structural unit can be adjusted with the usage-amount of the monomer used when manufacturing resin (A).
However, as the monomer (h), it is preferable to use a monomer in which the phenolic hydroxy group of the monomer is previously protected with a protecting group. Resin (A) can be manufactured by deprotecting after a polymerization reaction. The protecting group may be a protecting group that can be deprotected with an acid, but a protecting group that can be deprotected with a base is preferable in that the acid labile property of the structural unit (a1) is not significantly impaired. Examples of the protecting group include an acetyl group.
In addition, the structural unit (a1-4), the structural unit (a1-5), and the structural unit (a2-2) are obtained by polymerizing the monomer (h) corresponding thereto and then etherifying or esterifying the phenolic hydroxy group. It can introduce | transduce by performing a chemical reaction.

If the specific example of resin (A) is shown by the combination of a structural unit, resin represented by Formula (A-1)-Formula (A-8) will be mentioned, for example.

  The weight average molecular weight of the resin (A) is preferably 2,500 or more and 50,000 or less, and more preferably 3,000 or more and 30,000 or less. In addition, the weight average molecular weight here is calculated | required as a conversion value of a standard polystyrene reference | standard by gel permeation chromatography. Detailed analysis conditions for this analysis are described in the Examples of the present application.

  The content of the resin (A) is preferably 80% by mass or more and 99% by mass or less with respect to the total amount of the solid content. In the present specification, the “solid content” means the total of components excluding the solvent (D) from the resist composition of the present invention. The mass of the solid content and the content of each component contained in the resist composition of the present invention can be measured by known analysis means such as liquid chromatography or gas chromatography.

<Acid generator (B)>
The acid generator (B) is a compound that generates an acid when irradiated with radiation, and contains a nonionic acid generator and an ionic acid generator. The nonionic acid generator is an acid generator having no ionic bond in the molecule, and the ionic acid generator is an acid generator having an ionic bond in the molecule.

［式（ｂ−１）中、Ｒ^ｂ１及びＲ^ｂ２は、互いに独立に、炭素数１〜１０の炭化水素基を表す。］

［式（ｂ１−２）中、Ｒ^ｂ３は、フッ素原子を有してもよい炭素数１〜１８の炭化水素基を表し、該炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基で置換されてもよい。
Ｒ^ｂ４は、それぞれ独立に、水素原子、炭素数１〜５のアルキル基又はアルコキシ基を表す。］ <Acid generator (B1)>
Examples of the acid generator (B1) include organic halides, sulfonate esters (for example, 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4-sulfonate), And sulfones (for example, disulfone, ketosulfone, sulfonyldiazomethane) and the like. The acid generator (B1) is preferably a sulfonate ester and / or a sulfone, more preferably a compound represented by the formula (b1-1) and / or a formula (b1-2). A compound.

[In formula (b-1), R ^b1 and R ^b2 each independently represent a hydrocarbon group having 1 to 10 carbon atoms. ]

[In Formula (b1-2), R ^b3 represents a C 1-18 hydrocarbon group which may have a fluorine atom, and the methylene group contained in the hydrocarbon group is an oxygen atom or a carbonyl group. May be substituted.
R ^b4 each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group. ]

Examples of the hydrocarbon group for R ^b1 , R ^b2, and R ^b3 include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Specific examples include the same groups as those in R ^{a1 ′} and R ^{a2 ′} in formula (2).

Examples of the hydrocarbon group having a fluorine atom include a difluoromethyl group, a trifluoromethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, and a perfluoroethyl group. 1,1,2,2-tetrafluoropropyl group, 1,1,2,2,3,3-hexafluoropropyl group, perfluoroethylmethyl group, 1- (trifluoromethyl) -1,2,2, 2-tetrafluoroethyl group, perfluoropropyl group, 1,1,2,2-tetrafluorobutyl group, 1,1,2,2,3,3-hexafluorobutyl group, 1,1,2,2,3 , 3,4,4-octafluorobutyl group, perfluorobutyl group, 1,1-bis (trifluoro) methyl-2,2,2-trifluoroethyl group, 2- (perfluoropropylene ) Ethyl group, 1,1,2,2,3,3,4,4-octafluoropentyl group, perfluoropentyl group, 1,1,2,2,3,3,4,4,5,5-deca Fluoropentyl group, 1,1-bis (trifluoromethyl) -2,2,3,3,3-pentafluoropropyl group, perfluoropentyl group, 2- (perfluorobutyl) ethyl group, 1,1,2,2 3,3,4,4,5,5-decafluorohexyl group, 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyl group, perfluoropentylmethyl Groups and fluorinated alkyl groups such as perfluorohexyl groups;
An alicyclic hydrocarbon group having a fluorine atom such as a perfluorocyclohexyl group or a perfluoroadamantyl group;
Examples thereof include fluorinated aryl groups such as a fluorophenyl group, a perfluorophenyl group, and a fluoronaphthyl group.
The hydrocarbon group having 1 to 18 carbon atoms having a fluorine atom is preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom or an aromatic hydrocarbon group having 6 to 14 carbon atoms having a fluorine atom, More preferably, it is a C1-C8 perfluoroalkyl group, More preferably, it is a C1-C4 perfluoroalkyl group.

Examples of the group in which the methylene group contained in the hydrocarbon group is substituted with an oxygen atom or a carbonyl group include groups represented by any of formulas (Y1) to (Y12). Preferably, it is group represented by either of Formula (Y7)-Formula (Y9), More preferably, it is group represented by Formula (Y9).

R ^b1 and R ^b2 are preferably independently of each other an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms. Or it is a C4-C10 hydrocarbon group which combined the aliphatic hydrocarbon group and the alicyclic hydrocarbon group.
R ^b3 is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or an aliphatic hydrocarbon. A hydrocarbon group having 4 to 10 carbon atoms, which is a combination of a group and an alicyclic hydrocarbon group, and the methylene group contained in these groups may be replaced by a carbonyl group.

Specific examples of the acid generator represented by the formula (b1-1) include the following compounds.

Specific examples of the acid generator represented by the formula (b1-2) include the following compounds.

  The content of the acid generator (B1) is usually 0.5 parts by mass or more and 20 parts by mass or less, preferably 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the resin (A). More preferably, it is 2 parts by mass or less and 5 parts by mass or less.

［ 式（ｂ２）中、
Ｒ^ｂ５は、フッ素原子を有してもよい炭素数１〜３２の炭化水素基を表し、該炭化水素基を構成するメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。
Ａ^＋は有機カチオンを表す。］ <Acid generator (B2)>
Examples of the acid generator (B2) include onium salts containing onium cations (for example, diazonium salts, phosphonium salts, sulfonium salts, iodonium salts) and the like. Examples of the anion of the onium salt include a sulfonate anion, a sulfonylimide acid anion, and a sulfonylmethide acid anion. Preferred is a sulfonate anion, and more preferred is an acid generator represented by the formula (b2).

[In Formula (b2),
R ^b5 represents a hydrocarbon group having 1 to 32 carbon atoms which may have a fluorine atom, a methylene group constituting the hydrocarbon group may be replaced by an oxygen atom or a carbonyl group.
A ⁺ represents an organic cation. ]

The hydrocarbon group of R ^b5 is, for example, an aliphatic hydrocarbon group having 1 to 32 carbon atoms, an alicyclic hydrocarbon group having 3 to 32 carbon atoms, an aromatic hydrocarbon group having 6 to 32 carbon atoms, and a combination thereof. And a group having 32 or less carbon atoms, specifically, the same groups as those described for R ^b3 in formula (b1-2).
The number of carbon atoms in the hydrocarbon group R ^b5 is preferably 1 to 20, more preferably 1 to 15.

Examples of R ^b5 —SO ₃ ^{— in} formula (b2) include an anion represented by any one of formula (b2-5-1) to formula (b2-5-15), and preferably formula (b2 −5-4) to an anion represented by any one of formulas (B2-5-11).

Examples of the organic cation of A ⁺ include organic onium cations such as organic sulfonium cation, organic iodonium cation, organic ammonium cation, benzothiazolium cation, and organic phosphonium cation, and preferably organic sulfonium cation or organic iodonium cation. More preferably an arylsulfonium cation.

A ⁺ in the formula (b2) is preferably a cation represented by any one of the formulas (b2-1) to (b2-4) [hereinafter referred to as “cation (b2-1)” or the like depending on the formula number] There is a case. ].

In formula (b2-1) to formula (b2-4),
R ^{b4 to} R ^b6 each independently represents an alkyl group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 24 carbon atoms, and the alkyl group The hydrogen atom contained in is optionally substituted with a hydroxy group, an alkoxy group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group Is optionally substituted with a halogen atom, an alkyl group having 1 to 18 carbon atoms, an acyl group having 2 to 4 carbon atoms or a glycidyloxy group, and the hydrogen atom contained in the aromatic hydrocarbon group is a halogen atom, It may be substituted with a hydroxy group or an alkoxy group having 1 to 12 carbon atoms.
R ^b4 and R ^b5 may together form a 3- to 12-membered ring (preferably a 3- to 7-membered ring) with the sulfur atom to which they are bonded.

R ^b7 and R ^b8 each independently represent a hydroxy group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
m2 and n2 each independently represent an integer of 0 to 5.

R ^b9 and R ^b10 each independently represent an alkyl group having 1 to 18 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms.
R ^b9 and R ^b10 may together form a 3- to 12-membered ring (preferably a 3- to 7-membered ring) with the sulfur atom to which they are bonded. —CH ₂ — contained in the ring may be replaced by —O—, —SO— or —CO—.
R ^b11 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms.
R ^b12 represents an alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the aromatic hydrocarbon group has It may be substituted with an alkoxy group having 1 to 12 or an alkylcarbonyloxy group having 1 to 12 carbon atoms.
R ^b11 and R ^b12 may form a 3- to 12-membered ring (preferably a 3- to 7-membered ring) together with —CH—CO— to which they are bonded. —CH ₂ — contained in the ring may be replaced by —O—, —SO— or —CO—.

R ^{b13 to} R ^b18 each independently represent a hydroxy group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
L ^b11 represents -S- or -O-.
o2, p2, s2, and t2 each independently represents an integer of 0 to 5.
q2 and r2 each independently represents an integer of 0 to 4.
u2 represents 0 or 1.
When o2 is 2 or more, the plurality of R ^b13 may be the same or different. When p2 is 2 or more, the plurality of R ^b14 may be the same or different. When q2 is 2 or more, the plurality of R ^b15 is When r2 is 2 or more, a plurality of R ^b16 may be the same or different. When s2 is 2 or more, a plurality of R ^b17 may be the same or different, and t2 is 2 or more. Sometimes, the plurality of R ^b18 may be the same or different.

特に、Ｒ^b9〜Ｒ^b11の脂環式炭化水素基は、好ましくは炭素数３〜１８、より好ましくは炭素数４〜１２である。 Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and 2-ethylhexyl group. . In particular, the alkyl group of R ^{b9 to} R ^b12 preferably has 1 to 12 carbon atoms.
The alicyclic hydrocarbon group may be monocyclic or polycyclic, and the hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with an alkyl group. In this case, the carbon number of the alicyclic hydrocarbon group is 20 or less including the carbon number of the alkyl group. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclodecyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group, and the following groups.

In particular, the alicyclic hydrocarbon group of R ^{b9 to} R ^b11 preferably has 3 to 18 carbon atoms, more preferably 4 to 12 carbon atoms.

  Examples of the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an alkyl group include a methylcyclohexyl group, a dimethylcyclohexyl group, a 2-alkyladamantan-2-yl group, a methylnorbornyl group, and an isobornyl group. Can be mentioned.

Examples of the aromatic hydrocarbon group include phenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl group, p-cyclohexylphenyl group, p-adamantyl group. Examples thereof include a phenyl group, a biphenylyl group, a naphthyl group, a phenanthryl group, a 2,6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group.
Examples of the aromatic hydrocarbon group in which a hydrogen atom is substituted with an alkoxy group include a p-methoxyphenyl group.
Examples of the alkyl group in which a hydrogen atom is substituted with an aromatic hydrocarbon group, that is, an aralkyl group, include a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, and a naphthylethyl group.

Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group and dodecyloxy group.
Examples of the acyl group include an acetyl group, a propionyl group, and a butyryl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alkylcarbonyloxy group include methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, isopropylcarbonyloxy group, n-butylcarbonyloxy group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy group. Group, pentylcarbonyloxy group, hexylcarbonyloxy group, octylcarbonyloxy group, 2-ethylhexylcarbonyloxy group and the like.

The ring containing a sulfur atom which may be formed by combining R ^b4 and R ^b5 is any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. If it contains one or more sulfur atoms, it may further contain one or more sulfur atoms and / or one or more oxygen atoms. As the ring, a ring having 3 to 18 carbon atoms is preferable, and a ring having 4 to 18 carbon atoms is more preferable.

Examples of the ring formed together with the sulfur atom to which R ^b9 and R ^b10 are bonded include, for example, a thiolane-1-ium ring (tetrahydrothiophenium ring), a thian-1-ium ring, and a 1,4-oxathian-4-ium. A ring etc. are mentioned.
Examples of the ring formed with —CH—CO— in which R ^b11 and R ^b12 are bonded include an oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, and an oxoadamantane ring.

Among the cation (b2-1) to cation (b2-4), the cation (b2-1) is preferable, more preferably a cation represented by the formula (b2-1-1) (hereinafter referred to as “cation ( more preferably triphenylsulfonium cation (in formula (b2-1-1), v2 = w2 = x2 = 0), diphenyltolylsulfonium cation (formula In (b2-1-1), v2 = w2 = 0, x2 = 1, and R ^b21 is a methyl group.) Or a tolylsulfonium cation (in the formula (b2-1-1), v2 = w2 = x2 = 1, and R ^b19 , R ^b20 and R ^b21 are all methyl groups.).

式（ｂ２−１−１）中、
Ｒ^b19、Ｒ^b20及びＲ^b21は、それぞれ独立に、ハロゲン原子（より好ましくはフッ素原子）、ヒドロキシ基、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基又は炭素数３〜１８の脂環式炭化水素基を表す。また、Ｒ^b19〜Ｒ^b21から選ばれる２つが一緒になって硫黄原子を含む環を形成してもよい。
ｖ２、ｗ２及びｘ２は、それぞれ独立に０〜５の整数（好ましくは０又は１）を表す。
ｖ２が２以上のとき、複数のＲ^b19は同一又は相異なり、ｗ２が２以上のとき、複数のＲ^b20は同一又は相異なり、ｘ２が２以上のとき、複数のＲ^b21は同一又は相異なる。

In formula (b2-1-1),
R ^b19 , R ^b20 and R ^b21 each independently represent a halogen atom (more preferably a fluorine atom), a hydroxy group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or 3 to 18 carbon atoms. Represents an alicyclic hydrocarbon group. It is also possible that two selected from R ^b19 to R ^b21 together form a ring containing a sulfur atom.
v2, w2 and x2 each independently represent an integer of 0 to 5 (preferably 0 or 1).
When v2 is 2 or more, the plurality of R ^b19 are the same or different, when w2 is 2 or more, the plurality of R ^b20 are the same or different, and when x2 is 2 or more, the plurality of R ^b21 are the same or different. .

Among them, R ^b19 , R ^b20 and R ^b21 are preferably each independently a halogen atom (more preferably a fluorine atom), a hydroxy group, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. It is.

  Specific examples of the cation represented by the formula (b2-1-1) include cations described in JP 2010-204646 A.

The salt represented by the formula (b2) is a combination of the above organic cation and the above anion. These can be arbitrarily combined. A preferable combination is, for example, a salt represented by the following formula.

The content of the acid generator (B2) is 0.5 parts by mass or more and 20 parts by mass or less, preferably 0.5 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the resin (A). More preferably, they are 0.7 mass part or more and 15 mass parts or less, More preferably, they are 0.8 mass part or more and 10 mass parts or less.
The content of the acid generator (B) is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 2 parts by mass or more and 25 parts by mass or less, with respect to 100 parts by mass of the resin (A). Preferably they are 3 to 25 mass parts.
The content ratio (mass basis) of the acid generator (B1) and the acid generator (B2) is usually acid generator (B1): acid generator (B2) = 40: 60 to 95: 5, Preferably, the acid generator (B1): acid generator (B2) = 50: 50 to 95: 5, more preferably the acid generator (B1): acid generator (B2) = 60: 40 to 90:10. It is.

式（ｅ−１）中、
Ｒ^ｅ１は、水素原子、炭素数１〜６のアルキル基、炭素数３〜１０の脂環式炭化水素基及び炭素数３〜６のオキソアルキル基を表す。
オキソアルキル基としては、２−オキソプロピル基、２−オキソブチル基、２−オキソペンチル基、２−オキソヘキシル基等が挙げられる。 <Crosslinking agent (E)>
A crosslinking agent (E) is a compound which raise | generates a crosslinking reaction by the effect | action of an acid, for example, is a compound which has group represented by Formula (e-1).

In formula (e-1),
R ^e1 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and an oxoalkyl group having 3 to 6 carbon atoms.
Examples of the oxoalkyl group include a 2-oxopropyl group, a 2-oxobutyl group, a 2-oxopentyl group, and a 2-oxohexyl group.

式（ｅ−２）及び式（ｅ−３）中、
Ｒ^ｅ１は、上記と同じ意味を表し、複数のＲ^ｅ１は、互いに同一でも異なってもよい。
Ｒ^ｅ２及びＲ^ｅ３は、互いに独立に、水素原子、炭素数１〜６のアルキル基、炭素数３〜１０の脂環式炭化水素基、炭素数２〜６のアルコキシアルキル基を表すか、一緒になって−Ｎ−ＣＯ−Ｎ−とともに環を形成してもよく、該環は炭素数１〜４のアルコキシ基を有していてもよい。 Examples of the compound having a group represented by the formula (e-1) include urea compounds and melamine compounds.
As the urea compound, a compound represented by the formula (e-2) and a compound represented by the formula (e-3) are preferable.

In formula (e-2) and formula (e-3),
R ^e1 represents the same meaning as described above, and a plurality of R ^e1 may be the same as or different from each other.
R ^e2 and R ^e3 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, an alkoxyalkyl group having 2 to 6 carbon atoms, or together And may form a ring together with -N-CO-N-, and the ring may have an alkoxy group having 1 to 4 carbon atoms.

Examples of the compound represented by the formula (e-2) include the following compounds.

Examples of the compound represented by formula (e-3) include the following compounds.

式（ｅ−３）中、
Ｒ^ｅ１は、上記と同じ意味を表し、複数のＲ^ｅ１は、互いに同一でも異なってもよい。
Ｒ^ｅ４は、水素原子、炭素数１〜６のアルキル基、炭素数〜１０の脂環式炭化水素基又は−ＮＲ^ｅ７−ＣＨ_２−Ｏ−Ｒ^ｅ１を表す。
Ｒ^ｅ５、Ｒ^ｅ６及びＲ^ｅ７は、互いに独立に、水素原子、炭素数１〜６のアルキル基、炭素数３〜１０の脂環式炭化水素基又は−ＣＨ_２−Ｏ−Ｒ^ｅ１を表す。 As the melamine compound, a compound represented by the formula (e-3) is preferable.

In formula (e-3),
R ^e1 represents the same meaning as described above, and a plurality of R ^e1 may be the same as or different from each other.
R ^e4 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 10 to 10 carbon atoms, or —NR ^e7 —CH ₂ —O—R ^e1 .
R ^e5 , R ^e6 and R ^e7 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or —CH ₂ —O—R ^e1 .

Examples of the compound represented by formula (e-3) include the following compounds.

  The content of the crosslinking agent (E) is preferably 4 parts by mass or more and 25 parts by mass or less, and more preferably 5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the resin (A).

<Quencher (C)>
The quencher in the resist composition of the present invention may be any compound that has an acid diffusion suppressing action, that is, a compound that traps an acid generated from an acid generator upon exposure. In addition to this action, the quencher generates an acid itself. It may be a compound obtained. Examples of the quencher include basic nitrogen-containing organic compounds and weak acid salts.

Examples of basic nitrogen-containing organic compounds include amines and ammonium salts. Examples of amines include aliphatic amines and aromatic amines. Examples of amines include primary amines, secondary amines, and tertiary amines.
The amine is preferably a compound represented by any one of formula (C1) to formula (C8) and formula (C1-1).

［式（Ｃ１）中、
Ｒ^c1、Ｒ^c2及びＲ^c3は、互いに独立に、水素原子、炭素数１〜６のアルキル基、炭素数５〜１０の脂環式炭化水素基又は炭素数６〜１０の芳香族炭化水素基を表し、該アルキル基及び該脂環式炭化水素基に含まれる水素原子は、ヒドロキシ基、アミノ基又は炭素数１〜６のアルコキシ基で置換されていてもよく、該芳香族炭化水素基に含まれる水素原子は、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、炭素数５〜１０の脂環式炭化水素又は炭素数６〜１０の芳香族炭化水素基で置換されていてもよい。］

[In the formula (C1),
R ^c1 , R ^c2 and R ^c3 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 5 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms. The hydrogen atom contained in the alkyl group and the alicyclic hydrocarbon group may be substituted with a hydroxy group, an amino group, or an alkoxy group having 1 to 6 carbon atoms, and the aromatic hydrocarbon group The hydrogen atom contained is substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alicyclic hydrocarbon having 5 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms. It may be. ]

［式（Ｃ１−１）中、
Ｒ^c2及びＲ^c3は、前記と同義である。
Ｒ^c4は、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、炭素数５〜１０の脂環式炭化水素又は炭素数６〜１０の芳香族炭化水素基を表す。
ｍ３は０〜３の整数を表し、ｍ３が２以上のとき、複数のＲ^c4は、互いに同一でも異なってもよい。］

[In the formula (C1-1),
R ^c2 and R ^c3 are as defined above.
R ^c4 represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alicyclic hydrocarbon having 5 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms.
m3 represents an integer of 0 to 3, and when m3 is 2 or more, a plurality of R ^{c4 s} may be the same as or different from each other. ]

［式（Ｃ２）、式（Ｃ３）及び式（Ｃ４）中、
Ｒ^c5、Ｒ^c6、Ｒ^c7及びＲ^c8は、互いに独立に、Ｒ^c1と同義である。
Ｒ^c9は、炭素数１〜６のアルキル基、炭素数３〜６の脂環式炭化水素基又は炭素数２〜６のアルカノイル基を表す。
ｎ３は０〜８の整数を表し、ｎ３が２以上のとき、複数のＲ^c9は、互いに同一でも異なってもよい。］

[In Formula (C2), Formula (C3) and Formula (C4),
R ^c5 , R ^c6 , R ^c7 and R ^c8 are the same as R ^c1 independently of each other.
R ^c9 represents an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, or an alkanoyl group having 2 to 6 carbon atoms.
n3 represents an integer of 0 to 8, and when n3 is 2 or more, the plurality of R ^c9 may be the same as or different from each other. ]

［式（Ｃ５）及び式（Ｃ６）中、
Ｒ^c10、Ｒ^c11、Ｒ^c12、Ｒ^c13及びＲ^c16は、互いに独立に、Ｒ^c1と同義である。
Ｒ^c14、Ｒ^c15及びＲ^c17は、互いに独立に、Ｒ^c4と同義である。
ｏ３及びｐ３は、互いに独立に０〜３の整数を表し、ｏ３が２以上のとき、複数のＲ^c14は互いに同一でも異なってもよく、ｐ３が２以上のとき、複数のＲ^c15は互いに同一でも異なってもよい。
Ｌ^c1は、炭素数１〜６のアルカンジイル基、−ＣＯ−、−Ｃ（＝ＮＨ）−、−Ｓ−又はこれらを組合せた２価の基を表す。］

[In Formula (C5) and Formula (C6),
R ^c10 , R ^c11 , R ^c12 , R ^c13 and R ^c16 have the same ^meaning as R ^c1 independently of each other.
R ^c14 , R ^c15 and R ^c17 have the same ^meaning as R ^c4 independently of each other.
o3 and p3 each independently represent an integer of 0 to 3, and when o3 is 2 or more, the plurality of R ^c14 may be the same or different from each other. When p3 is 2 or more, the plurality of R ^c15 are the same as each other But it may be different.
L ^c1 represents an alkanediyl group having 1 to 6 carbon atoms, —CO—, —C (═NH) —, —S—, or a divalent group obtained by combining these. ]

［式（Ｃ７）及び式（Ｃ８）中、
Ｒ^c18、Ｒ^c19及びＲ^c20は、互いに独立に、Ｒ^c4と同義である。
ｑ３、ｒ３及びｓ３は、互いに独立に０〜３の整数を表し、ｑ３が２以上のとき、複数のＲ^c18は互いに同一でも異なってもよく、ｒ３が２以上のとき、複数のＲ^c19は互いに同一でも異なってもよく、ｓ３が２以上のとき、複数のＲ^c20は互いに同一でも異なってもよい。
Ｌ^c2は、単結合又は炭素数１〜６のアルカンジイル基、−ＣＯ−、−Ｃ（＝ＮＨ）−、−Ｓ−又はこれらを組合せた２価の基を表す。］

[In Formula (C7) and Formula (C8),
R ^c18, R ^c19 and R ^{c 20} are each independently the same meaning as R ^c4.
q3, r3 and s3 each independently represent an integer of 0 to 3. When q3 is 2 or more, a plurality of R ^c18 may be the same or different from each other. When r3 is 2 or more, a plurality of R ^c19 is They may be the same or different, and when s3 is 2 or more, the plurality of R ^c20 may be the same or different.
L ^c2 represents a single bond or an alkanediyl group having 1 to 6 carbon atoms, —CO—, —C (═NH) —, —S—, or a divalent group obtained by combining these. ]

In formula (C1) to formula (C8) and formula (C1-1), the alkyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group, alkoxy group and alkanediyl group are the same as those described above. Is mentioned.
Examples of the alkanoyl group include acetyl group, 2-methylacetyl group, 2,2-dimethylacetyl group, propionyl group, butyryl group, isobutyryl group, pentanoyl group, and 2,2-dimethylpropionyl group.

  Examples of the compound represented by the formula (C1) include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N, N- Dimethylaniline, diphenylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tri Pentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyl Hexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonyl Amine, ethyldidecylamine, dicyclohexylmethylamine, tris [2- (2-methoxyethoxy) ethyl] amine, triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diamino-1,2- Examples include diphenylethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, and 4,4′-diamino-3,3′-diethyldiphenylmethane. Ropiruanirin. Particularly preferred include 2,6-diisopropylaniline.

Examples of the compound represented by the formula (C2) include piperazine.
Examples of the compound represented by the formula (C3) include morpholine.
Examples of the compound represented by the formula (C4) include piperidine and hindered amine compounds having a piperidine skeleton described in JP-A No. 11-52575.
Examples of the compound represented by the formula (C5) include 2,2′-methylenebisaniline.
Examples of the compound represented by the formula (C6) include imidazole and 4-methylimidazole.
Examples of the compound represented by the formula (C7) include pyridine and 4-methylpyridine.
Examples of the compound represented by the formula (C8) include 1,2-di (2-pyridyl) ethane, 1,2-di (4-pyridyl) ethane, 1,2-di (2-pyridyl) ethene, 1, 2-di (4-pyridyl) ethene, 1,3-di (4-pyridyl) propane, 1,2-di (4-pyridyloxy) ethane, di (2-pyridyl) ketone, 4,4′-dipyridyl sulfide 4,4′-dipyridyl disulfide, 2,2′-dipyridylamine, 2,2′-dipiconylamine, bipyridine and the like.

  As ammonium salts, tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, 3- (trifluoromethyl) phenyltrimethyl Ammonium hydroxide, tetra-n-butylammonium salicylate, choline and the like can be mentioned.

  Examples of weak acid salts include acids generated from the structural unit (p) and acids weaker than acids generated from the acid generator (B), such as carboxylates and sulfonates. It is a salt represented by Formula (C10) or Formula (C11).

［式（Ｃ１０）中、
Ｒ^Ｃ２１は、置換基を有していてもよい炭素数１〜１０の脂肪族炭化水素基、置換基を有してもよい炭素数４〜３６の脂環式炭化水素基、置換基を有していてもよい炭素数３〜３６の芳香族炭化水素基又は置換基を有していてもよい炭素数３〜３６の複素環基を表し、該脂肪族炭化水素基及び該脂環式炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基で置換されていてもよい。
Ｚ６^＋は、有機カチオンを表す。］

[In the formula (C10),
R ^C21 has an optionally substituted aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 4 to 36 carbon atoms that may have a substituent, and a substituent. Represents an optionally substituted aromatic hydrocarbon group having 3 to 36 carbon atoms or an optionally substituted heterocyclic group having 3 to 36 carbon atoms, the aliphatic hydrocarbon group and the alicyclic carbonized group. The methylene group contained in the hydrogen group may be substituted with an oxygen atom or a carbonyl group.
Z6 ⁺ represents an organic cation. ]

［式（Ｃ１１）中、
Ｒ^Ｃ２２及びＲ^Ｃ２３は、互いに独立に、水素原子、炭素数１〜１２の脂肪族炭化水素基、炭素数３〜２０の脂環式飽和炭化水素基、炭素数６〜２０の芳香族炭化水素基又は炭素数７〜２１のアラルキル基を表し、該脂肪族炭化水素基、該脂環式飽和炭化水素基、該芳香族炭化水素基及びアラルキル基に含まれる水素原子は、ヒドロキシ基、シアノ基、フッ素原子、トリフルオロメチル基又はニトロ基で置換されていてもよく、該脂肪族炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基で置き換わっていてもよく、Ｒ^Ｃ２２及びＲ^Ｃ２３は互いに結合してこれらが結合する窒素原子とともに炭素数４〜２０の環を形成してもよい。
Ｚ７^＋は、有機カチオンを表す。］

[In the formula (C11),
R ^C22 and R ^C23 are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or an aromatic hydrocarbon having 6 to 20 carbon atoms. A hydrogen atom contained in the aliphatic hydrocarbon group, the alicyclic saturated hydrocarbon group, the aromatic hydrocarbon group and the aralkyl group is a hydroxy group or a cyano group. , A fluorine atom, a trifluoromethyl group or a nitro group, the methylene group contained in the aliphatic hydrocarbon group may be replaced by an oxygen atom or a carbonyl group, and R ^C22 and R ^C23 are A ring having 4 to 20 carbon atoms may be formed together with the nitrogen atom to which they are bonded to each other.
Z7 ⁺ represents an organic cation. ]

［式（Ｃ９）中、
Ｑ^C1及びＱ^C2は、互いに独立に、フッ素原子又は炭素数１〜６のペルフルオロアルキル基を表す。
Ｌ^C3は、単結合又は炭素数１〜１７の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。
Ｙ^Ｎは窒素原子を含む有機基を表す。
Ｚ５^＋は、有機カチオンを表す。］ Examples of the quencher include a sulfonate having a nitrogen atom, for example, a salt represented by the formula (C9).

[In the formula (C9),
Q ^C1 and Q ^C2 each independently represent a fluorine atom or a ^C 1-6 perfluoroalkyl group.
L ^C3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and the methylene group contained in the divalent saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
Y ^N represents an organic group containing a nitrogen atom.
Z5 ⁺ represents an organic cation. ]

Examples of Q ^C1 and Q ^C2 include the same groups as R ¹ and R ² in formula (I), and preferred examples are also the same.
Y ^N is preferably a heterocyclic group containing a nitrogen atom. Examples of the heterocyclic ring constituting the heterocyclic ring include an imidazole ring and a morpholine ring.

Examples of the saturated hydrocarbon group for L ^C3 include a linear alkanediyl group, a branched alkanediyl group, and a monocyclic or polycyclic alicyclic saturated hydrocarbon group, and two or more of these groups are included. It may be a combination.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 , 6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group , Dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane-1, Linear alkanediyl groups such as 17-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group and propane-2,2-diyl group;
1-methylbutane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1, Branched alkanediyl groups such as 4-diyl groups;
Monocyclic 2 which is a cycloalkanediyl group such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group Valent alicyclic saturated hydrocarbon group;
Polycyclic divalent alicyclic saturated hydrocarbon such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group, etc. Groups and the like.

式（ｃ９−１）〜式（ｃ９−７）中、
Ｌ^c4は、単結合又は炭素数１〜１５の２価の飽和炭化水素基を表す。
Ｌ^c5は、単結合又は炭素数１〜１２の２価の飽和炭化水素基を表す。
Ｌ^c6は、炭素数１〜１３の２価の飽和炭化水素基を表す。但しＬ^c5及びＬ^c6の合計炭素数の上限は１３である。
Ｌ^c７は、単結合又は炭素数１〜１４の２価の飽和炭化水素基を表す。
Ｌ^c８は、炭素数１〜１５の２価の飽和炭化水素基を表す。但しＬ^C7及びＬ^C8の合計炭素数の上限は１５である。
Ｌ^C9は、単結合又は炭素数１〜１５の２価の飽和炭化水素基を表す。
Ｌ^C10は、炭素数１〜１６の２価の飽和炭化水素基を表す。但しＬ^C9及びＬ^C10の合計炭素数の上限は１６である。
Ｌ^C11は、単結合又は炭素数１〜１３の２価の飽和炭化水素基を表す。
Ｌ^C12は、炭素数１〜１４の２価の飽和炭化水素基を表す。但しＬ^C11及びＬ^C12の合計炭素数の上限は１４である。
Ｌ^C13及びＬ^C14は、単結合又は炭素数１〜１１の２価の飽和炭化水素基を表す。
Ｌ^C15は、炭素数１〜１２の２価の飽和炭化水素基を表す。但しＬ^C13、Ｌ^c14及びＬ^C15の合計炭素数の上限は１２である。
Ｌ^C16及びＬ^C17は、それぞれ独立に、単結合又は炭素数１〜１３の２価の飽和炭化水素基を表す。
Ｌ^C18は、炭素数１〜１４の飽和炭化水素基を表す。但しＬ^C16、Ｌ^C17及びＬ^C18の合計炭素数の上限は１４である。 Examples of those in which the methylene group contained in the saturated hydrocarbon group of L ^C3 is replaced with an oxygen atom or a carbonyl group include groups represented by formulas (c9-1) to (c9-7), respectively. . * Represents a bond with C (Q ^C1 ) (Q ^C2 ). The same applies to specific examples of the following formulas (c9-1) to (c9-7).

In formula (c9-1) to formula (c9-7),
L ^c4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 15 carbon atoms.
L ^c5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 12 carbon atoms.
L ^c6 represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms. However, the upper limit of the total carbon number of L ^c5 and L ^c6 is 13.
L ^c7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 14 carbon atoms.
L ^c8 represents a divalent saturated hydrocarbon group having 1 to 15 carbon atoms. However, the upper limit of the total carbon number of L ^C7 and L ^C8 is 15.
L ^C9 represents a single bond or a divalent saturated hydrocarbon group having 1 to 15 carbon atoms.
L ^C10 represents a divalent saturated hydrocarbon group having 1 to 16 carbon atoms. However, the upper limit of the total carbon number of L ^C9 and L ^C10 is 16.
L ^C11 represents a single bond or a divalent saturated hydrocarbon group having 1 to 13 carbon atoms.
L ^C12 represents a divalent saturated hydrocarbon group having 1 to 14 carbon atoms. However, the upper limit of the total carbon number of L ^C11 and L ^C12 is 14.
L ^C13 and L ^C14 represent a single bond or a divalent saturated hydrocarbon group having 1 to 11 carbon atoms.
L ^C15 represents a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. However, the upper limit of the total carbon number of L ^C13 , L ^c14 and L ^C15 is 12.
L ^C16 and L ^C17 each independently represent a single bond or a divalent saturated hydrocarbon group having 1 to 13 carbon atoms.
L ^C18 represents a saturated hydrocarbon group having 1 to 14 carbon atoms. However, the upper limit of the total carbon number of L ^C16 , L ^C17 and L ^C18 is 14.

L ^C3 is preferably a group represented by the formula (c9-1), and a group represented by the formula (c9-1) in which L ^C4 is a single bond or an aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms. More preferred.

Examples of the group represented by the formula (c9-1) include the following.

Examples of the group represented by the formula (c9-2) include the following.

Examples of the group represented by the formula (c9-3) include the following.

Examples of the group represented by the formula (c9-4) include the following.

Examples of the group represented by the formula (c9-5) include the following.

Examples of the group represented by the formula (c9-6) include the following.

Examples of the group represented by the formula (c9-7) include the following.

Examples of the organic cation of Z5 ⁺ , Z6 ⁺ and Z7 ⁺ include the same organic cation as that of Z ⁺ in formula (B1-1), preferably an organic sulfonium cation or an organic iodonium cation, more preferably , A cation represented by any one of formulas (b2-1) to (b2-4).

Examples of the salt represented by the formula (C9) include salts represented by the following formula and salts described in JP 2012-6908 A and JP 2012-72109 A.

Examples of the salt represented by the formula (C10) include a salt represented by the following and a salt described in JP2011-39502A.

As a salt represented by a formula (C11), the salt represented by the following and the salt of Unexamined-Japanese-Patent No. 2011-191745 are mentioned, for example.

  When the resist composition of the present invention contains a quencher (C), the content is preferably 0.01 to 4% by mass with respect to the total amount of solids.

<Solvent (D)>
The solvent (D) is not particularly limited as long as it dissolves the components contained in the resist composition of the present invention. For example, glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate Glycol ethers such as propylene glycol monomethyl ether; esters such as ethyl lactate, butyl acetate, amyl acetate and ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone; lactones such as γ-butyrolactone; And mixed solvents thereof.

  The content of the solvent (D) is preferably 80% by mass or more, more preferably 85% by mass or more, still more preferably 88% by mass or more, and 99.9% by mass or less, based on the total amount of the resist composition of the present invention. Is preferable, and 99.5 mass% or less is more preferable.

<Other components (hereinafter sometimes referred to as “other components (F)”)>
The resist composition of this invention may contain the other component (F) as needed. The other component (F) is not particularly limited, and examples thereof include additives known in the resist field, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, and dyes. The content of the other component (F) is appropriately selected according to the type.

<Method for Producing Resist Composition of the Present Invention>
The resist composition of the present invention comprises a resin (A), an acid generator (B), a crosslinking agent (E), a solvent (D), a quencher (C) and other components (F) used as necessary. ) Can be mixed. The mixing order is arbitrary and is not particularly limited. The temperature at the time of mixing can be suitably selected in the range of 10-40 degreeC according to the kind etc. of resin, the solubility to a solvent (D), etc. The mixing time can be appropriately selected within the range of 0.5 to 24 hours depending on the mixing temperature. The mixing means is not particularly limited, and stirring and mixing can be used. After mixing each component, it is preferable to filter using a filter having a pore size of about 0.003 to 0.2 μm.

<Method for producing resist pattern>
The method for producing a resist pattern of the present invention comprises:
(1) The process of apply | coating the resist composition of this invention on a board | substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer;
(4) A step of heating the composition layer after exposure and (5) a step of developing the composition layer after heating.

  Application of the resist composition of the present invention on the substrate in the step (1) can be performed by a coating apparatus such as a spin coater, which is usually used in the field. Examples of the substrate include a silicon wafer. The substrate may be washed before applying the resist composition of the present invention.

In step (2), the composition after application is dried to remove the solvent and form a composition layer on the substrate. Drying is performed by, for example, heat drying using a heating device such as a hot plate (so-called pre-baking), vacuum drying using a decompression device, or a combination of these means. The temperature in this case is preferably about 50 to 200 ° C., for example. The pressure is preferably about 1 to 1.0 × 10 ⁵ Pa.

Step (3) is a step of exposing the composition layer, and preferably a step of exposing the composition layer using an exposure machine. Exposure light sources include those that emit laser light in the ultraviolet region such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ₂ excimer laser (wavelength 157 nm), electron beams, and ultra-ultraviolet light ( Use various types such as those that irradiate EUV), those that emit laser light from a solid-state laser light source (such as YAG or semiconductor laser) and radiate harmonic laser light in the far ultraviolet region or vacuum ultraviolet region. Can do. The exposure machine may be an immersion exposure machine. In this specification, the irradiation of these radiations may be collectively referred to as “exposure”. The exposure is usually performed through a mask corresponding to a desired resist pattern. When the exposure light source is an electron beam, a desired pattern may be directly drawn without using a photomask.

  Step (4) is a step of heating the composition layer after exposure (so-called post-exposure baking), and preferably a step of developing with a heating device. An example of the heating device is a hot plate. As heating temperature, it is 50-200 degreeC normally, Preferably, it is 70-150 degreeC. The heating time is usually 20 to 90 seconds, preferably 30 to 70 seconds.

  Step (5) is a step of developing the heated composition layer, and preferably a step of developing the heated composition layer with a developing device. Examples of the developing method include a dipping method, a paddle method, a spray method, and a dynamic dispensing method. The development temperature is preferably 5 to 60 ° C., for example, and the development time is preferably 5 to 300 seconds, for example.

By selecting the type of developer, a positive or negative resist pattern can be produced.
When producing a positive resist pattern from the resist composition of the present invention, an alkaline developer is used as the developer. The alkaline developer may be various alkaline aqueous solutions used in this field. Examples thereof include an aqueous solution of tetramethylammonium hydroxide and (2-hydroxyethyl) trimethylammonium hydroxide (commonly called choline). The alkali developer may contain a surfactant.
It is preferable to wash the resist pattern with ultrapure water after development, and then remove the water remaining on the substrate and the pattern.

In the case of producing a negative resist pattern from the resist composition of the present invention, a developer containing an organic solvent as a developer (hereinafter sometimes referred to as “organic developer”) is used.
Organic solvents contained in the organic developer include ketone solvents such as 2-hexanone and 2-heptanone; glycol ether ester solvents such as propylene glycol monomethyl ether acetate; ester solvents such as butyl acetate; glycols such as propylene glycol monomethyl ether Examples include ether solvents; amide solvents such as N, N-dimethylacetamide; aromatic hydrocarbon solvents such as anisole.
In the organic developer, the content of the organic solvent is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, and still more preferably only the organic solvent.
Among them, the organic developer is preferably a developer containing butyl acetate and / or 2-heptanone. In the organic developer, the total content of butyl acetate and 2-heptanone is preferably 50% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, and substantially butyl acetate and / or 2 -More preferred is heptanone alone.
The organic developer may contain a surfactant. The organic developer may contain a trace amount of water.
At the time of development, the development may be stopped by substituting a solvent of a different type from the organic developer.

It is preferable to wash the developed resist pattern with a rinse solution. The rinsing liquid is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used, and an alcohol solvent or an ester solvent is preferable.
After the cleaning, it is preferable to remove the rinse solution remaining on the substrate and the pattern.

<Application>
The resist composition of the present invention is useful as a resist composition for KrF excimer laser exposure, a resist composition for electron beam (EB) irradiation, or a resist composition for EUV exposure. In particular, it is useful for a resist composition for KrF excimer laser exposure, and further, it is useful for a resist composition for ion implantation because a resist pattern having an excellent shape can be produced even when an antireflection film is not used. .

The present invention will be described more specifically with reference to examples. In the examples, “%” and “parts” representing the content or amount used are based on mass unless otherwise specified.
The weight average molecular weight of the resin is a value determined by gel permeation chromatography under the following analysis conditions.
Apparatus: HLC-8120GPC type (manufactured by Tosoh Corporation)
Column: TSKgel Multipore H _XL -M x 3 + guardcolumn (manufactured by Tosoh Corporation)
Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min
Detector: RI detector Column temperature: 40 ° C
Injection volume: 100 μl
Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation)
The introduction ratio of each group in the resin (A) was determined from the ratio of peak areas by ¹ H-NMR.

Synthesis Synthesis Example 1 of Resin (A) [Synthesis of Resin A-1]
40 parts of polyvinylphenol (“VP-15000” manufactured by Nippon Soda Co., Ltd.), 240 parts of methyl isobutyl ketone and 0.006 part of p-toluenesulfonic acid dihydrate are added, and the total amount of this mixed solution becomes 200 parts. Until concentrated. To the concentrated resin solution, 10.55 parts of isobutyl vinyl ether was added dropwise and stirred for 2.5 hours. Thereafter, the mixture was diluted with 80 parts of methyl isobutyl ketone, 120 parts of ion-exchanged water and 0.005 part of triethylamine were added to the solution, stirred and separated. Subsequently, the operation of adding 120 parts of ion-exchanged water to the organic layer and separating the liquid was performed 4 times. The organic layer after washing was concentrated, added with 392 parts of propylene glycol monomethyl ether acetate, and concentrated again to obtain 157 parts of propylene glycol monomethyl ether acetate solution of resin A2-2 (solid content 31%). The weight average molecular weight of Resin A2-2 was 2.00 × 10 ⁴ , and the introduction ratio of isobutoxyethyl groups with respect to all the structural units was 27.2 mol%. Resin A-1 has the following structural units.

Synthesis Example 2 [Synthesis of Resin A-2]
100 parts of polyvinylphenol (“VP-15000” manufactured by Nippon Soda Co., Ltd.) and 400 parts of acetone were added, and then 46.0 parts of potassium carbonate, 28.3 parts of 2-iodopropane and 4.6 parts of water were added. The mixture was stirred and refluxed for 30 hours. Thereafter, 200 parts of methyl isobutyl ketone was added to the reaction solution, and then 258 parts of 2% oxalic acid water was added and stirred for separation. Further, 258 parts of 2% oxalic acid water was added to the organic layer, and the mixture was stirred and separated two times. The operation of separating and washing by adding 300 parts of methyl isobutyl ketone and 166 parts of ion-exchanged water to the organic layer after the separation was performed 4 times. The organic layer after washing was concentrated, 300 parts of methyl isobutyl ketone was further added, and the mixture was concentrated again to obtain 448 parts of a methyl isobutyl ketone solution of resin A-2-1 (solid content 22%).
176 parts of a methyl isobutyl ketone solution of resin A-2-1, 330 parts of methyl isobutyl ketone and 0.004 part of p-toluenesulfonic acid dihydrate were charged and concentrated until the total amount of this mixed solution was 273 parts. 8.01 parts of ethyl vinyl ether was added dropwise to the concentrated resin solution, and the mixture was stirred for 2.5 hours for reaction. Thereafter, 58.2 parts of ion-exchanged water and 0.005 part of triethylamine were added to the reaction solution, and the mixture was stirred and separated. Subsequently, 58.2 parts of ion-exchanged water was added to the organic layer and liquid separation was performed 4 times. The organic layer after washing was concentrated, 260 parts of propylene glycol monomethyl ether acetate was added, and the mixture was concentrated again to obtain 143 parts of a propylene glycol monomethyl ether acetate solution of resin A2-1 (solid content 30%). Resin A-2 had a weight average molecular weight of 1.70 × 10 ⁴ , an introduction rate of isopropyl groups with respect to all structural units was 14.2 mol%, and an introduction rate of ethoxyethyl groups was 29.7 mol%. Resin A-2 has the following structural units.

Synthesis Example 3 [Synthesis of Resin A-3]
30 parts of polyvinylphenol (“VP-15000” manufactured by Nippon Soda Co., Ltd.) was dissolved in 360 parts of methyl isobutyl ketone and concentrated by an evaporator. A four-necked flask equipped with a reflux condenser, a stirrer, and a thermometer is charged with 0.003 part of the concentrated resin solution and p-toluenesulfonic acid dihydrate, and the mixture is kept at 20 to 25 ° C. 6.09 parts of vinyl ether was added dropwise over 10 minutes. The mixture was stirred for 2 hours while maintaining the same temperature, then diluted with 200 parts of methyl isobutyl ketone and subjected to liquid separation washing 5 times with ion-exchanged water. The organic layer after washing was concentrated to 78 parts using an evaporator, and then 220 parts of propylene glycol monomethyl ether acetate was added and concentrated again, and 118 parts of a propylene glycol monomethyl ether acetate solution of resin A1-2. (Solid content 27%) was obtained. Resin A-3 had a weight average molecular weight of 1.90 × 10 ⁴ and an introduction rate of ethoxyethyl groups of 29.6%. Resin A-3 has the following structural units.

Synthesis Example 4 [Synthesis of Resin A-4]
20 parts of polyvinylphenol (“VP-15000” manufactured by Nippon Soda Co., Ltd.) was dissolved in 240 parts of methyl isobutyl ketone and concentrated with an evaporator. A four-necked flask equipped with a reflux condenser, a stirrer, and a thermometer is charged with 0.003 part of the concentrated resin solution and p-toluenesulfonic acid dihydrate, and the mixture is kept at 20 to 25 ° C. 5.05 parts of vinyl ether was added dropwise over 10 minutes. The mixture was stirred for 2 hours while maintaining the same temperature, then diluted with 200 parts of methyl isobutyl ketone and subjected to liquid separation washing 5 times with ion-exchanged water. The organic layer after completion of washing was concentrated to 45 parts using an evaporator, and then 150 parts of propylene glycol monomethyl ether acetate was added and concentrated again, and 78 parts of a propylene glycol monomethyl ether acetate solution of resin A1-2. (Solid content 29%) was obtained. Resin A-4 had a weight average molecular weight of 2.21 × 10 ⁴ and an introduction rate of ethoxyethyl groups of 38.5%. Resin A-4 has the following structural units.

Synthesis Example 5 [Synthesis of Resin A-5]
100 parts of polyvinylphenol (“VP-15000” manufactured by Nippon Soda Co., Ltd.) and 400 parts of acetone were added, then 13.6 parts of triethylamine was added and stirred, and 12.6 parts of benzoyl chloride was added dropwise. After stirring the mixed solution for 2 hours, 200 parts of methyl isobutyl ketone was added, and then 242 parts of 0.5% aqueous oxalic acid was added and stirred for liquid separation. Further, 242 parts of 0.5% oxalic acid water was added to the organic layer and stirred, followed by liquid separation twice. The operation of separating and washing by adding 300 parts of methyl isobutyl ketone and 166 parts of ion-exchanged water to the organic layer after the separation was performed 4 times. The organic layer after washing was concentrated, 300 parts of methyl isobutyl ketone was further added, and the mixture was concentrated again to obtain 356 parts of a methyl isobutyl ketone solution of resin A-5-1 (solid content 27%).
145 parts of a methyl isobutyl ketone solution of resin A-5-1, 375 parts of methyl isobutyl ketone and 0.004 part of p-toluenesulfonic acid dihydrate were charged and concentrated until the total amount of this mixed solution was 280 parts. To the resin solution after concentration, 9.66 parts of ethyl vinyl ether was added dropwise and stirred for 2.5 hours. Thereafter, 60.4 parts of ion-exchanged water and 0.005 part of triethylamine were added and stirred for separation. Subsequently, 60.4 parts of ion-exchanged water was added to the organic layer and liquid separation was performed 4 times. The organic layer after the washing was concentrated, 300 parts of propylene glycol monomethyl ether acetate was added, and the mixture was concentrated again to obtain 162 parts of a propylene glycol monomethyl ether acetate solution of resin A2-3 (solid content 29%). Resin A-5 had a weight average molecular weight of 1.80 × 10 ⁴ , a benzoyl group protection rate of 10.2%, and an ethoxyethyl group introduction rate of 35.3% with respect to all structural units. Resin A-5 has the following structural units.

Examples 1-18, Comparative Examples 1-4
(Preparation of resist composition)
Each of the following components was mixed in parts by mass shown in Table 1 and dissolved in a solvent, and then filtered through a fluororesin filter having a pore size of 0.2 μm to prepare a resist composition.

<Resin>
A-1: Resin A-1
A-2: Resin A-2
A-3: Resin A-3
A-4: Resin A-4
A-5: Resin A-5

Ｂ１−２：イルガキュア（登録商標） ＰＡＧ−１２１（ＢＡＳＦジャパン（株）製）

Ｂ２−１：４−メチルフェニルジフェニルスルホニウム ｐ−トルエンスルホナート；商品名「ＷＰＡＧ−３５０」（和光純薬工業（株）製）

Ｂ２−２：トリフェニルスルホニウム ２，４，６-トリイソプロピルベンゼンスルホナート（東洋合成工業（株）製）

Ｂ２−３：トリス（４‐ｔｅｒｔ‐ブチルフェニル）スルホニウム ｐ−トルエンスルホナート

＜架橋剤＞
Ｅ１：式（Ｅ１）で表される化合物；商品名「ニカラックＭＸ−２７０」（（株）三和ケミカル製）

＜クエンチャー＞
Ｃ１：Ｎ，Ｎ−ジシクロヘキシルメチルアミン（アルドリッチ社製）
Ｃ２:トリス［２-（２-メトキシエトキシ）エチル］アミン（アルドリッチ社製）
Ｃ３：８−モルホリノ−１−オクタノール（東洋合成工業（株）製）
Ｃ４：式（Ｃ４）で表される塩；特開２０１２−１９７２６１号公報記載の方法で合成

＜溶剤＞
プロピレングリコールモノメチルエーテルアセテート １３０部 <Acid generator>
B1-1: Bis (tert-butylsulfonyl) diazomethane; trade name “WPAG-170” (manufactured by Wako Pure Chemical Industries, Ltd.)

B1-2: Irgacure (registered trademark) PAG-121 (manufactured by BASF Japan Ltd.)

B2-1: 4-methylphenyldiphenylsulfonium p-toluenesulfonate; trade name “WPAG-350” (manufactured by Wako Pure Chemical Industries, Ltd.)

B2-2: Triphenylsulfonium 2,4,6-triisopropylbenzenesulfonate (manufactured by Toyo Gosei Co., Ltd.)

B2-3: Tris (4-tert-butylphenyl) sulfonium p-toluenesulfonate

<Crosslinking agent>
E1: Compound represented by the formula (E1); trade name “Nicalak MX-270” (manufactured by Sanwa Chemical Co., Ltd.)

<Quencher>
C1: N, N-dicyclohexylmethylamine (manufactured by Aldrich)
C2: Tris [2- (2-methoxyethoxy) ethyl] amine (Aldrich)
C3: 8-morpholino-1-octanol (manufactured by Toyo Gosei Co., Ltd.)
C4: salt represented by the formula (C4); synthesized by the method described in JP2012-197261A

<Solvent>
130 parts of propylene glycol monomethyl ether acetate

(Manufacture of negative resist patterns)
A 4-inch silicon wafer was treated with hexamethyldisilazane at 90 ° C. for 60 seconds on a direct hot plate. This silicon wafer was spin-coated with a resist composition so that the film thickness of the composition layer was 300 nm. Then, it prebaked at 90 degreeC for 60 second on the direct hotplate, and formed the composition layer. Using a KrF excimer laser exposure machine [NSR-2250EX12B; manufactured by Nikon Corporation, NA = 0.55, 2/3 Annular], the amount of exposure is changed stepwise for the composition layer formed on the wafer. A 1: 1 line and space pattern was exposed.
After exposure, a negative resist pattern was obtained by performing post-exposure baking at 110 ° C. for 60 seconds on a hot plate and further performing dynamic dispense development with butyl acetate for 30 seconds.
The obtained resist pattern (line and space pattern) was observed with a scanning electron microscope, and the exposure amount at which the line width and space width of the line and space pattern having a line width of 300 nm were 1: 1 was defined as effective sensitivity.

Resolution evaluation: The resist pattern obtained at the effective sensitivity was observed with a scanning electron microscope, and the minimum line width at which the resist pattern was resolved without falling down was defined as the resolution. The results are shown in Table 2.
Shape evaluation: A 300 nm line and space pattern obtained in effective sensitivity was observed with a scanning electron microscope. As shown in FIG. As shown in 1 (b), a taper-shaped one was judged as x. The results are shown in Table 2.
Scum evaluation: A resist pattern manufactured with effective sensitivity was observed with a scanning electron microscope, and no development residue (scum) was observed in the space part of the line-and-space pattern. The thing was set as x. The results are shown in Table 2.

(Manufacture of positive resist pattern)
A 4-inch silicon wafer was treated with hexamethyldisilazane at 90 ° C. for 60 seconds on a direct hot plate. This silicon wafer was spin-coated with a resist composition so that the film thickness of the composition layer was 300 nm. Then, it prebaked at 90 degreeC for 60 second on the direct hotplate, and formed the composition layer. Using a KrF excimer laser exposure machine [NSR-2250EX12B; manufactured by Nikon Corporation, NA = 0.55, 2/3 Annular], the amount of exposure is changed stepwise for the composition layer formed on the wafer. A 1: 1 line and space pattern was exposed.
After exposure, a positive exposure pattern is obtained by post-exposure baking at 120 ° C. for 60 seconds on a hot plate, and further paddle development for 60 seconds with an aqueous 2.38 mass% tetramethylammonium hydroxide solution. It was.
The obtained resist pattern (line and space pattern) was observed with a scanning electron microscope, and the exposure amount at which the line width and space width of the line and space pattern having a line width of 300 nm were 1: 1 was defined as effective sensitivity.

  Resolution evaluation: The resist pattern obtained at the effective sensitivity was observed with a scanning electron microscope, and the minimum line width at which the resist pattern was resolved without falling was defined as the resolution. The results are shown in Table 3.

  From the above results, it can be seen that the resist composition of the present invention can produce a negative resist pattern having an excellent shape and less scum generation. Furthermore, a positive resist pattern can also be produced from the resist composition of the present invention.

  According to the resist composition of the present invention, it is possible to produce a negative resist pattern with an excellent shape and less development residue (scum).

Claims (3)

(1) A resist composition containing a resin comprising a structural unit having an acid labile group and a structural unit having a phenolic hydroxy group, a nonionic acid generator, an ionic acid generator, and a crosslinking agent on a substrate Applying step,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer;
(4) a step of heating the composition layer after exposure, and
(5) The process of developing the composition layer after a heating using the organic type developing solution containing 90 mass% or more of organic solvents,
A negative resist pattern manufacturing method comprising: A resin containing a structural unit having an acid labile group and a structural unit having a phenolic hydroxy group, a nonionic acid generator, an ionic acid generator and a crosslinking agent;
The method for producing a negative resist pattern according to claim 1, wherein the content of the nonionic acid generator is 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the resin. The method for producing a negative resist pattern according to claim 1 or 2, wherein the content ratio of the nonionic acid generator to the ionic acid generator is 40:60 to 95: 5 on a mass basis.

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