JP2011197067A - Resist composition and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resist composition for acquiring a pattern having a high focus margin (DOF), CD uniformity (CDU), and a mask error factor (MEF), and a forming method of a resist pattern using the resist composition.SOLUTION: The resist composition includes resin that contains a group unstable to an acid is insoluble or difficult-soluble in an aqueous alkali solution, and acts with an acid to be dissolved in the aqueous alkali solution, an acid generator, a compound having a quinoid structure, and a quencher. The forming method of the resist pattern uses the resist composition.

Description

  The present invention relates to a resist composition and a method for manufacturing a resist pattern, and more particularly to a resist composition used for fine processing of a semiconductor and a method for manufacturing a resist pattern.

  A resist composition used for fine processing of a semiconductor using a lithography technique contains a salt that generates an acid upon exposure and a resin.

  Patent Document 1 is charged with 2-ethyl-2-adamantyl methacrylate, 3-hydroxy-1-adamantyl methacrylate and α-methacryloyloxy-γ-butyrolactone as a resin in a molar ratio of 50:25:25. A resist composition containing a resin obtained by polymerization and triphenylsulfonium 1-((3-hydroxyadamantyl) methoxycarbonyl) difluoromethanesulfonate as an acid generator is described.

JP 2006-257078 A

  Conventional resist compositions may not always satisfy the focus margin (DOF), CD uniformity (CDU) and mask error factor (MEF) of the resulting pattern.

The present application provides the following inventions.
[1] a resin having an acid labile group and insoluble or hardly soluble in an alkaline aqueous solution, which can be dissolved in an alkaline aqueous solution by acting with an acid, an acid generator, a compound having a quinoid structure, A resist composition containing a quencher.

［式（Ｉ）中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４、は、それぞれ独立に、水素原子、ハロゲン原子又はシアノ基を表す。
Ａ^１及びＡ^２は、それぞれ独立に、＝Ｏ、＝ＣＲ^５Ｒ^６又は＝ＮＲ^７を表す。
Ｒ^５、Ｒ^６及びＲ^７は、それぞれ独立に、水素原子又は炭素数１〜４のアルキル基を表す。］
〔３〕クエンチャーが、ベンジル基を有する化合物である〔１〕又は〔２〕記載のレジスト組成物。
〔４〕クエンチャーが、式（II）で表される化合物又は式（III）で表される化合物である〔１〕〜〔３〕のいずれか記載のレジスト組成物。

［式（II）中、
Ｒ^ｂ1、Ｒ^ｂ２及びＲ^ｂ３は、それぞれ独立に、水素原子又は炭素数１〜１２の炭化水素基を表すか、Ｒ^ｂ１及びＲ^ｂ２は互いに結合して炭素数３〜３６の環を形成してもよく、該炭化水素基及び環に含まれる水素原子は、−ＯＨで置換されていてもよく、該炭化水素基及び環に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−で置き換わっていてもよい。
Ｒ^ｂ４及びＲ^ｂ５は、それぞれ独立に、水素原子、炭素数１〜６のアルキル基、炭素数６〜１２の飽和環状炭化水素基、炭素数６〜１２の芳香族炭化水素基又は炭素数５〜９の芳香族複素環基を表すか、Ｒ^ｂ４及びＲ^ｂ５は互いに結合して５員又は６員の複素環を形成してもよく、該アルキル基に含まれる水素原子は、−ＯＨ、−ＳＨ、−ＮＨ_２、炭素数６〜１２の飽和環状炭化水素基、炭素数６〜１２の芳香族炭化水素基又は炭素数５〜９の芳香族複素環基で置換されていてもよく、該アルキル基に含まれる−ＣＨ_２−は、−Ｏ−、−Ｓ−、−ＣＯ−、−Ｃ（＝ＮＨ）−又は−ＮＨ−で置き換わっていてもよい。該飽和環状炭化水素基、該芳香族炭化水素基及び該芳香族複素環基に含まれる水素原子は、−ＯＨで置換されていてもよい。
Ｒ^ｂ６、Ｒ^ｂ７、Ｒ^ｂ８、Ｒ^ｂ９及びＲ^ｂ１０は、それぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、シアノ基、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２〜７のアルコキシカルボニル基又は置換基を有してもよい炭素数６〜１２の芳香族炭化水素基を表す。
式（III）中、
Ｒ^ｄ1及びＲ^ｄ２は、それぞれ独立に、置換基を有していてもよい炭素数１〜１８のアルキレン基を表す。
Ｒ^ｄ３、Ｒ^ｄ４、Ｒ^ｄ５、Ｒ^ｄ６及びＲ^ｄ７は、それぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、シアノ基、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２〜７のアルコキシカルボニル基又は置換基を有してもよい炭素数６〜１２の芳香族炭化水素基を表す。］ [2] The resist composition according to [1], wherein the compound having a quinoid structure is a compound represented by the formula (I).

[In formula (I), R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom, a halogen atom or a cyano group.
A ¹ and A ² each independently represent ═O, ═CR ⁵ R ⁶ or ═NR ⁷ .
R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]
[3] The resist composition according to [1] or [2], wherein the quencher is a compound having a benzyl group.
[4] The resist composition according to any one of [1] to [3], wherein the quencher is a compound represented by formula (II) or a compound represented by formula (III).

[In the formula (II),
R ^b1 , R ^b2 and R ^b3 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, or R ^b1 and R ^b2 are bonded to each other to form a ring having 3 to 36 carbon atoms. The hydrogen atom contained in the hydrocarbon group and the ring may be substituted with —OH, and —CH ₂ — contained in the hydrocarbon group and the ring is —O— or —CO—. It may be replaced.
R ^b4 and R ^b5 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a saturated cyclic hydrocarbon group having 6 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or 5 carbon atoms. Or an aromatic heterocyclic group of ˜9, or R ^b4 and R ^b5 may be bonded to each other to form a 5-membered or 6-membered heterocyclic ring, and the hydrogen atom contained in the alkyl group is —OH, -SH, -NH _2, it may be substituted by a saturated cyclic hydrocarbon group, aromatic hydrocarbon group or an aromatic heterocyclic group having a carbon number of 5 to 9 having 6 to 12 carbon atoms of 6 to 12 carbon atoms, —CH ₂ — contained in the alkyl group may be replaced by —O—, —S—, —CO—, —C (═NH) — or —NH—. Hydrogen atoms contained in the saturated cyclic hydrocarbon group, the aromatic hydrocarbon group, and the aromatic heterocyclic group may be substituted with —OH.
R ^b6 , R ^b7 , R ^b8 , R ^b9 and R ^b10 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Group, a C2-C4 acyl group, a C2-C7 alkoxycarbonyl group, or a C6-C12 aromatic hydrocarbon group which may have a substituent.
In formula (III),
R ^d1 and R ^d2 each independently represent an alkylene group having 1 to 18 carbon atoms which may have a substituent.
R ^d3 , R ^d4 , R ^d5 , R ^d6 and R ^d7 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Group, a C2-C4 acyl group, a C2-C7 alkoxycarbonyl group, or a C6-C12 aromatic hydrocarbon group which may have a substituent. ]

[5] (1) A step of applying the resist composition according to any one of [1] to [4] on a substrate,
(2) a step of removing the solvent from the composition after coating to form a composition layer;
(3) a step of exposing the composition layer using an exposure machine;
(4) A step of heating the composition layer after exposure,
(5) a step of developing the heated composition layer using a developing device;
A method for producing a resist pattern including:

  According to the resist composition of the present invention, a pattern having excellent focus margin (DOF), CD uniformity (CDU) and mask error factor (MEF) can be obtained.

The resist composition of the present invention comprises a resin (hereinafter sometimes referred to as “resin (A)”), an acid generator (hereinafter also referred to as “acid generator (B)”), and a compound having a quinoid structure ( Hereinafter, it may be referred to as “compound (D) having a quinoid structure”) and a quencher (hereinafter also referred to as “quencher (G)”).
<Resin (A)>
Resin (A) is a resin that has an acid labile group and is insoluble or hardly soluble in an aqueous alkali solution and can be dissolved in an aqueous alkali solution by acting with an acid, that is, “alkaline before contact with an acid. A resin that is insoluble or sparingly soluble in an aqueous solution but becomes soluble in an aqueous alkaline solution after contact with an acid.
This resin can be produced by polymerizing a monomer having an acid labile group (hereinafter sometimes referred to as “monomer having an acid labile group (a1)”). As the monomer (a1) having an acid labile group, one type may be used alone, or two or more types may be used in combination.

<Monomer (a1) having an acid labile group>
The term “acid-labile group” means a group that cleaves a leaving group upon contact with an acid to form a hydrophilic group (for example, a hydroxy group or a carboxy group). Examples of the acid labile group include an alkoxycarbonyl group represented by the formula (1) in which —O— is bonded to a tertiary carbon atom (excluding a bridgehead carbon atom of a bridged cyclic hydrocarbon group) (ie, An ester bond having a tertiary alcohol residue). Hereinafter, the group represented by the formula (1) may be referred to as “acid-labile group (1)”.

式（１）中、Ｒ^a1〜Ｒ^a3は、それぞれ独立に、脂肪族炭化水素基又は飽和環状炭化水素基を表すか或いはＲ^a1及びＲ^a2は互いに結合して環を形成していてもよい。＊は結合手を表す（以下同じ）。

In formula (1), R ^{a1 to} R ^a3 each independently represents an aliphatic hydrocarbon group or a saturated cyclic hydrocarbon group, or R ^a1 and R ^a2 may be bonded to each other to form a ring. . * Represents a bond (same below).

  Examples of the aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, 1-methylethyl group (isopropyl group), n-butyl group, 1,1-dimethylethyl group (tert-butyl group), 2, 2-dimethylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, 1-ethylpropyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, n-hexyl group, 1-propylbutyl group, pentyl group, 1-methylpentyl group, 1,4-dimethylhexyl group, heptyl group, 1-methylheptyl group, octyl group, Examples thereof include alkyl groups such as nonyl group, decyl group, undecyl group, and dodecyl group.

芳香族炭化水素基としては、フェニル基、ナフチル基、アントラニル基、ｐ−メチルフェニル基、ｐ−ｔｅｒｔ−ブチルフェニル基、ｐ−アダマンチルフェニル基、トリル基、キシリル基、クメニル基、メシチル基、ビフェニル基、アントリル基、フェナントリル基、２，６−ジエチルフェニル基、２−メチル−６−エチルフェニル等のアリール基等が挙げられる。 The saturated cyclic hydrocarbon group may be monocyclic or polycyclic, for example, a cycloalkyl group (for example, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, A monocyclic saturated cyclic hydrocarbon group such as a cyclooctyl group; a group obtained by hydrogenating a condensed aromatic hydrocarbon group (for example, a hydronaphthyl group), a bridged cyclic hydrocarbon group (for example, an adamantyl group, Norbornyl group, methylnorbornyl group) and the like. Further, a bridged ring (for example, norbornane ring, bicyclo [2.2.2] octane ring) and a single ring (for example, cycloheptane ring, cyclohexane ring) or a polycyclic (for example, decahydronaphthalene ring) as shown below. Examples thereof include a condensed group or a group in which bridging rings are condensed; a group in which these are combined (methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group) and the like. Moreover, (Y1)-(Y11) shown below may be sufficient.

As aromatic hydrocarbon group, phenyl group, naphthyl group, anthranyl group, p-methylphenyl group, p-tert-butylphenyl group, p-adamantylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, biphenyl Groups, anthryl groups, phenanthryl groups, 2,6-diethylphenyl groups, aryl groups such as 2-methyl-6-ethylphenyl, and the like.

Examples of the ring formed by combining R ^a1 and R ^a2 with each other include a saturated cyclic hydrocarbon group and an aromatic hydrocarbon group.

  In the present specification, any of the chemical structural formulas having similar substituents can apply the specific substituents described above or described later while appropriately selecting the number of carbon atoms. Those which can take any of linear, branched or cyclic are included unless otherwise specified, and in the same group, linear, branched and / or cyclic partial structures are mixed. It may be. When stereoisomers exist, all of those stereoisomers are included. Furthermore, each substituent can be a monovalent or divalent or higher substituent depending on the bonding site and the bonding mode.

In the formula (1), the saturated cyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms.
The ring formed by combining R ^a1 and R ^a2 with each other preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.

Examples of the acid labile group (1) include a 1,1-dialkylalkoxycarbonyl group (in the group (1), R ^{a1 to} R ^a3 are alkyl groups, preferably a tert-butoxycarbonyl group), 2-alkyl-2-adamantyloxycarbonyl group (in the formula (1), R ^a1 , R ^a2 and a carbon atom form an adamantyl group, and R ^a3 is an alkyl group) and 1- (1-adamantyl)- 1-alkylalkoxycarbonyl groups (in the formula (1), R ^a1 and R ^a2 are alkyl groups and R ^a3 is an adamantyl group) and the like.

  The monomer (a1) having an acid labile group is preferably a monomer having an acid labile group (1) and a carbon-carbon double bond, more preferably an acid labile group (1). (Meth) acrylic monomer having

  Among the (meth) acrylic monomers having the acid-labile group (1), those having a saturated cyclic hydrocarbon group having 5 to 20 carbon atoms are preferred. If a resin obtained by polymerizing the monomer (a1) having a bulky structure such as a saturated cyclic hydrocarbon group is used, the resolution of the resist can be improved.

  Among the (meth) acrylic monomers having the acid labile group (1) and the saturated cyclic hydrocarbon group, the acid labile group represented by the formula (a1-1) or the formula (a1-2) Monomers having are preferred. These may be used alone or in combination of two or more.

式（ａ１−１）及び式（ａ１−２）中、
Ｌ^a1及びＬ^a2は、それぞれ独立に、−Ｏ−又は−Ｏ−（ＣＨ₂）_k1−ＣＯ−Ｏ−を表し、ｋ１は１〜７の整数を表す。但しＬ^a1及びＬ^a2で列挙した−Ｏ−等は、それぞれ、左側で式（ａ１−１）及び式（ａ１−２）の−ＣＯ−と結合し、右側でアダマンチル基又はシクロへキシル基と結合することを意味する。
Ｒ^a4及びＲ^a5は、それぞれ独立に、水素原子又はメチル基を表す。
Ｒ^a6及びＲ^a7は、それぞれ独立に、炭素数１〜８の脂肪族炭化水素基又は炭素数３〜１０の飽和環状炭化水素基を表す。
ｍ１は０〜１４の整数を表す。
ｎ１は０〜１０の整数を表す。

In formula (a1-1) and formula (a1-2),
L ^a1 and L ^a2 each independently represent —O— or —O— (CH ₂ ) _k1 —CO—O—, and k1 represents an integer of 1 to 7. However, —O— and the like enumerated for L ^a1 and L ^a2 are respectively bonded to —CO— of the formula (a1-1) and the formula (a1-2) on the left side, and to an adamantyl group or cyclohexyl group on the right side. Means to join.
R ^a4 and R ^a5 each independently represent a hydrogen atom or a methyl group.
R ^a6 and R ^a7 each independently represent an aliphatic hydrocarbon group having 1 to 8 carbon atoms or a saturated cyclic hydrocarbon group having 3 to 10 carbon atoms.
m1 represents the integer of 0-14.
n1 represents an integer of 0 to 10.

In the formula (a1-1) and the formula (a1-2), L ^a1 and L ^a2 are preferably, -O- or _{-O- (CH 2) f1 -CO-} O- and is (wherein f1 is 1 to 4), and more preferably -O-.
R ^a4 and R ^a5 are preferably methyl groups.
The aliphatic hydrocarbon group represented by R ^a6 and R ^a7 preferably has 6 or less carbon atoms. The saturated cyclic hydrocarbon group preferably has 8 or less carbon atoms, more preferably 6 or less carbon atoms.
m1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 is preferably an integer of 0 to 3, more preferably 0 or 1.
k1 is preferably an integer of 1 to 4, more preferably 1.

  As a monomer (a1-1) which has an adamantyl group, the following are mentioned, for example. Among them, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate and 2-isopropyl-2-adamantyl (meth) acrylate are preferable, and those in the form of methacrylate are more preferable.

  As a monomer (a1-2) which has a cyclohexyl group, the following are mentioned, for example. Among these, 1-ethyl-1-cyclohexyl (meth) acrylate is preferable, and 1-ethyl-1-cyclohexyl methacrylate is more preferable.

  The content of the repeating unit derived from the monomer represented by the formula (a1-1) or the formula (a1-2) in the resin is usually 10 to 95 mol%, preferably 15 to 90, in all units of the resin. It is mol%, More preferably, it is 20-85 mol%.

  Examples of the monomer having an acid labile group (1) and a carbon-carbon double bond include a monomer having a norbornene ring represented by the formula (a1-3). Since the resin having a structural unit derived from the monomer (a1-3) having an acid labile group has a bulky structure, the resolution of the resist can be improved. Furthermore, the monomer (a1-3) having an acid labile group can improve the resistance to dry etching of a resist by introducing a rigid norbornane ring into the main chain of the resin.

式（ａ１−３）中、
Ｒ^a9は、水素原子、置換基（例えば、ヒドロキシ基）を有していてもよい炭素数１〜３の脂肪族炭化水素基、カルボキシ基、シアノ基又はアルコキシカルボニル基（−ＣＯＯＲ^a13）を表し、Ｒ^a13は、炭素数１〜８の脂肪族炭化水素基又は炭素数３〜８の飽和環状炭化水素基を表し、前記脂肪族炭化水素基及び前記飽和環状炭化水素基の水素原子はヒドロキシ基で置換されていてもよく、前記脂肪族炭化水素基及び前記飽和環状炭化水素基の−ＣＨ_２−は−Ｏ−又は−ＣＯ−で置き換わっていてもよい。
Ｒ^a10〜Ｒ^a12は、それぞれ独立に、炭素数１〜１２の脂肪族炭化水素基又は炭素数３〜１２の飽和環状炭化水素基を表すか、或いはＲ^a10及びＲ^a11は互いに結合して環を形成していてもよく、前記脂肪族炭化水素基及び前記飽和環状炭化水素基の水素原子はヒドロキシ基等で置換されていてもよく、前記脂肪族炭化水素基及び前記飽和環状炭化水素基の−ＣＨ_２−は−Ｏ−又は−ＣＯ−で置き換わっていてもよい。

In formula (a1-3),
R ^a9 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 3 carbon atoms which may have a substituent (for example, a hydroxy group), a carboxy group, a cyano group, or an alkoxycarbonyl group (—COOR ^a13 ). R ^a13 represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms or a saturated cyclic hydrocarbon group having 3 to 8 carbon atoms, and the hydrogen atom of the aliphatic hydrocarbon group and the saturated cyclic hydrocarbon group is a hydroxy group In the aliphatic hydrocarbon group and the saturated cyclic hydrocarbon group, —CH ₂ — may be replaced by —O— or —CO—.
R ^{a10 to} R ^a12 each independently represents an aliphatic hydrocarbon group having 1 to 12 carbon atoms or a saturated cyclic hydrocarbon group having 3 to 12 carbon atoms, or R ^a10 and R ^a11 are bonded to each other to form a ring The hydrogen atom of the aliphatic hydrocarbon group and the saturated cyclic hydrocarbon group may be substituted with a hydroxy group or the like, and the aliphatic hydrocarbon group and the saturated cyclic hydrocarbon group —CH ₂ — may be replaced by —O— or —CO—.

  Here, examples of the alkoxycarbonyl group include groups in which a carbonyl group is bonded to an alkoxy group such as a methoxycarbonyl group or an ethoxycarbonyl group.

Examples of the aliphatic hydrocarbon group which may have a substituent for R ^a9 include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a 2-hydroxyethyl group.
^Examples of R ^a13 include a methyl group, an ethyl group, a propyl group, a 2-oxo-oxolan-3-yl group, and a 2-oxo-oxolan-4-yl group.
Examples of R ^{a10 to} R ^a12 include a methyl group, an ethyl group, a cyclohexyl group, a methylcyclohexyl group, a hydroxycyclohexyl group, an oxocyclohexyl group, and an adamantyl group.
Examples of the ring formed by R ^a10 , R ^a11 and the carbon to which they are bonded include saturated cyclic hydrocarbon groups, and specific examples include a cyclohexyl group and an adamantyl group.

  Examples of the monomer (a1-3) having a norbornene ring include, for example, 5-norbornene-2-carboxylic acid-tert-butyl, 5-norbornene-2-carboxylic acid 1-cyclohexyl-1-methylethyl, 5-norbornene-2 -1-methylcyclohexyl carboxylate, 2-methyl-2-adamantyl 5-norbornene-2-carboxylate, 2-ethyl-2-adamantyl 5-norbornene-2-carboxylate, 5-norbornene-2-carboxylic acid 1- (4-methylcyclohexyl) -1-methylethyl, 5-norbornene-2-carboxylic acid 1- (4-hydroxycyclohexyl) -1-methylethyl, 5-norbornene-2-carboxylic acid 1-methyl-1- (4 -Oxocyclohexyl) ethyl, 5-norbornene-2-carboxylic acid 1- (1-adap Pentyl) -1-methylethyl and the like.

  The content of the repeating unit derived from the monomer represented by the formula (a1-3) in the resin is usually 10 to 95 mol%, preferably 15 to 90 mol%, more preferably in all units of the resin. Is 20 to 85 mol%.

［式（ａ１−４）中、
Ｒ¹⁰は、水素原子、ハロゲン原子又はハロゲン原子を有してもよい炭素数１〜６のアルキル基を表す。
Ｒ¹¹は、それぞれ独立に、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。
ｌａは０〜４の整数を表す。ｌａが２以上の整数である場合、複数のＲ¹¹は同一であっても異なってもよい。
Ｒ¹²及びＲ¹³はそれぞれ独立に、水素原子又は炭素数１〜１２の炭化水素基を表す。
Ｘ^ａ２は、単結合又は置換基を有していてもよい２価の炭素数１〜１７の飽和炭化水素基を表し、該飽和炭化水素基に含まれる−ＣＨ_２−は−ＣＯ−、−Ｏ−、−Ｓ−、−ＳＯ_２−又は−Ｎ（Ｒ^ｃ）−で置き換わっていてもよい。Ｒ^ｃは、水素原子又は炭素数１〜６のアルキル基を表す。
Ｙ^ａ３は、炭素数１〜１２の脂肪族炭化水素基、炭素数３〜１８の飽和環状炭化水素基又は炭素数６〜１８の芳香族炭化水素基であり、該脂肪族炭化水素基、飽和環状炭化水素基及び芳香族炭化水素基は、置換基を有していてもよい。］ Examples of the monomer having the acid labile group (1) and the carbon-carbon double bond include a monomer (a1-4) represented by the formula (a1-4).

[In the formula (a1-4),
R ¹⁰ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
R ¹¹ each independently represents 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, Represents an acryloyl group or a methacryloyl group.
la represents an integer of 0 to 4. When la is an integer of 2 or more, the plurality of R ¹¹ may be the same or different.
R ¹² and R ¹³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms.
X ^a2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms which may have a substituent, and —CH ₂ — contained in the saturated hydrocarbon group is —CO—, — O—, —S—, —SO ₂ — or —N (R ^c ) — may be substituted. R ^c represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Y ^a3 is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a saturated cyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the aliphatic hydrocarbon group, saturated The cyclic hydrocarbon group and the aromatic hydrocarbon group may have a substituent. ]

Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms.
Examples of the alkyl group that may have a halogen atom include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, and a perfluoropentyl group. Perfluorohexyl group, perchloromethyl group, perbromomethyl group, periodomethyl group and the like.
Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, an n-pentoxy group, and an n-hexoxy group. .
Examples of the acyl group include acetyl, propionyl, butyryl and the like.
Examples of the acyloxy group include acetyloxy, propionyloxy, butyryloxy and the like.
Examples of the hydrocarbon group include an aliphatic hydrocarbon group, a saturated cyclic hydrocarbon group, and an aromatic hydrocarbon group.

Examples of the divalent saturated hydrocarbon group include a linear alkylene group, a branched alkylene group, a monocyclic or polycyclic saturated cyclic hydrocarbon group, and a combination of two or more of these groups But you can.
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 alkylene groups such as 17-diyl group, methylidene group, ethylidene group, propylidene group, 2-propylidene group;
On the side of an alkyl group (particularly an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group) Having a chain, for example, 1-methyl-1,3-propylene group, 2-methyl-1,3-propylene group, 2-methyl-1,2-propylene group, 1-methyl-1,4-butylene Group, branched alkylene such as 2-methyl-1,4-butylene group;
Monocyclic saturated cyclic hydrocarbon groups which are cycloalkylene groups such as 1,3-cyclobutylene group, 1,3-cyclopentylene group, 1,4-cyclohexylene group, 1,5-cyclooctylene group;
Examples thereof include polycyclic saturated cyclic hydrocarbon groups such as 1,4-norbornylene group, 2,5-norbornylene group, 1,5-adamantylene group, 2,6-adamantylene group and the like.

In formula (a1-4), the alkyl group of R ¹⁰ and R ¹¹ preferably has 1 to 4 carbon atoms, more preferably 1 or 2 carbon atoms, and particularly preferably a methyl group.
As the alkoxy group for R ¹¹ , C 1 or 2 is more preferable, and a methoxy group is particularly preferable.
Examples of the hydrocarbon group for R ¹² and R ¹³ include isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, cyclohexyl group, adamantyl group, A 2-alkyl-2-adamantyl group, a 1- (1-adamantyl) -1-alkyl group, an isobornyl group, and the like are preferable.
Examples of the group that may be substituted with the groups X ^a2 and Y ^a3 include a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an acyl group having 2 to 4 carbon atoms. And an acyloxy group having 2 to 4 carbon atoms. Of these, a hydroxy group is preferable.

  As a monomer (a1-4), the following monomers are mentioned, for example.

  The content of the repeating unit derived from the monomer represented by the formula (a1-4) in the resin is usually 10 to 95 mol%, preferably 15 to 90 mol%, more preferably in all units of the resin. Is 20 to 85 mol%.

The resin (A) is preferably a co-polymerization of a monomer (a1) having an acid labile group and a monomer having no acid labile group (hereinafter sometimes referred to as “acid stable monomer”). It is a coalescence. An acid stable monomer may be used individually by 1 type, and may use 2 or more types together.
When the resin (A) is a copolymer of a monomer (a1) having an acid labile group and an acid stable monomer, the structural units derived from the monomer (a1) having an acid labile group are all Preferably it is 10-80 mol% with respect to 100 mol% of structural units, More preferably, it is 20-60 mol%. Further, the structural unit derived from the monomer having an adamantyl group (particularly the monomer (a1-1) having an acid labile group) is converted to 15 mol per 100 mol% of the monomer (a1) having an acid labile group. It is preferable to set it as mol% or more. When the ratio of the monomer having an adamantyl group increases, the dry etching resistance of the resist is improved.

  As the acid stable monomer, those having a hydroxy group or a lactone ring are preferred. Derived from an acid stable monomer having a hydroxy group (hereinafter referred to as “acid stable monomer having a hydroxy group (a2)”) or an acid stable monomer having a lactone ring (hereinafter referred to as “acid stable monomer having a lactone ring (a3)”) If a resin having a structural unit to be used is used, the resolution of the resist and the adhesion to the substrate can be improved.

<Acid-stable monomer having a hydroxy group (a2)>
When the resist composition is used for KrF excimer laser exposure (248 nm), high energy beam exposure such as electron beam or EUV light, an acid-stable monomer (a2) having a hydroxy group has an acid having a phenolic hydroxyl group which is a hydroxystyrene. It is preferable to use a stable monomer (a2-0). When using short wavelength ArF excimer laser exposure (193 nm) or the like, an acid stable monomer having a hydroxyadamantyl group represented by formula (a2-1) should be used as the acid stable monomer having a hydroxy group (a2). Is preferred. The acid-stable monomer (a2) having a hydroxy group may be used alone or in combination of two or more.

  Examples of the monomer (a2-0) having a phenolic hydroxyl group include styrene monomers such as p- or m-hydroxystyrene represented by the formula (a2-0).

［式（ａ２−０）中、
Ｒ^８は、水素原子、ハロゲン原子又はハロゲン原子を有してもよい炭素数１〜６のアルキル基を表す。
Ｒ^９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^９は同一であっても異なってもよい。］

[In the formula (a2-0),
R ⁸ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
R ⁹ 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 ⁹ may be the same or different. ]

As the alkyl group for R ^8, an alkyl group having 1 to 4 carbon atoms is preferable, an alkyl group having 1 or 2 carbon atoms is more preferable, and a methyl group is particularly preferable.
Moreover, as an alkoxy group, a C1-C4 alkoxy group is preferable, a C1-C2 alkoxy group is more preferable, and a methoxy group is especially preferable.
ma is preferably 0 to 2, more preferably 0 or 1, and particularly preferably 0.

When obtaining a copolymer resin having a structural unit derived from a monomer having such a phenolic hydroxyl group, the corresponding (meth) acrylic acid ester monomer, acetoxystyrene and styrene are radically polymerized and then deacetylated with an acid. Can be obtained by:
Examples of the monomer having a phenolic hydroxyl group include the following monomers.

  Of the above monomers, 4-hydroxystyrene or 4-hydroxy-α-methylstyrene is particularly preferred.

  The content of the repeating unit derived from the monomer represented by the formula (a2-0) in the resin is usually 5 to 90 mol%, preferably 10 to 85 mol%, more preferably in all units of the resin. Is 15 to 80 mol%.

  Examples of the acid stable monomer having a hydroxyadamantyl group include a monomer represented by the formula (a2-1).

式（ａ２−１）中、
Ｌ^a3は、−Ｏ−又は−Ｏ−（ＣＨ₂）_k2−ＣＯ−Ｏ−を表し、
ｋ２は１〜７の整数を表す。
Ｒ^a14は、水素原子又はメチル基を表す。
Ｒ^a15及びＲ^a16は、それぞれ独立に、水素原子、メチル基又はヒドロキシ基を表す。
ｏ１は、０〜１０の整数を表す。

In formula (a2-1),
L ^a3 represents —O— or —O— (CH ₂ ) _k2 —CO—O—,
k2 represents an integer of 1 to 7.
R ^a14 represents a hydrogen atom or a methyl group.
R ^a15 and R ^a16 each independently represent a hydrogen atom, a methyl group or a hydroxy group.
o1 represents an integer of 0 to 10.

In the formula (a2-1), L ^a3 is preferably, -O -, - O- (CH 2) f1 -CO-O- and is (wherein f1 is an integer from 1 to 4), more preferably Is —O—.
R ^a14 is preferably a methyl group.
R ^a15 is preferably a hydrogen atom.
R ^a16 is preferably a hydrogen atom or a hydroxy group.
o1 is preferably an integer of 0 to 3, more preferably 0 or 1.

  As an acid stable monomer (a2-1) which has a hydroxyadamantyl group, the following are mentioned, for example. Among them, 3-hydroxy-1-adamantyl (meth) acrylate, 3,5-dihydroxy-1-adamantyl (meth) acrylate, and 1- (3,5-dihydroxy-1-adamantyloxycarbonyl) methyl (meth) acrylate are Preferably, 3-hydroxy-1-adamantyl (meth) acrylate and 3,5-dihydroxy-1-adamantyl (meth) acrylate are more preferable, 3-hydroxy-1-adamantyl methacrylate and 3,5-dihydroxy-1-adamantyl methacrylate Is more preferable.

  The content of the repeating unit derived from the monomer represented by the formula (a2-1) in the resin is usually 3 to 40 mol%, preferably 5 to 35 mol%, more preferably in all units of the resin. Is 5 to 30 mol%.

<Acid-stable monomer having a lactone ring (a3)>
The lactone ring possessed by the acid stable monomer (a3) may be, for example, a monocyclic ring such as a β-propiolactone ring, γ-butyrolactone ring, or δ-valerolactone ring, or a monocyclic lactone ring and another ring. The condensed ring may be used. Among these lactone rings, a γ-butyrolactone ring and a condensed ring of a γ-butyrolactone ring and another ring are preferable.

  The acid-stable monomer (a3) having a lactone ring is preferably represented by the formula (a3-1), the formula (a3-2) or the formula (a3-3). These 1 type may be used independently and may use 2 or more types together.

式（ａ３−１）〜式（ａ３−３）中、
Ｌ^a4〜Ｌ^a6は、それぞれ独立に、−Ｏ−又は−Ｏ−（ＣＨ₂）_k3−ＣＯ−Ｏ−を表す。
ｋ３は１〜７の整数を表す。
Ｒ^a18〜Ｒ^a20は、それぞれ独立に、水素原子又はメチル基を表す。
Ｒ^a21は、炭素数１〜４の脂肪族炭化水素基を表す。
ｐ１は０〜５の整数を表す。
Ｒ^a22及びＲ^a23は、それぞれ独立に、カルボキシ基、シアノ基又は炭素数１〜４の脂肪族炭化水素基を表す。
ｑ１及びｒ１は、それぞれ独立に０〜３の整数を表す。ｐ１、ｑ１又はｒ１が２以上のとき、それぞれ、複数のＲ^a21、Ｒ^a22又はＲ^a23は、互いに同一でも異なってもよい。

In formula (a3-1) to formula (a3-3),
L ^{a4 to} L ^a6 each independently represent —O— or —O— (CH ₂ ) _k3 —CO—O—.
k3 represents an integer of 1 to 7.
R ^{a18 to} R ^a20 each independently represents a hydrogen atom or a methyl group.
R ^a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
p1 represents an integer of 0 to 5.
R ^a22 and R ^a23 each independently represent a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
q1 and r1 each independently represents an integer of 0 to 3. When p1, q1 or r1 is 2 or more, a plurality of R ^a21 , R ^a22 or R ^a23 may be the same as or different from each other.

In the formula (a3-1) to the formula (a3-3), examples of L ^{a4 to} L ^a6 include those described for L ^a3 .
L ^{a4 to} L ^a6 are each independently preferably —O—, —O— (CH ₂ ) _d1 —CO—O— (wherein d1 is an integer of 1 to 4), more preferably -O-. However, —O— and the like enumerated in L ^{a4 to} L ^a6 mean that they are bonded to —CO— of the formula (a3-1) to the formula (a3-3) on the left side and to the lactone ring on the right side. To do.
R ^{a18 to} R ^a21 are preferably methyl groups.
R ^a22 and R ^a23 are each independently preferably a carboxy group, a cyano group or a methyl group.
p1 to r1 are each independently preferably 0 to 2, more preferably 0 or 1.

  Examples of the acid stable monomer (a3-1) having a γ-butyrolactone ring include the following.

  As the acid stable monomer (a3-1) having a γ-butyrolactone ring, an acid labile monomer can also be exemplified. For example, the following are mentioned.

  Examples of the acid stable monomer (a3-2) having a condensed ring of γ-butyrolactone ring and norbornane ring include the following.

  As the acid stable monomer (a3-2) having a condensed ring of γ-butyrolactone ring and norbornane ring, an acid labile monomer can be exemplified. For example, the following are mentioned.

  Examples of the acid stable monomer (a3-3) having a condensed ring of γ-butyrolactone ring and cyclohexane ring include the following.

  An acid labile monomer can also be exemplified as the monomer (a3-3) having a condensed ring of γ-butyrolactone ring and cyclohexane ring. For example, the following are mentioned.

Among acid-stable monomers (a3) having a lactone ring, (meth) acrylic acid (5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl, (meth) acrylic Acid tetrahydro-2-oxo-3-furyl, 2- (5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yloxy) -2-oxoethyl (meth) acrylate Are preferred, and those in the form of methacrylate are more preferred.

  The content of the repeating unit derived from the monomer represented by the formula (a3-1), the formula (a3-2) or the formula (a3-3) in the resin is usually 5 to 50 mol% in all the units of the resin. Yes, preferably 10 to 45 mol%, more preferably 15 to 40 mol%.

<Other acid stable monomers (a4)>
Examples of the other acid stable monomer (a4) include maleic anhydride represented by formula (a4-1), itaconic anhydride represented by formula (a4-2), and formula (a4-3). And acid-stable monomers having a norbornene ring.

式（ａ４−３）中、
Ｒ^a25及びＲ^a26は、それぞれ独立に、水素原子、置換基（例えば、ヒドロキシ基）を有していてもよい炭素数１〜３の脂肪族炭化水素基、シアノ基、カルボキシ基又はアルコキシカルボニル基（−ＣＯＯＲ^a27）を表すか、或いはＲ^a25及びＲ^a26は互いに結合して−ＣＯ−Ｏ−ＣＯ−を形成し、
Ｒ^a27は、炭素数１〜３６の脂肪族炭化水素基又は炭素数３〜３６の飽和環状炭化水素基を表し、脂肪族炭化水素基及び飽和環状炭化水素基の−ＣＨ_２−は、−Ｏ−又は−ＣＯ−で置き換わっていてもよい。但し−ＣＯＯＲ^a27が酸不安定基となるものは除く（即ちＲ^a27は、３級炭素原子が−Ｏ−と結合するものを含まない）。

In formula (a4-3),
R ^a25 and R ^a26 each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 3 carbon atoms which may have a substituent (for example, a hydroxy group), a cyano group, a carboxy group, or an alkoxycarbonyl group. (—COOR ^a27 ) or R ^a25 and R ^a26 combine with each other to form —CO—O—CO—,
R ^a27 represents an aliphatic hydrocarbon group having 1 to 36 carbon atoms or a saturated cyclic hydrocarbon group having 3 to 36 carbon atoms, and —CH ₂ — of the aliphatic hydrocarbon group and the saturated cyclic hydrocarbon group is —O _2. -Or -CO- may be substituted. However, those in which —COOR ^a27 is an acid labile group are excluded (that is, R ^a27 does not include those in which a tertiary carbon atom is bonded to —O—).

^Examples of the aliphatic hydrocarbon group which may have a substituent for R ^a25 and R ^a26 include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a 2-hydroxyethyl group.
The aliphatic hydrocarbon group for R ^a27 preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms. The saturated cyclic hydrocarbon group preferably has 4 to 36 carbon atoms, more preferably 4 to 12 carbon atoms.
^Examples of R ^a27 include a methyl group, an ethyl group, a propyl group, a 2-oxo-oxolan-3-yl group, and a 2-oxo-oxolan-4-yl group.

  Examples of the acid-stable monomer (a4-3) having a norbornene ring include 2-norbornene, 2-hydroxy-5-norbornene, 5-norbornene-2-carboxylic acid, methyl 5-norbornene-2-carboxylate, 5- Examples include norbornene-2-carboxylic acid 2-hydroxy-1-ethyl, 5-norbornene-2-methanol, and 5-norbornene-2,3-dicarboxylic acid anhydride.

  The content of the repeating unit derived from the monomer represented by the formula (a4-1), the formula (a4-2) or the formula (a4-3) in the resin is usually 2 to 40 mol% in all the units of the resin. Yes, preferably 3-30 mol%, more preferably 5-20 mol%.

  A preferred resin (A) is a copolymer obtained by polymerizing at least a monomer (a1) having an acid labile group, an acid stable monomer (a2) having a hydroxy group, and / or an acid stable monomer (a3) having a lactone ring. It is a polymer. In this preferred copolymer, the monomer (a1) having an acid labile group is more preferably at least one of a monomer (a1-1) having an adamantyl group and a monomer (a1-2) having a cyclohexyl group. A species (more preferably a monomer (a1-1) having an adamantyl group), and an acid stable monomer (a2) having a hydroxy group, preferably an acid stable monomer (a2-1) having a hydroxyadamantyl group, and a lactone The acid-stable monomer (a3) having a ring is more preferably an acid-stable monomer (a3-1) having a γ-butyrolactone ring and an acid-stable monomer (a3-2) having a condensed ring of a γ-butyrolactone ring and a norbornane ring At least one of the following. Resin (A) can be manufactured by a well-known polymerization method (for example, radical polymerization method).

The weight average molecular weight of the resin (A) is preferably 2,500 or more (more preferably 3,000 or more) and 50,000 or less (more preferably 30,000 or less).
It is preferable that content of resin (A) is 80 mass% or more in solid content of a composition.
In the present specification, the “solid content in the composition” means the total of resist composition components excluding the solvent (E) described later. The solid content in the composition and the content of the resin (A) relative thereto can be measured by a known analysis means such as liquid chromatography or gas chromatography.

<Acid generator (B)>
The acid generator (B) is a sulfonate represented by the formula (B1).

［式（Ｂ１）中、
Ｑ¹及びＱ²は、それぞれ独立に、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^b1は、単結合又は２価の炭素数１〜１７の飽和炭化水素基を表し、前記２価の飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−で置き換わっていてもよい。
Ｙは、置換基を有していてもよいＣ₁〜Ｃ_１８脂肪族炭化水素基又は置換基を有していてもよい炭素数３〜１８の飽和環状炭化水素基を表し、前記脂肪族炭化水素基及び前記飽和環状炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＳＯ_２−又は−ＣＯ−で置き換わっていてもよい。
Ｚ⁺は、有機カチオンを表す。］

[In the formula (B1),
Q ¹ and Q ² each independently represents a fluorine atom or a C 1-6 perfluoroalkyl group.
L ^b1 represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and —CH ₂ — contained in the divalent saturated hydrocarbon group is replaced by —O— or —CO—. May be.
Y represents a saturated cyclic hydrocarbon group which has good C ₁ -C ₁₈ aliphatic hydrocarbon group or a substituted carbon atoms which may based on have 3-18 have a substituent, wherein the aliphatic hydrocarbon —CH ₂ — contained in the hydrogen group and the saturated cyclic hydrocarbon group may be replaced by —O—, —SO ₂ — or —CO—.
Z ⁺ represents an organic cation. ]

Examples of the perfluoroalkyl group include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluoro sec-butyl group, a perfluoro tert-butyl group, a perfluoropentyl group, and a perfluorohexyl group. It is done.
In formula (B1), Q ¹ and Q ² are each independently preferably a perfluoromethyl group or a fluorine atom, more preferably a fluorine atom.

Examples of the group in which —CH ₂ — contained in the saturated hydrocarbon group of L ^b1 is replaced by —O— or —CO— include formula (b1-1) to formula (b1-6). L ^b1 is preferably any one of formulas (b1-1) to (b1-4), more preferably formula (b1-1) or formula (b1-2). Incidentally, the formula (b1-1) ~ formula (b1-6) are described together the left and right in the equation (B1), the left ^{C (Q 1) (Q 2} ) - bound to, the right side Combines with -Y. The same applies to specific examples of the following formulas (b1-1) to (b1-6).

式（ｂ１−１）〜式（ｂ１−６）中、
Ｌ^b2は、単結合又は炭素数１〜１５のアルキレン基を表す。
Ｌ^b3は、単結合又は炭素数１〜１２のアルキレン基を表す。
Ｌ^b4は、炭素数１〜１３のアルキレン基を表す。但しＬ^b3及びＬ^b4の炭素数上限は１３である。
Ｌ^b5は、Ｃ₁〜Ｃ₁₅アルキレン基を表す。
Ｌ^b6及びＬ^b7は、それぞれ独立に、炭素数１〜１５のアルキレン基を表す。但しＬ^b6及びＬ^b7の炭素数上限は１６である。
Ｌ^b8は、炭素数１〜１４のアルキレン基を表す。
Ｌ^b9は、炭素数１〜１１のアルキレン基を表す。
Ｌ^b10は、炭素数１〜１１の飽和炭化水素基を表す。但しＬ^ｂ９及びＬ^ｂ１０の炭素数上限は１２である。
中でも、式（ｂ１−１）で表される２価の基が好ましく、Ｌ^b2が単結合又は−ＣＨ_２−である式（ｂ１−１）で表される２価の基がより好ましい。

In formula (b1-1) to formula (b1-6),
L ^b2 represents a single bond or an alkylene group having 1 to 15 carbon atoms.
L ^b3 represents a single bond or an alkylene group having 1 to 12 carbon atoms.
L ^b4 represents an alkylene group having 1 to 13 carbon atoms. However, the upper limit of the carbon number of L ^b3 and L ^b4 is 13.
L ^b5 represents a C _{1 to} C ₁₅ alkylene group.
L ^b6 and L ^b7 each independently represent an alkylene group having 1 to 15 carbon atoms. However, the upper limit of the carbon number of L ^b6 and L ^b7 is 16.
L ^b8 represents an alkylene group having 1 to 14 carbon atoms.
L ^b9 represents an alkylene group having 1 to 11 carbon atoms.
L ^b10 represents a saturated hydrocarbon group having 1 to 11 carbon atoms. However, the upper limit of the carbon number of L ^b9 and L ^b10 is 12.
Among these, a divalent group represented by the formula (b1-1) is preferable, and a divalent group represented by the formula (b1-1) in which L ^b2 is a single bond or —CH ₂ — is more preferable.

Examples of the divalent group represented by the formula (b1-1) include the following.

Examples of the divalent group represented by the formula (b1-2) include the following.

Examples of the divalent group represented by the formula (b1-3) include the following.

Examples of the divalent group represented by the formula (b1-4) include the following.

Examples of the divalent group represented by the formula (b1-5) include the following.

Examples of the divalent group represented by the formula (b1-6) include the following.

The saturated hydrocarbon group for L ^b1 may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, a carboxy group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, an acyl group having 2 to 4 carbon atoms, and a glycidyloxy group. Is mentioned.
Examples of the aralkyl group include benzyl, phenethyl, phenylpropyl, trityl, naphthylmethyl group, naphthylethyl group, and the like.

Examples of the substituent for the aliphatic hydrocarbon group and saturated cyclic hydrocarbon group in Y include, for example, a halogen atom (excluding a fluorine atom), a hydroxy group, an oxo group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, hydroxy Group-containing C1-C12 aliphatic hydrocarbon group, C3-C16 saturated cyclic hydrocarbon group, C1-C12 alkoxy group, C6-C18 aromatic hydrocarbon group, C7 aralkyl group to 21, an acyl group having 2 to 4 carbon atoms, glycidyloxy group or a _{- (CH 2) j2 -O-} CO-R b1 group (wherein, R ^b1 is an aliphatic C1-16 hydrocarbon Represents a hydrogen group, a saturated cyclic hydrocarbon group having 3 to 16 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms, j2 represents an integer of 0 to 4).
The aliphatic hydrocarbon group, saturated cyclic hydrocarbon group, aromatic hydrocarbon group, aralkyl group, and the like, which are substituents for Y, may further have a substituent. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, and an oxo group.
Here, examples of the hydroxy group-containing aliphatic hydrocarbon group include a hydroxymethyl group and a hydroxyethyl group.
Examples of the group in which —CH ₂ — in the aliphatic hydrocarbon group and saturated cyclic hydrocarbon group of Y is replaced by —O—, —SO ₂ — or —CO— include, for example, an ether bond or a cyclic ether (—CH ₂ — Is a group in which —O— is substituted, a saturated cyclic hydrocarbon group having an oxo group (a group in which —CH ₂ — is replaced by —CO—), and a sultone ring group (two adjacent —CH ₂ — groups are A group substituted with —O— or —SO ₂ —) or a lactone ring group (a group in which two adjacent —CH ₂ — are each substituted with —O— or —CO—).
Among such groups, examples of the saturated cyclic hydrocarbon group include groups represented by formulas (Y1) to (Y26).

The saturated cyclic hydrocarbon group for Y is preferably a group represented by any one of formulas (Y1) to (Y19), more preferably formula (Y11), formula (Y14), formula (Y15) or formula A group represented by (Y19), and more preferably a group represented by formula (Y11) or formula (Y14).
As the aliphatic hydrocarbon group for Y, an alkyl group having 1 to 6 carbon atoms is preferable.

Examples of Y, which is a saturated cyclic hydrocarbon group substituted with an aliphatic hydrocarbon group, include the following.

  Examples of Y that is a saturated cyclic hydrocarbon group substituted with a hydroxy group or a hydroxy group-containing aliphatic hydrocarbon group include the following.

  Examples of Y, which is a saturated cyclic hydrocarbon group substituted with an aromatic hydrocarbon group, include the following.

Examples of Y that is a saturated cyclic hydrocarbon group in which the — (CH ₂ ) _j2 —O—CO—R ^b1 group is substituted include the following.

  Y is preferably an adamantyl group which may have a substituent (for example, an oxo group or the like), more preferably an adamantyl group or an oxoadamantyl group.

Saturated cyclic substituted with a sulfonate anion or an aliphatic hydrocarbon group containing Y which is an aliphatic hydrocarbon group or an unsubstituted saturated cyclic hydrocarbon group and a divalent group represented by the formula (b1-1) Examples of the sulfonate anion containing Y which is a hydrocarbon group and the divalent group represented by the formula (b1-1) include the following.

As the sulfonate anion containing Y which is a saturated cyclic hydrocarbon group substituted with — (CH ₂ ) _j2 —O—CO—R ^b1 group and a divalent group represented by the formula (b1-1), For example, the following are mentioned.

  Examples of the sulfonate anion containing Y which is a saturated cyclic hydrocarbon group substituted with a hydroxy group or a hydroxy group-containing aliphatic hydrocarbon group and a divalent group represented by the formula (b1-1) include the following: Things.

  Examples of the sulfonate anion containing Y which is a saturated cyclic hydrocarbon group substituted with an aromatic hydrocarbon group or an aralkyl group and a divalent group represented by the formula (b1-1) include the following. It is done.

Examples of the sulfonate anion containing Y which is a cyclic ether and the divalent group represented by the formula (b1-1) include the following.

Examples of the sulfonate anion containing Y which is a lactone ring and the divalent group represented by the formula (b1-1) include the following.

  Examples of the sulfonate anion containing Y which is a saturated cyclic hydrocarbon having an oxo group and a divalent group represented by the formula (b1-1) include the following.

Examples of the sulfonate anion containing Y which is a sultone ring and the divalent group represented by the formula (b1-1) include the following.

Saturated cyclic substituted with a sulfonate anion or an aliphatic hydrocarbon group containing Y which is an aliphatic hydrocarbon group or an unsubstituted saturated cyclic hydrocarbon group and a divalent group represented by the formula (b1-2) Examples of the sulfonate anion containing Y which is a hydrocarbon group and the divalent group represented by the formula (b1-2) include the following.

As the sulfonate anion containing Y which is a saturated cyclic hydrocarbon group substituted with — (CH ₂ ) _j2 —O—CO—R ^b1 group and a divalent group represented by the formula (b1-2), For example, the following are mentioned.

  Examples of the sulfonate anion containing Y which is a saturated cyclic hydrocarbon group substituted with a hydroxy group or a hydroxy group-containing aliphatic hydrocarbon group and a divalent group represented by the formula (b1-2) include the following: Things.

  Examples of the sulfonate anion containing Y, which is a saturated cyclic hydrocarbon group substituted with an aromatic hydrocarbon group, and a divalent group represented by the formula (b1-2) include the following.

  Examples of the sulfonate anion containing Y which is a cyclic ether and the divalent group represented by the formula (b1-2) include the following.

  Examples of the sulfonate anion containing Y which is a lactone ring and the divalent group represented by the formula (b1-2) include the following.

  Examples of the sulfonate anion containing Y having an oxo group and the divalent group represented by the formula (b1-2) include the following.

  Examples of the sulfonate anion containing Y which is a sultone ring and the divalent group represented by the formula (b1-2) include the following.

  Y which is an aliphatic hydrocarbon group or a saturated cyclic hydrocarbon group substituted with a sulfonate anion or an aliphatic hydrocarbon group containing an unsubstituted Y and a divalent group represented by the formula (b1-3) Examples of the sulfonate anion containing the divalent group represented by the formula (b1-3) include the following.

  Examples of the sulfonate anion containing Y, which is a saturated cyclic hydrocarbon group substituted with an alkoxy group, and a divalent group represented by the formula (b1-3) include the following.

  Examples of the sulfonate anion containing Y which is a saturated cyclic hydrocarbon group substituted with a hydroxy group or a hydroxy group-containing aliphatic hydrocarbon group and a divalent group represented by the formula (b1-3) include the following: Things.

  Examples of the sulfonate anion containing Y having an oxo group and the divalent group represented by the formula (b1-3) include the following.

  Examples of the sulfonate anion containing Y, which is a saturated cyclic hydrocarbon group substituted with an aliphatic hydrocarbon group, and a divalent group represented by the formula (b1-4) include the following.

  Examples of the sulfonate anion containing Y which is a saturated cyclic hydrocarbon group substituted with an alkoxy group and a divalent group represented by the formula (b1-4) include the following.

  Examples of the sulfonate anion containing Y which is a saturated cyclic hydrocarbon group substituted with a hydroxy group or a hydroxy group-containing aliphatic hydrocarbon group and a divalent group represented by the formula (b1-4) include the following: Things.

  Examples of the sulfonate anion containing Y which is a saturated cyclic hydrocarbon group having an oxo group and a divalent group represented by the formula (b1-4) include the following.

Among these, the following sulfonate anions having a divalent group represented by the formula (b1-1) are more preferable.

Examples of the sulfonate anion in the salt represented by the formula (B1) include, for example, the following formulas (b1-1-1) to (b1-1-1-) in which the substituent L ^b1 is the formula (b1-1). The anion represented by 9) is preferred. In the following formulas, the definition of the substituent has the same meaning as described above, and each of the substituents R ^b2 and R ^b3 independently represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms (preferably a methyl group). To express.

  Examples of the cation contained in the acid generator (B) include an onium cation such as a sulfonium cation, an iodonium cation, an ammonium cation, a benzothiazolium cation, and a phosphonium cation. Among these, a sulfonium cation and an iodonium cation are preferable, and an arylsulfonium cation is more preferable.

Z ⁺ in formula (B1) is preferably represented by any of formula (b2-1) to formula (b2-4).

In these formulas (b2-1) to (b2-4),
R ^{b4 to} R ^b6 each independently represent an aliphatic hydrocarbon group having 1 to 30 carbon atoms, a saturated cyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The aliphatic hydrocarbon group may be 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 the saturated cyclic hydrocarbon group includes a halogen atom, The aromatic hydrocarbon group which may be substituted with an acyl group having 2 to 4 carbon atoms or a glycidyloxy group is a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 36 carbon atoms, or 3 to 3 carbon atoms. It may be substituted with 36 saturated cyclic hydrocarbon groups or C1-C12 alkoxy groups.

R ^b7 and R ^b8 each independently represent a hydroxy group, an aliphatic hydrocarbon 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 aliphatic hydrocarbon group having 1 to 36 carbon atoms or a saturated cyclic hydrocarbon group having 3 to 36 carbon atoms.
R ^b11 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 36 carbon atoms, a saturated cyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms.
The aliphatic hydrocarbon group of R ^{b9 to} R ^b11 preferably has 1 to 12 carbon atoms, and the saturated cyclic hydrocarbon group preferably has 3 to 36 carbon atoms, more preferably 4 to 12 carbon atoms.
R ^b12 represents an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a saturated cyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The aromatic hydrocarbon group is substituted with an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a saturated cyclic hydrocarbon group having 3 to 18 carbon atoms, or an alkylcarbonyloxy group. Also good.
R ^b9 and R ^b10 , and R ^b11 and R ^b12 may be independently bonded to each other to form a 3- to 12-membered ring (preferably a 3- to 7-membered ring), These rings —CH ₂ — may be replaced by —O—, —S— or —CO—.

R ^{b13 to} R ^b18 each independently represent a hydroxy group, an aliphatic hydrocarbon 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 any of o2 to t2 is 2, any of the plurality of R ^{b13 to} R ^b18 may be the same as or different from each other.

  Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, an n-butylcarbonyloxy group, a sec-butylcarbonyloxy group, a tert-butylcarbonyloxy group, Examples thereof include a pentylcarbonyloxy group, a hexylcarbonyloxy group, an octylcarbonyloxy group, and a 2-ethylhexylcarbonyloxy group.

Preferred aliphatic hydrocarbon groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl and 2-ethylhexyl. It is.
Preferred saturated cyclic hydrocarbon groups are cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclodecyl group, 2-alkyl-2-adamantyl group, 1- (1-adamantyl) -1-alkyl group, And an isobornyl group.
Preferred aromatic hydrocarbon groups are phenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-tert-butylphenyl group, 4-cyclohexylphenyl group, 4-methoxyphenyl group, biphenylyl group, naphthyl group. It is.
Examples of the aliphatic hydrocarbon group (aralkyl group) whose substituent is an aromatic hydrocarbon group include a benzyl group.
Examples of the ring formed by R ^b9 and R ^b10 include a thiolane-1-ium ring (tetrahydrothiophenium ring), a thian-1-ium ring, and a 1,4-oxathian-4-ium ring.
^Examples of the ring formed by R ^b11 and R ^b12 include an oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, and an oxoadamantane ring.

  Among the cations (b2-1) to (b2-4), the cation (b2-1) is preferable, the cation represented by the formula (b2-1-1) is more preferable, and the triphenylsulfonium cation (formula (b2) In (1-1), v2 = w2 = x2 = 0) is more preferable.

式（ｂ２−１−１）中、
Ｒ^b19〜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１〜３６の脂肪族炭化水素基、炭素数３〜３６の飽和環状炭化水素基又は炭素数１〜１２のアルコキシ基を表す。
脂肪族炭化水素基は、好ましくは炭素数１〜１２であり、飽和環状炭化水素基は、好ましくは炭素数４〜３６である。
前記脂肪族炭化水素基は、ヒドロキシ基、炭素数１〜１２のアルコキシ基又は炭素数６〜１８の芳香族炭化水素基で置換されていてもよい。
前記飽和環状炭化水素基は、ハロゲン原子、炭素数２〜４のアシル基又はグリシジルオキシ基で置換されていてもよい。
ｖ２〜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〜ｘ２のいずれかが２以上のとき、それぞれ、複数のＲ^b19〜Ｒ^b21のいずれかは、互いに同一でも異なってもよい。
なかでも、Ｒ^b19〜Ｒ^b21は、それぞれ独立に、好ましくは、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のアルキル基又は炭素数１〜１２のアルコキシ基である。

In formula (b2-1-1),
R ^{b19 to} R ^b21 each independently represent a halogen atom (more preferably a fluorine atom), a hydroxy group, an aliphatic hydrocarbon group having 1 to 36 carbon atoms, a saturated cyclic hydrocarbon group having 3 to 36 carbon atoms, or a carbon number. 1 to 12 alkoxy groups are represented.
The aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, and the saturated cyclic hydrocarbon group preferably has 4 to 36 carbon atoms.
The aliphatic hydrocarbon group may be 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.
The saturated cyclic hydrocarbon group may be substituted with a halogen atom, an acyl group having 2 to 4 carbon atoms, or a glycidyloxy group.
v2 to x2 each independently represents an integer of 0 to 5 (preferably 0 or 1). When any one of v2 to x2 is 2 or more, any one of the plurality of R ^{b19 to} R ^b21 may be the same as or different from each other.
Among these, R ^{b19 to} 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.

Specific examples of the cation (b2-1-1) include the following.

Specific examples of the cation (b2-2) include the following.

Specific examples of the cation (b2-3) include the following.

Specific examples of the cation (b2-4) include the following.

  The acid generator (B1) is a combination of the above-described sulfonate anion and organic cation. The above-mentioned anion and cation can be arbitrarily combined, but any one of anion (b1-1-1) to anion (b1-1-9) and a cation (b2-1-1), and an anion ( A combination of any one of b1-1-3) to (b1-1-5) and a cation (b2-3) is preferable.

  Preferred acid generators (B1) are those represented by formula (B1-1) to formula (B1-17). Among them, acid generators (B1-1), (B1-2), (B1-6), (B1-11), (B1-12), (B1-13) and (B1-14) containing a triphenylsulfonium cation ) Is more preferable.

  The content of the acid generator (B) is preferably 1 part by mass or more (more preferably 3 parts by mass or more), preferably 30 parts by mass or less (more preferably 25 parts by mass) with respect to 100 parts by mass of the resin (A). Part or less).

［式（Ｉ）中、
Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、それぞれ独立に、水素原子、ハロゲン原子又はシアノ基を表す。
Ａ^１及びＡ^２は、それぞれ独立に、＝Ｏ、＝ＣＲ^５Ｒ^６又は＝ＮＲ^７を表す。
Ｒ^５、Ｒ^６及びＲ^７は、それぞれ独立に、水素原子又は炭素数１〜４のアルキル基を表す。］ <Compound (D) having quinoid structure>
A compound having a quinoid structure refers to a compound having a structure in which an aromatic compound has one intracyclic double bond reduced and has two exocyclic double bonds at the para or ortho position. Those with an exocyclic double bond oxygen are quinones, those with oxygen and nitrogen atoms are quinoneimines, those with nitrogen atoms are quinonediimines, those with oxygen and carbon are quinomethanes, and carbon atoms Things are called quinodimethanes. Especially, the compound represented by Formula (I) is mentioned.

[In the formula (I),
R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom, a halogen atom or a cyano group.
A ¹ and A ² each independently represent ═O, ═CR ⁵ R ⁶ or ═NR ⁷ .
R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

［式（Ｉａ）中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、上記と同じ意味である。］ In the formula (I), quinones represented by the formula (Ia) in which both A ¹ and A ² are oxygen atoms are preferable.

[In formula (Ia), R ¹ , R ² , R ³ and R ⁴ have the same meaning as described above. ]

  Specifically, compounds having a quinoid structure are p-benzoquinone, 2,5-dichloro-p-benzoquinone, 2,6-dichloro-p-benzoquinone, 2,3-dichloro-5,6-dicyano-p- Examples include benzoquinone. Of these, 2,3-dichloro-5,6-dicyano-p-benzoquinone is preferable.

［式（II）中、
Ｒ^ｂ1、Ｒ^ｂ２及びＲ^ｂ３は、それぞれ独立に、水素原子又は炭素数１〜１２の炭化水素基を表すか、Ｒ^ｂ１及びＲ^ｂ２は互いに結合して炭素数３〜３６の環を形成してもよく、該炭化水素基及び環に含まれる水素原子は、−ＯＨで置換されていてもよく、該炭化水素基及び環に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−で置き換わっていてもよい。
Ｒ^ｂ４及びＲ^ｂ５は、それぞれ独立に、水素原子、炭素数１〜６のアルキル基、炭素数６〜１２の飽和環状炭化水素基、炭素数６〜１２の芳香族炭化水素基又は炭素数５〜９の芳香族複素環基を表すか、Ｒ^ｂ４及びＲ^ｂ５は互いに結合して５員又は６員の複素環を形成してもよく、該アルキル基に含まれる水素原子は、−ＯＨ、−ＳＨ、−ＮＨ_２、炭素数６〜１２の飽和環状炭化水素基、炭素数６〜１２の芳香族炭化水素基又は炭素数５〜９の芳香族複素環基で置換されていてもよく、該アルキル基に含まれる−ＣＨ_２−は、−Ｏ−、−Ｓ−、−ＣＯ−、−Ｃ（＝ＮＨ）−又は−ＮＨ−で置き換わっていてもよい。該飽和環状炭化水素基、該芳香族炭化水素基及び該芳香族複素環基に含まれる水素原子は、−ＯＨで置換されていてもよい。
Ｒ^ｂ６、Ｒ^ｂ７、Ｒ^ｂ８、Ｒ^ｂ９及びＲ^ｂ１０は、それぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、シアノ基、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２〜７のアルコキシカルボニル基又は置換基を有してもよい炭素数６〜１２の芳香族炭化水素基を表す。
式（III）中、
Ｒ^ｄ1及びＲ^ｄ２は、それぞれ独立に、置換基を有していてもよい炭素数１〜１８のアルキレン基を表す。
Ｒ^ｄ３、Ｒ^ｄ４、Ｒ^ｄ５、Ｒ^ｄ６及びＲ^ｄ７は、それぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、シアノ基、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２〜７のアルコキシカルボニル基又は置換基を有してもよい炭素数６〜１２の芳香族炭化水素基を表す。］ <Quencher (G)>
An example of the quencher (G) is a compound having a benzyl group.
The compound having a benzyl group is preferably, for example, one selected from a compound represented by the formula (II) and a compound represented by the formula (III).

[In the formula (II),
R ^b1 , R ^b2 and R ^b3 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, or R ^b1 and R ^b2 are bonded to each other to form a ring having 3 to 36 carbon atoms. The hydrogen atom contained in the hydrocarbon group and the ring may be substituted with —OH, and —CH ₂ — contained in the hydrocarbon group and the ring is —O— or —CO—. It may be replaced.
R ^b4 and R ^b5 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a saturated cyclic hydrocarbon group having 6 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or 5 carbon atoms. Or an aromatic heterocyclic group of ˜9, or R ^b4 and R ^b5 may be bonded to each other to form a 5-membered or 6-membered heterocyclic ring, and the hydrogen atom contained in the alkyl group is —OH, -SH, -NH _2, it may be substituted by a saturated cyclic hydrocarbon group, aromatic hydrocarbon group or an aromatic heterocyclic group having a carbon number of 5 to 9 having 6 to 12 carbon atoms of 6 to 12 carbon atoms, —CH ₂ — contained in the alkyl group may be replaced by —O—, —S—, —CO—, —C (═NH) — or —NH—. Hydrogen atoms contained in the saturated cyclic hydrocarbon group, the aromatic hydrocarbon group, and the aromatic heterocyclic group may be substituted with —OH.
R ^b6 , R ^b7 , R ^b8 , R ^b9 and R ^b10 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Group, a C2-C4 acyl group, a C2-C7 alkoxycarbonyl group, or a C6-C12 aromatic hydrocarbon group which may have a substituent.
In formula (III),
R ^d1 and R ^d2 each independently represent an alkylene group having 1 to 18 carbon atoms which may have a substituent.
R ^d3 , R ^d4 , R ^d5 , R ^d6 and R ^d7 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Group, a C2-C4 acyl group, a C2-C7 alkoxycarbonyl group, or a C6-C12 aromatic hydrocarbon group which may have a substituent. ]

Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an unsaturated hydrocarbon group, a saturated cyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which these are combined. Specifically, an alkyl group, an alkenyl group, and the like. Cycloalkyl group, aryl group, aralkyl group and the like.
Examples of the unsaturated hydrocarbon group include alkenyl groups such as a vinyl group and an allyl group.
Examples of the ring formed by combining R ^b1 and R ^b2 with each other include saturated cyclic hydrocarbons and aromatic hydrocarbons. In addition to those described above, the following rings are also included. The bond can be at any position (the same applies hereinafter).

Examples of the group in which —CH ₂ — contained in the hydrocarbon group is replaced by —O— or —CO— include groups represented by the above-described formulas (b1-1) to (b1-6).
Examples of the group in which —CH ₂ — contained in the hydrocarbon group and the ring is replaced by —O— or —CO— include the groups shown below.

複素環基としては、芳香族複素環基に加え、テトラヒドロフラニル基、テトラヒドピラニル基、ピロリジニル基、ピペリジニル基、ピペラジニル基、オキサゾリジニル基、イソオキサゾリル基等が挙げられる。
炭素数２〜７のアルコキシカルボニル基とは、カルボニル基に炭素数１〜６のアルコキシ基が結合した基を意味する。 Examples of the aromatic heterocyclic group include a furyl group, a thienyl group, a pyrrolyl group, a pyridyl group, an imidazolyl group, an oxazolyl group, a quinolyl group, and an isoquinolyl group described below. The bond is two positions of the nitrogen atom and the element adjacent to it.

Examples of the heterocyclic group include a tetrahydrofuranyl group, a tetrahydropyranyl group, a pyrrolidinyl group, a piperidinyl group, a piperazinyl group, an oxazolidinyl group, and an isoxazolyl group in addition to an aromatic heterocyclic group.
A C2-C7 alkoxycarbonyl group means the group which the C1-C6 alkoxy group couple | bonded with the carbonyl group.

炭化水素基の水素原子が−ＯＨで置換された環としては、下記に示す環が挙げられる。

飽和環状炭化水素基としては、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、ノルボルニル基、ビシクロ［２．２．２］オクチル基、アダマンチル基（１−アダマンチル基、２−アダマンチル基）等が挙げられる。 In the formulas (II) and (III), examples of the hydrocarbon group include aliphatic hydrocarbon groups and the groups shown below. * Represents a bond.

Examples of the ring in which the hydrogen atom of the hydrocarbon group is substituted with —OH include the rings shown below.

Examples of the saturated cyclic hydrocarbon group include cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, bicyclo [2.2.2] octyl group, adamantyl group (1-adamantyl group, 2-adamantyl group) and the like. .

Especially, in the compound represented by the formula (II),
R ^b1 , R ^b2 and R ^b3 are each independently an aliphatic hydrocarbon having 1 to 6 carbon atoms, a saturated cyclic hydrocarbon group having 3 to 12 carbon atoms formed by bonding of R ^b1 and R ^b2 to each other, and It is preferable that —CH ₂ — contained in the saturated cyclic hydrocarbon group is a group replaced by —O— or —CO—.
R ^b4 and R ^b5 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms that may be substituted with a hydroxy group, or a 5-membered or 6-membered member formed by combining R ^b4 and R ^b5 with each other. It is preferably a heterocyclic group.
R ^b6 , R ^b7 , R ^b8 , R ^b9 and R ^b10 are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a halogen group, a nitro group, a cyano group, or an alkoxy having 1 to 6 carbon atoms. Group, an acyl group having 2 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms is preferable.

In the compound represented by the formula (III),
R ^d1 and R ^d2 are preferably each independently an alkylene group having 3 to 6 carbon atoms.
R ^d3 , R ^d4 , R ^d5 , R ^d6 and R ^d7 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a halogen group, a nitro group, a cyano group, or an alkoxy having 1 to 6 carbon atoms. Group, an acyl group having 2 to 4 carbon atoms, and an alkoxycarbonyl group having 2 to 7 carbon atoms are preferable.

Examples of the compound having a benzyl group represented by the formula (II) include the following compounds.

Examples of the compound having a benzyl group represented by the formula (III) include the following compounds.

<Basic compound (C)>
It is suitable that the resist composition of the present invention further contains a basic compound (C). This basic compound (C) can function as a quencher.
The content of the basic compound (C) is preferably about 0.01 to 1% by mass based on the solid content of the resist composition.

  The basic compound (C) is preferably a basic nitrogen-containing organic compound (for example, an amine). The amine may be an aliphatic amine or an aromatic amine. As the aliphatic amine, any of primary amine, secondary amine and tertiary amine can be used. The aromatic amine may be any of an amino group bonded to an aromatic ring such as aniline and a heteroaromatic amine such as pyridine. Preferable basic compound (C) includes an aromatic amine represented by the formula (C2), particularly an aniline represented by the formula (C2-1).

ここで、Ａｒ^c1は、芳香族炭化水素基を表す。
Ｒ^c5及びＲ^c6は、それぞれ独立に、水素原子、脂肪族炭化水素基（好ましくはアルキル基又はシクロアルキル基）、飽和環状炭化水素基或いは芳香族炭化水素基を表す。但し前記脂肪族炭化水素基、前記飽和環状炭化水素基又は前記芳香族炭化水素基の水素原子は、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、前記アミノ基は、炭素数１〜４のアルキル基で置換されていてもよい。
前記脂肪族炭化水素基は、好ましくは炭素数１〜６程度であり、前記飽和環状炭化水素基は、好ましくは炭素数５〜１０程度であり、前記芳香族炭化水素基は、好ましくは炭素数６〜１０程度である。
Ｒ^c7は、脂肪族炭化水素基（好ましくはアルキル基又はシクロアルキル基）、アルコキシ基、飽和環状炭化水素基或いは芳香族炭化水素基を表す。但し脂肪族炭化水素基、アルコキシ基、飽和環状炭化水素基及び芳香族炭化水素基の水素原子は、上記と同様の置換基を有していてもよい。
ｍ３は０〜３の整数を表す。ｍ３が２以上のとき、複数のＲ^c7は、互いに同一でも異なってもよい。
Ｒ^c7の脂肪族炭化水素基、飽和環状炭化水素基及び芳香族炭化水素基の好ましい炭素数は、上記と同じであり、Ｒ^c7のアルコキシ基は、好ましくは炭素数１〜６程度である。

Here, Ar ^c1 represents an aromatic hydrocarbon group.
R ^c5 and R ^c6 each independently represent a hydrogen atom, an aliphatic hydrocarbon group (preferably an alkyl group or a cycloalkyl group), a saturated cyclic hydrocarbon group, or an aromatic hydrocarbon group. However, the hydrogen atom of the aliphatic hydrocarbon group, the saturated cyclic hydrocarbon group or the aromatic hydrocarbon group may be substituted with a hydroxy group, an amino group, or an alkoxy group having 1 to 6 carbon atoms, The amino group may be substituted with an alkyl group having 1 to 4 carbon atoms.
The aliphatic hydrocarbon group preferably has about 1 to 6 carbon atoms, the saturated cyclic hydrocarbon group preferably has about 5 to 10 carbon atoms, and the aromatic hydrocarbon group preferably has about carbon atoms. It is about 6-10.
R ^c7 represents an aliphatic hydrocarbon group (preferably an alkyl group or a cycloalkyl group), an alkoxy group, a saturated cyclic hydrocarbon group, or an aromatic hydrocarbon group. However, the hydrogen atom of an aliphatic hydrocarbon group, an alkoxy group, a saturated cyclic hydrocarbon group, and an aromatic hydrocarbon group may have a substituent similar to the above.
m3 represents an integer of 0 to 3. When m3 is 2 or more, the plurality of R ^c7 may be the same as or different from each other.
Aliphatic hydrocarbon group R ^c7, preferable number of carbon atoms of the saturated cyclic hydrocarbon group and the aromatic hydrocarbon group are the same as above, an alkoxy group of R ^c7 is independently in, preferably about 1 to 6 carbon atoms.

Examples of the aromatic amine (C2) include 1-naphthylamine and 2-naphthylamine.
Examples of aniline (C2-1) include aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N, N-dimethylaniline, diphenylamine and the like.
Of these, diisopropylaniline (particularly 2,6-diisopropylaniline) is preferable.

ここで、
Ｒ^c8は、上記Ｒ^c7で説明したいずれかの基を表す。
窒素原子と結合するＲ^c9、Ｒ^c10、Ｒ^c11〜Ｒ^c14、Ｒ^c16〜Ｒ^c19及びＲ^c22は、それぞれ独立に、Ｒ^c5及びＲ^c6で説明したいずれかの基を表す。
芳香族炭素と結合するＲ^c20、Ｒ^c21、Ｒ^c23〜Ｒ^c28は、それぞれ独立に、Ｒ^c7で説明したいずれかの基を表す。
ｏ３〜ｕ３は、それぞれ独立に０〜３の整数を表す。ｏ３〜ｕ３のいずれかが２以上であるとき、それぞれ、複数のＲ^c20〜Ｒ^c28のいずれかは互いに同一でも異なってもよい。
Ｒ^c15は、脂肪族炭化水素基、飽和環状炭化水素基又はアルカノイル基を表す。
ｎ３は０〜８の整数を表す。ｎ３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。
Ｒ^c15の脂肪族炭化水素基は、好ましくは炭素数１〜６程度であり、飽和環状炭化水素基は、好ましくは炭素数３〜６程度であり、アルカノイル基は、好ましくは炭素数２〜６程度である。
Ｌ^c1及びＬ^c2は、それぞれ独立に、２価の脂肪族炭化水素基（好ましくはアルキレン基）、−ＣＯ−、−Ｃ（＝ＮＨ）−、−Ｃ（＝ＮＲ^c3）−、−Ｓ−、−Ｓ−Ｓ−又はこれらの組合せを表す。前記２価の脂肪族炭化水素基は、好ましくは炭素数１〜６程度である。
Ｒ^c3は、炭素数１〜４のアルキル基を表す。 Examples of the basic compound (C) include compounds represented by the formulas (C3) to (C11).

here,
R ^c8 represents any of the groups described for R ^c7 above.
R ^c9 , R ^c10 , R ^{c11 to} R ^c14 , R ^{c16 to} R ^c19 and R ^c22 bonded to the nitrogen atom each independently represent any of the groups described for R ^c5 and R ^c6 .
R ^c20 , R ^c21 and R ^{c23 to} R ^c28 bonded to the aromatic carbon each independently represents any of the groups described for R ^c7 .
o3 to u3 each independently represents an integer of 0 to 3. When any of o3 to u3 is 2 or more, any of the plurality of R ^{c20 to} R ^c28 may be the same as or different from each other.
R ^c15 represents an aliphatic hydrocarbon group, a saturated cyclic hydrocarbon group or an alkanoyl group.
n3 represents an integer of 0 to 8. When n3 is 2 or more, the plurality of R ^c15 may be the same as or different from each other.
The aliphatic hydrocarbon group represented by R ^c15 preferably has about 1 to 6 carbon atoms, the saturated cyclic hydrocarbon group preferably has about 3 to 6 carbon atoms, and the alkanoyl group preferably has 2 to 6 carbon atoms. Degree.
L ^c1 and L ^c2 are each independently a divalent aliphatic hydrocarbon group (preferably an alkylene group), —CO—, —C (═NH) —, —C (═NR ^c3 ) —, —S—. , -SS- or a combination thereof. The divalent aliphatic hydrocarbon group preferably has about 1 to 6 carbon atoms.
R ^c3 represents an alkyl group having 1 to 4 carbon atoms.

  Examples of the compound (C3) include hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, Tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctyl Amine, methyl dinonyl amine, methyl didecyl amine, ethyl dibutyl amine, ethyl dipentyl amine, ethyl di Silamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexylmethylamine, tris [2- (2-methoxyethoxy) ethyl] amine, triisopropanolamine ethylenediamine, tetramethylenediamine, hexamethylene Examples include diamine, 4,4′-diamino-1,2-diphenylethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-diamino-3,3′-diethyldiphenylmethane, and the like.

Examples of the compound (C4) include piperazine.
Examples of the compound (C5) include morpholine.
Examples of the compound (C6) include piperidine and hindered amine compounds having a piperidine skeleton described in JP-A No. 11-52575.
Examples of the compound (C7) include 2,2′-methylenebisaniline.
Examples of the compound (C8) include imidazole and 4-methylimidazole.
Examples of the compound (C9) include pyridine and 4-methylpyridine.
Examples of the compound (C10) include 1,2-di (2-pyridyl) ethane, 1,2-di (4-pyridyl) ethane, 1,2-di (2-pyridyl) ethene, and 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'-dipicolylamine and the like can be mentioned.
Examples of the compound (C11) include bipyridine.

<Solvent (sometimes referred to as "solvent (E)")
The resist composition of the present invention may contain the solvent (E) in an amount of 90% by mass or more in the composition. The resist composition of the present invention containing the solvent (E) is suitable for producing a thin film resist. The content of the solvent (E) is 90% by mass or more (preferably 92% by mass or more, more preferably 94% by mass or more) and 99.9% by mass or less (preferably 99% by mass or less) in the composition.
The content of the solvent (E) can be measured by a known analysis means such as liquid chromatography or gas chromatography.

  Examples of the solvent (E) include 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; ethyl lactate, butyl acetate, amyl acetate and And esters such as ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone; cyclic esters such as γ-butyrolactone; A solvent (E) may be used individually by 1 type, and may use 2 or more types together.

<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 component (F) is not particularly limited, and additives known in the resist field, for example, sensitizers, dissolution inhibitors, surfactants, stabilizers, dyes and the like can be used.

<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 mentioned above on a board | substrate,
(2) a step of removing the solvent from the composition after coating to form a composition layer;
(3) a step of exposing the composition layer using an exposure machine;
(4) A step of heating the composition layer after exposure,
(5) The process which develops the composition layer after a heating using a image development apparatus is included.

  Application of the resist composition onto the substrate can be performed by a commonly used apparatus such as a spin coater.

The removal of the solvent is performed, for example, by evaporating the solvent using a heating device such as a hot plate or by using a decompression device to form a composition layer from which the solvent has been removed. As for the temperature in this case, about 50-200 degreeC is illustrated, for example. The pressure is exemplified by about 1 to 1.0 × 10 ⁵ Pa.

The obtained composition layer is exposed using an exposure machine. The exposure machine may be an immersion exposure machine. At this time, exposure is usually performed through a mask corresponding to a required pattern. The exposure light source emits ultraviolet laser light such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ₂ laser (wavelength 157 nm), solid-state laser light source (YAG or semiconductor laser, etc.) Various types of laser beam can be used, such as those that convert the wavelength of the laser beam from) to radiate a harmonic laser beam in the far ultraviolet region or the vacuum ultraviolet region.

The composition layer after the exposure is subjected to heat treatment for promoting the deprotection group reaction. As heating temperature, it is about 50-200 degreeC normally, Preferably it is about 70-150 degreeC.
The heated composition layer is usually developed using an alkali developer using a developing device.
The alkaline developer used here 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).
After development, it is preferable to rinse with ultrapure water to remove water remaining on the substrate and the pattern.

<Application>
The resist composition of the present invention is suitable as a resist composition for KrF excimer laser exposure, a resist composition for ArF excimer laser exposure, a resist composition for EB, or a resist composition for EUV exposure machines.

Hereinafter, the present invention will be described in detail by way of examples.
In Examples and Comparative Examples, “%” and “part” representing content and use amount are based on mass unless otherwise specified.
The weight average molecular weight is a value obtained by gel permeation chromatography (HLC-8120GPC, manufactured by Tosoh Corporation, three columns are “TSKgel Multipore HXL-M”, and the solvent is tetrahydrofuran) using polystyrene as a standard product.
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 structure of the compound was confirmed using MASS; LC / MSD type or LC / MSD TOF type; manufactured by Agilent).

Synthesis of Compound (bb1) In a solution obtained by mixing 12.0 parts of a compound represented by the formula (bb1-a) (leucine, Sigma-Aldrich), 36 parts of dioxane and 36 parts of ion-exchanged water, 30 parts of triethylamine and the formula A compound represented by (bb1-b) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred overnight at room temperature. The obtained mixed solution was extracted with heptane, and the organic layer containing heptane was removed. To the aqueous layer was added 216 g of 5% aqueous hydrochloric acid, and the mixture was extracted with ethyl acetate. Magnesium sulfate was added to the organic layer containing ethyl acetate, and the mixture was stirred and filtered. The obtained filtrate was distilled off under reduced pressure to obtain 23.1 parts of a compound represented by the formula (bb1-c).

  To a mixed solution of 4.0 parts of the compound represented by the formula (bb1-c) and 25 parts of N, N-dimethylformamide, 1.33 parts of potassium carbonate and 0.40 parts of potassium iodide are added, and 40 ° C. For 1 hour. Thereafter, 2.70 parts of a compound represented by the formula (bb1-d) (methyl 4- (chloromethyl) benzoate, manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 40 ° C. for 2 hours. The obtained mixed solution was cooled to room temperature, 75 parts of ion exchange water was added, and extraction was performed with 150 parts of ethyl acetate. The operation of washing the obtained organic layer containing ethyl acetate with water and liquid separation was repeated 5 times. The obtained ethyl acetate layer was distilled off under reduced pressure to obtain 4.4 parts of a compound represented by the formula (bb1). MASS: 393.2

Synthesis of Compound (bb2) In a solution obtained by mixing 12.0 parts of a compound represented by the formula (bb1-a) (leucine, Sigma-Aldrich), 36 parts of dioxane and 36 parts of ion-exchanged water, 30 parts of triethylamine and the formula 20.4 parts of a compound represented by (bb2-b) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred at room temperature overnight. The obtained mixed solution was extracted with heptane, and the organic layer containing heptane was removed. To the aqueous layer was added 216 g of 5% aqueous hydrochloric acid, and the mixture was extracted with ethyl acetate. Magnesium sulfate was added to the organic layer containing ethyl acetate, and the mixture was stirred and filtered. The obtained filtrate was distilled off under reduced pressure to obtain 20.1 parts of a compound represented by the formula (bb2-c).

  To a mixed solution of 4.0 parts of the compound represented by the formula (bb2-c) and 25 parts of N, N-dimethylformamide, 1.33 parts of potassium carbonate and 0.40 parts of potassium iodide are added, and 40 ° C. For 1 hour. Thereafter, 2.67 parts of a compound represented by the formula (bb1-d) (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred at 40 ° C. for 2 hours. The obtained mixed solution was cooled to room temperature, 75 parts of ion exchange water was added, and extraction was performed with 150 parts of ethyl acetate. The operation of washing the obtained organic layer containing ethyl acetate with water and liquid separation was repeated 5 times. The obtained ethyl acetate layer was distilled off under reduced pressure to obtain 4.0 parts of a compound represented by the formula (bb2). MASS: 366.2

The monomers used for resin synthesis are shown below.

[Synthesis of Resin A1]
Monomer D, monomer E, monomer B, monomer C and monomer F were charged at a molar ratio of 30: 14: 6: 20: 30. Subsequently, 1.5 mass times dioxane was added with respect to the total mass of all the monomers. Into the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were respectively added to 1.00 mol% and 3.00 mol% with respect to the total number of moles of all monomers. And heated at 73 ° C. for about 5 hours. Thereafter, the reaction solution is purified by performing the operation of pouring into a large amount of methanol / water mixed solvent (4: 1) and precipitating three times, and the weight average molecular weight is about 8.1 × 10 ^3. The coalescence was obtained with a yield of 65%. This copolymer has a repeating unit of the following formula, and this is designated as resin A1.

[Synthesis of Resin A2]
Monomer A, monomer B and monomer C were charged in a molar ratio of 50:25:25, and then 1.5 mass times dioxane was added to the total mass of all monomers. To the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators in proportions of 1 mol% and 3 mol%, respectively, with respect to the total number of moles of all monomers. This was heated at 77 ° C. for about 5 hours. Thereafter, the reaction solution is purified by pouring it into a large amount of methanol / water mixed solvent (3: 1) and precipitating three times, and the weight average molecular weight is about 8.0 × 10 ^3. The coalescence was obtained in 60% yield. This copolymer has a repeating unit of the following formula, and this is designated as resin A2.

Examples and Comparative Examples As shown in Table 1, chemical amplification was performed by filtering a mixture obtained by mixing and dissolving the above components and the following components through a fluororesin filter having a pore size of 0.2 μm. Type photoresist composition was prepared.

酸発生剤Ｂ２：

<Acid generator>
Acid generator B1:

Acid generator B2:

＜式（II）で表される化合物＞
化合物ｂｂ１：

化合物ｂｂ２：

＜式（III）で表される化合物＞
化合物ｃｃ１：５−（４’−シアノベンジル）−１，５−ジアザビシクロ［４．３．０］ノナン（この化合物は、特表２００５−５１１５３６号公報の実施例４に記載の方法に従って合成した。）

＜塩基性化合物：クエンチャー＞
クエンチャーＣ１：２，６−ジイソプロピルアニリン
＜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 ２６５部
２−ヘプタノン ２０．０部
プロピレングリコールモノメチルエーテル ２０．０部
γ−ブチロラクトン ３．５部 <Compound represented by formula (I)>
Compound aa1: 2,3-dichloro-5,6-dicyano-p-benzoquinone

<Compound represented by formula (II)>
Compound bb1:

Compound bb2:

<Compound represented by formula (III)>
Compound cc1: 5- (4′-cyanobenzyl) -1,5-diazabicyclo [4.3.0] nonane (This compound was synthesized according to the method described in Example 4 of JP-T-2005-511536. )

<Basic compound: Quencher>
Quencher C1: 2,6-diisopropylaniline <Solvent>
Propylene glycol monomethyl ether acetate 265 parts 2-heptanone 20.0 parts Propylene glycol monomethyl ether 20.0 parts γ-butyrolactone 3.5 parts

An organic antireflective coating composition (ARC-29; manufactured by Nissan Chemical Co., Ltd.) is applied to a silicon wafer and baked at 205 ° C. for 60 seconds to form an organic antireflective coating having a thickness of 78 nm. Formed. Next, the above resist composition was spin-coated on the organic antireflection film so that the film thickness after drying was 85 nm. The silicon wafer coated with the resist composition was pre-baked on a direct hot plate at a temperature described in the “PB” column of Table 1 for 60 seconds to form a resist film.
ArF excimer stepper for immersion exposure (XT: 1900Gi; manufactured by ASML, NA = 1.35, 3/4 Annular XY polarized light) on a silicon wafer on which a resist film is formed, and a contact hole pattern (hole pitch 100 nm / Using a mask for forming a hole diameter of 70 nm, exposure was performed while changing the exposure amount stepwise.
After the exposure, the silicon wafer was post-exposure baked on a hot plate at a temperature described in the “PEB” column of Table 1 for 60 seconds.
Next, this silicon wafer was subjected to paddle development for 60 seconds with a 2.38% tetramethylammonium hydroxide aqueous solution.

In each resist film, an exposure amount at which the hole diameter of a pattern formed with a mask having a hole diameter of 70 nm was 55 nm was defined as effective sensitivity.
Focus margin (DOF) evaluation: In the case of effective sensitivity, the focus range in which the hole diameter is maintained at 52.2 nm or more and 57.7 nm or less is defined as DOF, and the case where DOF is greater than 0.15 μm (in particular, DOF is 0.17 μm) The above was evaluated as ◎), and the case where the DOF was less than 0.15 μm was judged as x.
CD uniformity (CDU) evaluation: In terms of effective sensitivity, the hole diameter of a pattern formed with a mask having a hole diameter of 70 nm was measured 24 times per hole, and the average value was defined as the average hole diameter of one hole. The standard deviation is obtained from a population obtained by measuring 400 average hole diameters of a pattern formed with a mask having a hole diameter of 70 nm in the same wafer, and the standard deviation is less than 2.00 nm. Is judged as x when the standard deviation is larger than 2.00 nm.
Mask error factor (MEF) evaluation: In the effective sensitivity, the mask hole diameter of a pattern formed with a mask having a hole diameter of 72 nm, 71 nm, 70 nm, 69 nm, and 68 nm, respectively, is plotted on the horizontal axis, and the hole diameter of each pattern is plotted on the vertical axis. The slope of the straight line when plotted was calculated as MEF. A sample having an inclination of less than 3.0 was evaluated as ◯ (in particular, a sample having an inclination of less than 2.9), and a sample having an inclination of more than 3.0 was evaluated as x.
These results are shown in Table 2.

  The resist composition of the present invention can form a pattern having excellent focus margin (DOF), CD uniformity (CDU) and mask error factor (MEF).

Claims (5)

  A resin having an acid labile group and insoluble or hardly soluble in an alkaline aqueous solution, acting with an acid and soluble in an alkaline aqueous solution, an acid generator, a compound having a quinoid structure, a quencher, Containing a resist composition. The resist composition according to claim 1, wherein the compound having a quinoid structure is a compound represented by the formula (I).

[In formula (I), R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom, a halogen atom or a cyano group.
A ¹ and A ² each independently represent ═O, ═CR ⁵ R ⁶ or ═NR ⁷ .
R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]   The resist composition according to claim 1 or 2, wherein the quencher is a compound having a benzyl group. The resist composition according to claim 1, wherein the quencher is a compound represented by formula (II) or a compound represented by formula (III).

[In the formula (II),
R ^b1 , R ^b2 and R ^b3 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, or R ^b1 and R ^b2 are bonded to each other to form a ring having 3 to 36 carbon atoms. The hydrogen atom contained in the hydrocarbon group and the ring may be substituted with —OH, and —CH ₂ — contained in the hydrocarbon group and the ring is —O— or —CO—. It may be replaced.
R ^b4 and R ^b5 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a saturated cyclic hydrocarbon group having 6 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or 5 carbon atoms. Or an aromatic heterocyclic group of ˜9, or R ^b4 and R ^b5 may be bonded to each other to form a 5-membered or 6-membered heterocyclic ring, and the hydrogen atom contained in the alkyl group is —OH, -SH, -NH _2, it may be substituted by a saturated cyclic hydrocarbon group, aromatic hydrocarbon group or an aromatic heterocyclic group having a carbon number of 5 to 9 having 6 to 12 carbon atoms of 6 to 12 carbon atoms, —CH ₂ — contained in the alkyl group may be replaced by —O—, —S—, —CO—, —C (═NH) — or —NH—. Hydrogen atoms contained in the saturated cyclic hydrocarbon group, the aromatic hydrocarbon group, and the aromatic heterocyclic group may be substituted with —OH.
R ^b6 , R ^b7 , R ^b8 , R ^b9 and R ^b10 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Group, a C2-C4 acyl group, a C2-C7 alkoxycarbonyl group, or a C6-C12 aromatic hydrocarbon group which may have a substituent.
In formula (III),
R ^d1 and R ^d2 each independently represent an alkylene group having 1 to 18 carbon atoms which may have a substituent.
R ^d3 , R ^d4 , R ^d5 , R ^d6 and R ^d7 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Group, a C2-C4 acyl group, a C2-C7 alkoxycarbonyl group, or a C6-C12 aromatic hydrocarbon group which may have a substituent. ] (1) The process of apply | coating the resist composition in any one of Claims 1-4 on a board | substrate,
(2) a step of removing the solvent from the composition after coating to form a composition layer;
(3) a step of exposing the composition layer using an exposure machine;
(4) A step of heating the composition layer after exposure,
(5) a step of developing the heated composition layer using a developing device;
A method for producing a resist pattern including: