JP5612867B2 - Resist composition and pattern forming method - Google Patents

Description

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

Conventionally, a resist composition containing a resin and two types of acid generators of a salt represented by the following formula and triphenylsulfonium trifluoromethanesulfonate has been proposed (Patent Document 1).

JP 2009-19028 A

  In the case of conventional resist compositions, there are cases where the pattern shape and focus margin obtained are not always satisfactory.

［式（Ｉ）中、
Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立に、Ｃ_１〜Ｃ_６アルキル基、Ｃ_３〜Ｃ_１８飽和環状炭化水素基、Ｃ_６〜Ｃ_１２アリール基又はＣ_７〜Ｃ_１３アラルキル基を表すか、或いは、Ｒ^１及びＲ^２が互いに結合してＣ_５〜Ｃ_１２環を形成する。該環に含まれる−ＣＨ_２−は−Ｏ−又は−ＣＯ−で置き換わっていてもよい。］

［式（ＩＩ）中、
Ｒ^４及びＲ^５は、それぞれ独立に、水素原子又はＣ_１〜Ｃ_６アルキル基を表す。
Ｒ^６は、Ｃ_１〜Ｃ_６アルキル基を表す。］ The present invention includes the following inventions [1] to [10].
[1] A resist composition comprising a resin, an acid generator (B-1) and an acid generator (B-2),
The acid generator (B-1) is an anion having a group represented by the formula (I) or a group represented by the formula (II), a group represented by the formula (I), and a formula (II). An acid generator comprising a cation that does not have any of the groups
The acid generator (B-2) includes an anion having neither the group represented by the formula (I) nor the group represented by the formula (II), the group represented by the formula (I), and the formula (I A resist composition comprising an acid generator comprising a cation having no group represented by II).

[In the formula (I),
R ¹ , R ² and R ³ each independently represent a C ₁ -C ₆ alkyl group, a C ₃ -C ₁₈ saturated cyclic hydrocarbon group, a C ₆ -C ₁₂ aryl group or a C ₇ -C ₁₃ aralkyl group. Alternatively, R ¹ and R ² are bonded together to form a C ₅ -C ₁₂ ring. —CH ₂ — contained in the ring may be replaced by —O— or —CO—. ]

[In the formula (II),
R ⁴ and R ⁵ each independently represents a hydrogen atom or a C ₁ -C ₆ alkyl group.
R ⁶ represents a C ₁ -C ₆ alkyl group. ]

［式（ＩＩＩ）中、
Ｑ^１及びＱ^２は、それぞれ独立に、フッ素原子又はＣ_１〜Ｃ_６ペルフルオロアルキル基を表す。
Ｘ^１は、Ｃ_１〜Ｃ_６アルキレン基を表し、該アルキレン基に含まれる−ＣＨ_２−は−Ｏ−又は−ＣＯ−で置き換わっていてもよい。
Ｙ^１は、Ｃ_３〜Ｃ_１８飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、ヒドロキシル基、Ｃ_１〜Ｃ_６アルキル基、Ｃ_１〜Ｃ_６ヒドロキシアルキル基、Ｃ_１〜Ｃ_６アルコキシル基、Ｃ_６〜Ｃ_１２アリール基、Ｃ_３〜Ｃ_１８飽和環状炭化水素基又は−（ＣＨ_２）_ａ−Ｏ−ＣＯ−（ＣＨ_２）_ｂ−Ｒで置換されていてもよく、該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。該アリール基に含まれる水素原子は、Ｃ_１〜Ｃ_６アルキル基又はＣ_１〜Ｃ_６アルコキシル基で置換されていてもよい。
ａ及びｂは、それぞれ独立に、０〜４の整数を表す。
Ｒは、Ｃ_３〜Ｃ_１８飽和環状炭化水素基又はＣ_６〜Ｃ_１２アリール基を表し、該飽和環状炭化水素基及びアリール基に含まれる水素原子は、Ｃ_１〜Ｃ_６アルキル基又はＣ_１〜Ｃ_６アルコキシル基で置換されていてもよい。］ [2] The resist composition according to [1], wherein the anion of the acid generator (B-2) is an anion represented by the formula (III).

[In the formula (III),
Q ¹ and Q ² each independently represents a fluorine atom or a C _{1 to} C ₆ perfluoroalkyl group.
X ¹ represents a C _{1 to} C ₆ alkylene group, and —CH ₂ — contained in the alkylene group may be replaced by —O— or —CO—.
Y ¹ represents a C _{3 to} C ₁₈ saturated hydrocarbon group, and the hydrogen atom contained in the saturated hydrocarbon group is a hydroxyl group, a C _{1 to} C ₆ alkyl group, a C _{1 to} C ₆ hydroxyalkyl group, or C _1. -C ₆ alkoxyl _groups, C 6 _{-C 12} aryl _group, C 3 _{-C 18} saturated cyclic hydrocarbon group or _{- (CH 2) a -O-} CO- (CH 2) b -R may be substituted by In the saturated hydrocarbon group, —CH ₂ — may be replaced by —O— or —CO—. The hydrogen atom contained in the aryl group may be substituted with a C _{1 to} C ₆ alkyl group or a C _{1 to} C ₆ alkoxyl group.
a and b represent the integer of 0-4 each independently.
R _is, C 3 _{-C 18} represents a saturated cyclic hydrocarbon group or a _C 6 _{-C 12} aryl group, a hydrogen atom contained in the saturated cyclic hydrocarbon group and aryl _group, C 1 -C ₆ alkyl or _{C 1} it may be substituted by -C ₆ alkoxyl groups. ]

[3] In formula (I), R ¹ and R ² are bonded to each other to form a C _{5 to} C ₁₂ ring, R ³ represents a C _{1 to} C ₆ alkyl group, and —CH ₂ contained in the ring The resist composition according to [1] or [2], wherein-may be replaced by -O- or -CO-.

［式（Ｉ−１）中、Ｒ^３は上記と同じ意味を表す。］ [4] The resist composition according to any one of [1] to [4], wherein the group represented by the formula (I) is a group represented by the formula (I-1).

[In formula (I-1), R ³ represents the same meaning as described above. ]

［式（ＩＶ）中、
Ｒ^７は、式（Ｉ）で表される基又は式（ＩＩ）で表される基を表す。
Ｒ^８は、水素原子、Ｃ_１〜Ｃ_６アルキル基又はＣ_１〜Ｃ_６アルコキシ基を表す。
ｍは１〜５の整数を表す。］ [5] The resist composition according to any one of [1] to [4], wherein the anion of the acid generator (B-1) is an anion represented by the formula (IV).

[In the formula (IV),
R ⁷ represents a group represented by the formula (I) or a group represented by the formula (II).
R ⁸ represents a hydrogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ alkoxy group.
m represents an integer of 1 to 5. ]

［式（Ｖ）中、
Ｑ^１１及びＱ^１２は、それぞれ独立に、フッ素原子又はＣ_１〜Ｃ_６ペルフルオロアルキル基を表す。
Ｘ^１１は、単結合又はＣ_１〜Ｃ_６アルキレン基を表し、該アルキレン基に含まれる−ＣＨ_２−は−Ｏ−又は−ＣＯ−で置き換わっていてもよい。
Ｙ^１１は、（ｎ＋１）価のＣ_３〜Ｃ_１８飽和環状炭化水素基又は（ｎ＋１）価のＣ_３〜Ｃ_１８芳香族炭化水素基を表し、該飽和環状炭化水素基及び該芳香族炭化水素基に含まれる水素原子は、ヒドロキシル基又はＣ_１〜Ｃ_６アルキル基で置換されていてもよく、該飽和環状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。
Ｒ^９は、式（Ｉ）で表される基又は式（ＩＩ）で表される基を表す。
ｎは、１〜３の整数を表す。］ [6] The resist composition according to any one of [1] to [4], wherein the anion of the acid generator (B-1) is an anion represented by the formula (V).

[In the formula (V),
Q ¹¹ and Q ¹² each independently represent a fluorine atom or a C _{1 to} C ₆ perfluoroalkyl group.
X ¹¹ represents a single bond or a C _{1 to} C ₆ alkylene group, and —CH ₂ — contained in the alkylene group may be replaced by —O— or —CO—.
Y ¹¹ represents a (n + 1) -valent C _{3 to} C ₁₈ saturated cyclic hydrocarbon group or a (n + 1) -valent C _{3 to} C ₁₈ aromatic hydrocarbon group, and the saturated cyclic hydrocarbon group and the aromatic hydrocarbon The hydrogen atom contained in the group may be substituted with a hydroxyl group or a C _{1 to} C ₆ alkyl group, and —CH ₂ — contained in the saturated cyclic hydrocarbon group is replaced with —O— or —CO—. May be.
R ⁹ represents a group represented by the formula (I) or a group represented by the formula (II).
n represents an integer of 1 to 3. ]

[7] Any of [1] to [6], wherein the ratio of the content of the acid generator (B-1) and the acid generator (B-2) is from 1:10 to 7:10 by mass ratio. The resist composition as described.
[8] The resin has an acid labile group and is insoluble or hardly soluble in an aqueous alkali solution, and the resin that has reacted with an acid is a resin that can be dissolved in an aqueous alkali solution [1] to [7] The resist composition according to any one of the above.
[9] The resist composition according to any one of [1] to [8], which contains a basic compound.

[10] (1) A step of applying the resist composition according to any one of [1] to [9] 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 pattern forming method including a step of developing the heated composition layer using a developing device.

  According to the resist composition of the present invention, a pattern having an excellent shape and a good focus margin can be formed.

  The resist composition of the present invention comprises a resin (hereinafter sometimes referred to as “resin (A)”) and at least two acid generators (hereinafter referred to as “acid generator (B-1) and acid generator (B-2)”. In some cases).

<Resin (A)>
Resin (A) is a resin that becomes alkali-soluble by the action of an acid. A resin that becomes alkali-soluble by the action of an acid can be produced by polymerizing a monomer having an acid-labile group (hereinafter sometimes referred to as “monomer having an acid-labile group (a1)”), It becomes alkali-soluble by the action of acid. “Becomes soluble in alkali by the action of an acid” means “insoluble or hardly soluble in an aqueous alkali solution before contact with an acid, but soluble in an aqueous alkali solution after contact with an acid”. To do. 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, 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。

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.

ここで、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。
Ｒ^a1及びＲ^a2が互いに結合して形成する環としては、飽和環状炭化水素基、芳香族炭化水素基等が挙げられる。このような環は、好ましくはＣ_３〜Ｃ_２０であり、より好ましくはＣ_３〜Ｃ_１２である。 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.
The saturated cyclic hydrocarbon group may be monocyclic or polycyclic. Examples thereof include monocyclic saturated cyclic hydrocarbon groups such as a cycloalkyl group (for example, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, and a cyclooctyl group). Polycyclic saturation such as groups obtained by hydrogenating condensed aromatic hydrocarbon groups (for example, hydronaphthyl group) and bridged cyclic hydrocarbon groups (for example, adamantyl group, norbornyl group, methylnorbornyl group) A cyclic hydrocarbon group is mentioned. Further, a group in which a bridged ring (for example, norbornane ring) and a single ring (for example, cycloheptane ring, cyclohexane ring) or a polycyclic (for example, decahydronaphthalene ring) or bridged rings are condensed as shown below. Groups; groups in which these are combined (methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group) and the like.

Here, as the 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 Groups, 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. Such rings are preferably _C 3 _{-C 20,} more preferably _C 3 _{-C 12.}

In the present specification, unless otherwise specified, specific substituents to be described later can be applied to any chemical structural formula having the same substituents 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.
Further, "(meth) acrylic monomer" means at least one monomer having a structure of "CH ₂ = CH-CO-" or _{"CH 2 = C (CH 3)} -CO- ". Similarly, “(meth) acrylate” and “(meth) acrylic acid” mean “at least one of acrylate and methacrylate” and “at least one of acrylic acid and methacrylic acid”, respectively.

In equation (1), an aliphatic hydrocarbon group, preferably a _C 1 _{-C 20,} more preferably a _C 1 _{-C 12.}
The saturated cyclic hydrocarbon group is preferably C _{3 to} C ₂₀ , more preferably C _{3 to} C ₁₂ .

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 C _{5 to} C ₂₀ saturated cyclic hydrocarbon group 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、Ｃ₁〜Ｃ₈脂肪族炭化水素基又はＣ₃〜Ｃ₁₀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 a C _{1 to} C ₈ aliphatic hydrocarbon group or a C _{3 to} C ₁₀ saturated cyclic hydrocarbon group.
m1 represents the integer of 0-14.
n1 represents an integer of 0 to 10.

L ^a1 and L ^a2 are preferably —O— or —O— (CH ₂ ) _f1 —CO—O— (wherein f1 is an integer of 1 to 4), more preferably —O—. is there.
R ^a4 and R ^a5 are preferably methyl groups.
The aliphatic hydrocarbon group for R ^a6 and R ^a7 is preferably C ₆ or less, and the saturated cyclic hydrocarbon group is preferably C ₈ or less, more preferably C ₆ or less.
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 them, 1-ethyl-1-cyclohexyl (meth) acrylate is preferable, and 1-ethyl-1-cyclohexyl methacrylate is more preferable.

  The content of the structural 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Ｃ₁〜Ｃ₃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）を表す。
Ｒ^a13は、Ｃ₁〜Ｃ₈脂肪族炭化水素基又はＣ₃〜Ｃ₈飽和環状炭化水素基を表す。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、Ｃ₁〜Ｃ₁₂脂肪族炭化水素基又はＣ₃〜Ｃ₁₂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, a C _{1 to} C ₃ aliphatic hydrocarbon group, a carboxy group, a cyano group or an alkoxycarbonyl group (—COOR ^a13 ) which may have a substituent (for example, a hydroxy group).
R ^a13 represents a C _{1 to} C ₈ aliphatic hydrocarbon group or a C _{3 to} C ₈ saturated cyclic hydrocarbon group. A hydrogen atom of the aliphatic hydrocarbon group and the saturated cyclic hydrocarbon group may be substituted with a hydroxy group, and —CH ₂ — of the aliphatic hydrocarbon group and the saturated cyclic hydrocarbon group is —O— or It may be replaced by -CO-.
R ^{a10 to} R ^a12 each independently represent a C _{1 to} C ₁₂ aliphatic hydrocarbon group or a C _{3 to} C ₁₂ saturated cyclic hydrocarbon group, or R ^a10 and R ^a11 are bonded to each other to form a ring. The aliphatic hydrocarbon group and the hydrogen atom of the saturated cyclic hydrocarbon group may be substituted with a hydroxy group or the like, and —CH of the aliphatic hydrocarbon group and the saturated cyclic hydrocarbon group _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 structural 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Ｃ₁〜Ｃ₆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、Ｃ₁〜Ｃ₆アルキル基、Ｃ₁〜Ｃ₆アルコキシ基、Ｃ₂〜Ｃ₄アシル基、Ｃ₂〜Ｃ₄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。
ｌ_ａは０〜４の整数を表す。ｌ_ａ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Ｃ₁〜Ｃ₁₂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Ｃ₁〜Ｃ₁₇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Ｃ₁〜Ｃ₆アルキル基を表す。
Ｙ^ａ３は、Ｃ₁〜Ｃ₁₂脂肪族炭化水素基、Ｃ₃〜Ｃ₁₈飽和環状炭化水素基又はＣ₆〜Ｃ₁₈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 formula (a1-4),
R ¹⁰ represents a hydrogen atom, a halogen atom or a C ₁ -C ₆ alkyl group which may have a halogen atom.
R ¹¹ is independently a halogen atom, a hydroxy group, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, a C ₂ -C ₄ acyl group, a C ₂ -C ₄ acyloxy group, an acryloyl group or a methacryloyl group. Represents a group.
l _a represents an integer of 0 to 4; If l _a is an integer of 2 or more, plural R ¹¹ may be the same or different.
R ¹² and R ¹³ each independently represents a hydrogen atom or a C _{1 to} C ₁₂ hydrocarbon group.
X ^a2 represents a divalent C _{1 to} C ₁₇ saturated hydrocarbon group which may have a single bond or a substituent, and —CH ₂ — contained in the saturated hydrocarbon group represents —CO—, —O -, - S -, - SO 2 - or -N ^{(R c)} - it may be replaced by.
R ^c represents a hydrogen atom or a C ₁ -C ₆ alkyl group.
Y ^a3 is a C _{1 to} C ₁₂ aliphatic hydrocarbon group, a C _{3 to} C ₁₈ saturated cyclic hydrocarbon group or a C _{6 to} C ₁₈ aromatic hydrocarbon group, and the aliphatic hydrocarbon group and saturated cyclic hydrocarbon The 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. And perfluorohexyl group.
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, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.
Examples of the saturated hydrocarbon group include aliphatic hydrocarbons and saturated cyclic hydrocarbons.

In the formula (a1-4), the alkyl group is preferably a C ₁ -C ₄ alkyl group, C ₁ -C more preferably ₂ alkyl group, a methyl group is particularly preferred.
The alkoxy group is preferably a C ₁ -C ₄ alkoxy group, more preferably C ₁ -C ₂ alkoxy group, a methoxy group is particularly preferred.
Examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, and a 2-ethylhexyl group. A cyclohexyl group, an adamantyl group, a 2-alkyl-2-adamantyl group, a 1- (1-adamantyl) -1-alkyl group, an isobornyl group, and the like are suitable.
Examples of the substituent which may be substituted with a divalent saturated hydrocarbon group and the substituent which may be substituted with an aliphatic hydrocarbon group, a saturated cyclic hydrocarbon group and an aromatic hydrocarbon group include, for example, a halogen atom , hydroxy group, C ₁ -C ₆ alkyl groups include C ₁ -C ₆ alkoxy group.

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

  The content of the structural 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 added in an amount of 15 mol with respect to 100 mol% of the monomer (a1) having an acid labile group. % Or more is preferable. When the ratio of the monomer having an adamantyl group is increased, 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, it has a phenolic hydroxyl group which is a hydroxystyrene as an acid stable monomer (a2) having a hydroxy group It is preferable to use an acid 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Ｃ₁〜Ｃ₆アルキル基を表す。
Ｒ^９は、ハロゲン原子、ヒドロキシ基、Ｃ₁〜Ｃ₆アルキル基、Ｃ₁〜Ｃ₆アルコキシ基、Ｃ₂〜Ｃ₄アシル基、Ｃ₂〜Ｃ₄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 formula (a2-0),
R ⁸ represents a C ₁ -C ₆ alkyl group which may have a hydrogen atom, a halogen atom or a halogen atom.
R ⁹ represents a halogen atom, a hydroxy group, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, a C ₂ -C ₄ acyl group, a C ₂ -C ₄ acyloxy group, an acryloyl group or a methacryloyl 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. ]

In the formula (a2-0), the alkyl group is preferably an C ₁ -C ₄ alkyl group, C ₁ -C more preferably ₂ alkyl group, a methyl group is particularly preferred.
The alkoxy group is preferably a C ₁ -C ₄ alkoxy group, more preferably C ₁ -C ₂ alkoxy group, a methoxy group is particularly preferred.
ma is preferably 0 to 2, more preferably 0 or 1, and particularly preferably 0.

In order to obtain 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.
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 structural unit derived from the monomer represented by the formula (a2-0) in the resin is usually from 5 to 90 mol%, preferably from 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—, and 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 structural 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 a monocycle such as a β-propiolactone ring, γ-butyrolactone ring, or δ-valerolactone ring, or a monocyclic lactone ring and other rings. 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−を表し、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、Ｃ₁〜Ｃ₄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Ｃ₁〜Ｃ₄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—, and 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 a C _{1 to} C ₄ aliphatic hydrocarbon group.
p1 represents an integer of 0 to 5.
R ^a22 and R ^a23 each independently represent a carboxy group, a cyano group, or a C ₁ -C ₄ aliphatic hydrocarbon group.
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 ^a20 are preferably methyl groups.
R ^a21 is preferably a methyl group.
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.

  Content of the structural unit derived from the monomer represented by Formula (a3-1), Formula (a3-2), or Formula (a3-3) in the resin is usually 5 to 50 mol% in all 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Ｃ₁〜Ｃ₃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−を形成する。
Ｒ^a27は、Ｃ₁〜Ｃ_１８脂肪族炭化水素基又はＣ₃〜Ｃ_１８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, a C ₁ -C ₃ aliphatic hydrocarbon 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 a C _{1 to} C ₁₈ aliphatic hydrocarbon group or a C _{3 to} C ₁₈ saturated cyclic hydrocarbon group, and —CH ₂ — of the aliphatic hydrocarbon group and the saturated cyclic hydrocarbon group is —O— or It may be replaced by -CO-. 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 is preferably C _{1 to} C ₈ , more preferably C _{1 to} C ₆ . The saturated cyclic hydrocarbon group is preferably C _{4 to} C ₁₈ , more preferably C _{4 to} C ₁₂ .
^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.

  Content of the structural unit derived from the monomer represented by Formula (a4-1), Formula (a4-2), or Formula (a4-3) in the resin is usually 2 to 40 mol% in all 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 the composition components excluding the solvent (E). The solid content in the composition and the content of the resin (A) relative thereto can be measured by known analytical means such as liquid chromatography or gas chromatography.

［式（Ｉ）中、
Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立に、Ｃ_１〜Ｃ_６アルキル基、Ｃ_３〜Ｃ_１８飽和環状炭化水素基、Ｃ_６〜Ｃ_１２アリール基又はＣ_７〜Ｃ_１３アラルキル基を表すか、或いは、Ｒ^１及びＲ^２が互いに結合してＣ_５〜Ｃ_１２環を形成する。該環に含まれる−ＣＨ_２−は−Ｏ−又は−ＣＯ−で置き換わっていてもよい。］

［式（ＩＩ）中、
Ｒ^４及びＲ^５は、それぞれ独立に、水素原子又はＣ_１〜Ｃ_６アルキル基を表す。
Ｒ^６は、Ｃ_１〜Ｃ_６アルキル基を表す。］ <Acid generator (B-1)>
The acid generator (B-1) is an anion having a group represented by the formula (I) or a group represented by the formula (II), a group represented by the formula (I), and a formula (II). It is an acid generator composed of a cation that does not have any of the above groups.

[In the formula (I),
R ¹ , R ² and R ³ each independently represent a C ₁ -C ₆ alkyl group, a C ₃ -C ₁₈ saturated cyclic hydrocarbon group, a C ₆ -C ₁₂ aryl group or a C ₇ -C ₁₃ aralkyl group. Alternatively, R ¹ and R ² are bonded together to form a C ₅ -C ₁₂ ring. —CH ₂ — contained in the ring may be replaced by —O— or —CO—. ]

[In the formula (II),
R ⁴ and R ⁵ each independently represents a hydrogen atom or a C ₁ -C ₆ alkyl group.
R ⁶ represents a C ₁ -C ₆ alkyl group. ]

  Examples of the aralkyl group include benzyl group, phenethyl group, phenylpropyl group, trityl group, naphthylmethyl group, and naphthylethyl group.

In the formula (I) and Formula (II), the alkyl group _is preferably a C 1 -C ₄ alkyl _group, C 1 -C more preferably ₂ alkyl group, a methyl group is particularly preferred.
Examples of the ring formed by combining R ¹ and R ² with each other include saturated cyclic hydrocarbons and aromatic hydrocarbons, and saturated cyclic hydrocarbons are particularly preferable.

Examples of —CR ¹ R ² R ³ in formula (I) include the following groups.

なかでも、Ｒ^１及びＲ^２は、互いに結合してＣ_６〜Ｃ_１０環を形成するものが好ましく、アダマンタン環を形成するものがより好ましい。Ｒ^３は、メチル基又はエチル基であることが好ましい。 When R ¹ and R ² are bonded to each other to form a C _{5 to} C ₁₂ ring as —CR ¹ R ² R ³ , for example, the following groups are exemplified.

Among these, R ¹ and R ² are preferably bonded to each other to form a C _{6 to} C ₁₀ ring, more preferably an adamantane ring. R ³ is preferably a methyl group or an ethyl group.

［式（Ｉ−１）中、Ｒ^３は上記と同じ意味を表す。］ That is, the group represented by the formula (I) is preferably a group represented by the formula (I-1).

[In formula (I-1), R ³ represents the same meaning as described above. ]

［式（ＩＶ）中、
Ｒ^７は、式（Ｉ）で表される基又は式（ＩＩ）で表される基を表す。
Ｒ^８は、水素原子、Ｃ_１〜Ｃ_６アルキル基又はＣ_１〜Ｃ_６アルコキシ基を表す。
ｍは１〜５の整数を表す。］ In the acid generator (B-1), the anion having the group represented by formula (I) or the group represented by formula (II) is preferably an anion represented by formula (IV), for example. .

[In the formula (IV),
R ⁷ represents a group represented by the formula (I) or a group represented by the formula (II).
R ⁸ represents a hydrogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ alkoxy group.
m represents an integer of 1 to 5. ]

In the formula (IV), the alkoxy group is preferably C _{1 to} C ₄ , more preferably C _{1 to} C ₂ , and particularly preferably a methoxy group.

Among the anions represented by the formula (IV), examples of the anion having a group represented by the formula (I) include the following anions.

Among the anions represented by the formula (IV), the anions having the group represented by the formula (II) include the following anions.

［式（Ｖ）中、
Ｑ^１１及びＱ^１２は、それぞれ独立に、フッ素原子又はＣ_１〜Ｃ_６ペルフルオロアルキル基を表す。
Ｘ^１１は、Ｃ_１〜Ｃ_６アルキレン基を表し、該アルキレン基に含まれる−ＣＨ_２−は−Ｏ−又は−ＣＯ−で置き換わっていてもよい。
Ｙ^１１は、（ｎ＋１）価のＣ_３〜Ｃ_１８飽和環状炭化水素基又は（ｎ＋１）価のＣ_３〜Ｃ_１８芳香族炭化水素基を表し、該飽和環状炭化水素基及び該芳香族炭化水素基に含まれる水素原子は、ヒドロキシル基又はＣ_１〜Ｃ_６アルキル基で置換されていてもよく、該飽和環状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。
Ｒ^９は、式（Ｉ）で表される基又は式（ＩＩ）で表される基を表す。
ｎは、１〜３の整数を表す。］ The anion having a group represented by formula (I) or a group represented by formula (II) in the acid generator (B-1) is, for example, an anion represented by formula (V) Also good.

[In the formula (V),
Q ¹¹ and Q ¹² each independently represent a fluorine atom or a C _{1 to} C ₆ perfluoroalkyl group.
X ¹¹ represents a C _{1 to} C ₆ alkylene group, and —CH ₂ — contained in the alkylene group may be replaced by —O— or —CO—.
Y ¹¹ represents a (n + 1) -valent C _{3 to} C ₁₈ saturated cyclic hydrocarbon group or a (n + 1) -valent C _{3 to} C ₁₈ aromatic hydrocarbon group, and the saturated cyclic hydrocarbon group and the aromatic hydrocarbon The hydrogen atom contained in the group may be substituted with a hydroxyl group or a C _{1 to} C ₆ alkyl group, and —CH ₂ — contained in the saturated cyclic hydrocarbon group is replaced with —O— or —CO—. May be.
R ⁹ represents a group represented by the formula (I) or a group represented by the formula (II).
n represents an integer of 1 to 3. ]

Examples of the perfluoroalkyl group include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, and a perfluorohexyl group. It is done.
Examples of the alkylene group include methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, and 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 Straight chain such as a group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane-1,17-diyl group Jo alkylene group; a straight-chain alkylene group, C ₁ -C ₄ alkyl group (e.g. methyl group, an ethyl group, a propyl group, an isopropyl group, butyl group, sec- butyl group, tert- butyl Include branched alkylene groups added to the side chains etc.).

In the formula (V), 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 alkylene group of X ¹¹ is replaced by —O— or —CO— include any of formulas (b1-1) to (b1-6). Preferably it is represented by Formula (b1-1)-Formula (b1-4), More preferably, it is represented by Formula (b1-1) or Formula (b1-2). Incidentally, the formula (b1-1) ~ formula (b1-6) has its left and right are described in accordance with the formula (B1), the left ^CQ 11 ^{Q 12} - combined with, combined with ^{-Y 11} in the right To do. 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Ｃ₁〜Ｃ₁₅アルキレン基を表す。
Ｌ^b3は、単結合又はＣ₁〜Ｃ₁₂アルキレン基を表す。
Ｌ^b4は、Ｃ₁〜Ｃ₁₃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、Ｃ₁〜Ｃ₁₅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、Ｃ₁〜Ｃ₁₄アルキレン基を表す。
Ｌ^b9及びＬ^b10は、それぞれ独立に、Ｃ₁〜Ｃ₁₁アルキレン基を表す。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 a C _{1 to} C ₁₅ alkylene group.
L ^b3 represents a single bond or a C _{1 to} C ₁₂ alkylene group.
L ^b4 represents a C _{1 to} C ₁₃ alkylene group. 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 a C _{1 to} C ₁₅ alkylene group. However, the upper limit of the carbon number of L ^b6 and L ^b7 is 16.
L ^b8 represents a C _{1 to} C ₁₄ alkylene group.
L ^b9 and L ^b10 each independently represent a C _{1 to} C ₁₁ alkylene group. 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.

（ｎ＋１）価のＣ_３〜Ｃ_１８芳香族炭化水素基としては、ベンゼン環に由来する（ｎ＋１）価の基が挙げられる。 Examples of the (n + 1) -valent C ₃ -C ₁₈ saturated cyclic hydrocarbon group include (n + 1) -valent groups derived from the following compounds.

Examples of the (n + 1) -valent C _{3 to} C ₁₈ aromatic hydrocarbon group include an (n + 1) -valent group derived from a benzene ring.

Among the anions represented by the formula (V), examples of the anion having a group represented by the formula (I) include the following anions.

Among the anions represented by the formula (V), examples of the anion having a group represented by the formula (II) include the following anions.

  In the acid generator (B-1), an anion containing either the group represented by formula (I) or the group represented by formula (II), an anion represented by formula (IV), or formula (V) The represented anion can be produced using a known method.

  Examples of the cation having neither the group represented by the formula (I) or the group represented by the formula (II) in the acid generator (B-1) include an onium cation such as a sulfonium cation, an iodonium cation, and ammonium. A cation, a benzothiazolium cation, a phosphonium cation, etc. are mentioned. Among these, a sulfonium cation and an iodonium cation are preferable, and an arylsulfonium cation is more preferable.

Examples thereof include cations represented by formula (b2-1) to formula (b2-4).

In formula (b2-1) to formula (b2-4),
R ^{b4 to} R ^b6 each independently represent a C _{1 to} C ₃₀ aliphatic hydrocarbon group, a C _{3 to} C ₁₈ saturated cyclic hydrocarbon group, or a C _{6 to} C ₁₈ aromatic hydrocarbon group. The aliphatic hydrocarbon group may be substituted with a hydroxy group, a C _{1 to} C ₁₂ alkoxy group or a C _{6 to} C ₁₈ aromatic hydrocarbon group, and the saturated cyclic hydrocarbon group is a halogen atom, C ₂ -C ₄ acyl group or glycidyloxy group may be substituted with, the aromatic hydrocarbon group, a halogen atom, hydroxy group, C ₁ -C ₁₈ aliphatic hydrocarbon group, C ₃ -C ₁₈ saturated cyclic hydrocarbon hydrogen radical or C ₁ -C ₁₂ alkoxy group may be substituted.
R ^b7 and R ^b8 each independently represent a hydroxy group, a C _{1 to} C ₁₂ aliphatic hydrocarbon group or a C _{1 to} C ₁₂ alkoxy group, and m 2 and n 2 each independently represent an integer of 0 to 5 .
R ^b9 and R ^b10 each independently represent a C _{1 to} C ₁₈ aliphatic hydrocarbon group or a C _{3 to} C ₁₈ saturated cyclic hydrocarbon group.
R ^b11 represents a hydrogen atom, a C _{1 to} C ₁₈ aliphatic hydrocarbon group, a C _{3 to} C ₁₈ saturated cyclic hydrocarbon group, or a C _{6 to} C ₁₈ aromatic hydrocarbon group. The aliphatic hydrocarbon group for R ^{b9 to} R ^b11 is preferably C _{1 to} C ₁₂ , and the saturated cyclic hydrocarbon group is preferably C _{3 to} C ₁₈ , more preferably C _{4 to} C ₁₂ .
R ^b12 represents a C _{1 to} C ₁₂ aliphatic hydrocarbon group, a C _{3 to} C ₁₈ saturated cyclic hydrocarbon group, or a C _{6 to} C ₁₈ aromatic hydrocarbon group. The aromatic hydrocarbon groups, C ₁ -C ₁₂ aliphatic hydrocarbon group, C ₁ -C ₁₂ alkoxy group, C ₃ -C ₁₈ saturated cyclic hydrocarbon group or alkylcarbonyloxy group may be substituted.
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), In these rings, —CH ₂ — may be replaced by —O—, —S—, or —CO—.
R ^{b13 to} R ^b18 each independently represents a hydroxy group, a C _{1 to} C ₁₂ aliphatic hydrocarbon group or a C _{1 to} C ₁₂ alkoxy group.
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.

In the formulas (b2-1) to (b2-4), preferred aliphatic hydrocarbon groups are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl. Group, pentyl group, hexyl group, octyl group and 2-ethylhexyl group.
Preferred saturated cyclic hydrocarbon groups include 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 represented by formula (b2-1) to formula (b2-4), the cation represented by formula (b2-1) is preferable, and the cation represented by formula (b2-1-1) is more preferable. The triphenylsulfonium cation (v2 = w2 = x2 = 0 in the formula (b2-1-1) 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、ヒドロキシ基、Ｃ₁〜Ｃ_１８脂肪族炭化水素基、Ｃ₃〜Ｃ_１８飽和環状炭化水素基又はＣ₁〜Ｃ₁₂アルコキシ基を表す。前記脂肪族炭化水素基は、好ましくはＣ_１〜Ｃ_１２であり、飽和環状炭化水素基は、好ましくはＣ_４〜Ｃ_１８である。前記脂肪族炭化水素基は、ヒドロキシ基、Ｃ₁〜Ｃ₁₂アルコキシ基或いはＣ₆〜Ｃ₁₈芳香族炭化水素基で置換されていてもよく、前記飽和環状炭化水素基は、ハロゲン原子、Ｃ₂〜Ｃ₄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。

In formula (b2-1-1),
R ^{b19 to} R ^b21 each independently represents a halogen atom, a hydroxy group, a C _{1 to} C ₁₈ aliphatic hydrocarbon group, a C _{3 to} C ₁₈ saturated cyclic hydrocarbon group or a C _{1 to} C ₁₂ alkoxy group. The aliphatic hydrocarbon group is preferably C _{1 to} C ₁₂ , and the saturated cyclic hydrocarbon group is preferably C _{4 to} C ₁₈ . The aliphatic hydrocarbon group may be substituted with a hydroxy group, a C _{1 to} C ₁₂ alkoxy group or a C _{6 to} C ₁₈ aromatic hydrocarbon group, and the saturated cyclic hydrocarbon group is a halogen atom, C ₂ -C ₄ acyl group or glycidyl group may be substituted.
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.

In the formula (b2-1-1), R ^{b19 to} R ^b21 are preferably each independently a halogen atom (more preferably a fluorine atom), a hydroxy group, a C _{1 to} C ₁₂ alkyl group, or a C _{1 to} C _{12 is an} alkoxy group, and v2 to x2 are each independently an integer of 0 to 5 (preferably 0 or 1).

Specific examples of the cation (b2-1-1) contained in the acid generator (B-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 (B-1) can be an arbitrary combination of the above-mentioned anions and cations.
Preferred acid generators (B-1) include the following acid generators.

<Acid generator (B-2)>
The acid generator (B-2) includes an anion having neither the group represented by the formula (I) nor the group represented by the formula (II), the group represented by the formula (I), and the formula (I It is an acid generator comprising a cation that does not have any of the groups represented by II).

［式（ＩＩＩ）中、
Ｑ^１及びＱ^２は、それぞれ独立に、フッ素原子又はＣ_１〜Ｃ_６ペルフルオロアルキル基を表す。
Ｘ^１は、Ｃ_１〜Ｃ_６アルキレン基を表し、該アルキレン基に含まれる−ＣＨ_２−は−Ｏ−又は−ＣＯ−で置き換わっていてもよい。
Ｙ^１は、Ｃ_３〜Ｃ_１８飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、ヒドロキシル基、Ｃ_１〜Ｃ_６アルキル基、Ｃ_１〜Ｃ_６ヒドロキシアルキル基、Ｃ_１〜Ｃ_６アルコキシル基、Ｃ_６〜Ｃ_１２アリール基、Ｃ_３〜Ｃ_１８飽和環状炭化水素基又は−（ＣＨ_２）_ａ−Ｏ−ＣＯ−（ＣＨ_２）_ｂ−Ｒで置換されていてもよく、該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。該アリール基に含まれる水素原子は、Ｃ_１〜Ｃ_６アルキル基又はＣ_１〜Ｃ_６アルコキシル基で置換されていてもよい。
ａ及びｂは、それぞれ独立に、０〜４の整数を表す。
Ｒは、Ｃ_３〜Ｃ_１８飽和環状炭化水素基又はＣ_６〜Ｃ_１２アリール基を表し、該飽和環状炭化水素基及びアリール基に含まれる水素原子は、Ｃ_１〜Ｃ_６アルキル基又はＣ_１〜Ｃ_６アルコキシル基で置換されていてもよい。］ Examples of the anion having neither the group represented by the formula (I) nor the group represented by the formula (II) include anions represented by the following formula (III).

[In the formula (III),
Q ¹ and Q ² each independently represents a fluorine atom or a C _{1 to} C ₆ perfluoroalkyl group.
X ¹ represents a C _{1 to} C ₆ alkylene group, and —CH ₂ — contained in the alkylene group may be replaced by —O— or —CO—.
Y ¹ represents a C _{3 to} C ₁₈ saturated hydrocarbon group, and the hydrogen atom contained in the saturated hydrocarbon group is a hydroxyl group, a C _{1 to} C ₆ alkyl group, a C _{1 to} C ₆ hydroxyalkyl group, or C _1. -C ₆ alkoxyl _groups, C 6 _{-C 12} aryl _group, C 3 _{-C 18} saturated cyclic hydrocarbon group or _{- (CH 2) a -O-} CO- (CH 2) b -R may be substituted by In the saturated hydrocarbon group, —CH ₂ — may be replaced by —O— or —CO—. The hydrogen atom contained in the aryl group may be substituted with a C _{1 to} C ₆ alkyl group or a C _{1 to} C ₆ alkoxyl group.
a and b represent the integer of 0-4 each independently.
R _is, C 3 _{-C 18} represents a saturated cyclic hydrocarbon group or a _C 6 _{-C 12} aryl group, a hydrogen atom contained in the saturated cyclic hydrocarbon group and aryl _group, C 1 -C ₆ alkyl or _{C 1} it may be substituted by -C ₆ alkoxyl groups. ]

  Examples of the hydroxyalkyl group include hydroxymethyl group, dihydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1,1′-dihydroxyethyl group, 1,2-dihydroxyethyl group, 1-hydroxypropyl group, 1 , 2-dihydroxypropyl group, hydroxyisopropyl group, hydroxybutyl group, hydroxypentyl group, hydroxyhexyl group and the like.

なかでも、式（Ｗ４）、式（Ｗ１３）、式（Ｗ１６）、式（Ｗ１７）及び式（Ｗ２１）等が好ましい。言い換えると、Ｙ^１として、シクロヘキシル基、アダマンタン基又はオキソ−アダマンタン基を有するものが好ましい。 In the formula (III), examples of the saturated hydrocarbon group for Y ¹ include the following groups.

Especially, Formula (W4), Formula (W13), Formula (W16), Formula (W17), Formula (W21), etc. are preferable. In other words, Y ¹ preferably has a cyclohexyl group, an adamantane group or an oxo-adamantane group.

置換基としてＣ_１〜Ｃ_６アルキル基を有するＹ^１としては、例えば、以下の基が挙げられる。なお、結合手は以下に示した位置以外の任意の位置とすることができる（以下同じ）

Examples of Y ¹ having a hydroxyl group or a C ₁ -C ₆ hydroxyalkyl group as a substituent include the following groups.

Examples of Y ¹ having a C ₁ -C ₆ alkyl group as a substituent include the following groups. The bond can be at any position other than the positions shown below (the same applies hereinafter).

Examples of Y ¹ having a C ₆ -C ₁₂ aryl group as a substituent include the following groups.

Examples of Y ¹ having — (CH ₂ ) _a —O—CO— (CH ₂ ) _b —R as a substituent include the following groups.

Specific examples of the anion represented by the formula (III) include the following.

Among these anions, the following anions are preferable.

  In the acid generator (B-2), an anion not containing any of the group represented by the formula (I) and the group represented by the formula (II) and the anion represented by the formula (III) are known methods. Can be manufactured.

  As a cation which does not have any of the group represented by the formula (I) and the group represented by the formula (II) in the acid generator (B-2), the cation exemplified in the acid generator (B-1) The same thing is mentioned.

An acid generator (B-2) can combine the above-mentioned anion and cation arbitrarily.
Preferred acid generators (B-2) are the following acid generators.

In the resist composition of the present invention, the acid generator (B) is preferably at least 1 part by mass (more preferably at least 3 parts by mass), preferably at most 30 parts by mass with respect to 100 parts by mass of the resin (A). (More preferably 25 parts by mass or less).
The acid generator (B-1) and the acid generator (B-2) are preferably contained in a mass ratio of 1:10 to 7:10.

<Basic compound (hereinafter sometimes referred to as “basic compound (C)”)>
The resist composition of the present invention may contain a basic compound (C). 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 either an aromatic ring such as aniline bonded with an amino group or 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).

In formula (C2) and formula (C2-1),
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 a C _{1 to} C ₆ alkoxy group, and the amino group it may be substituted by C ₁ -C ₄ alkyl group.
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 the aliphatic hydrocarbon group, alkoxy group, saturated cyclic hydrocarbon group or aromatic hydrocarbon group may have a substituent in R ^c5 and R ^c6 .
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.
In formula (C2) and formula (C2-1), the aliphatic hydrocarbon group is preferably about C _{1 to} C ₆ , and the saturated cyclic hydrocarbon group is preferably about C _{5 to} C ₁₀ , The group hydrocarbon group is preferably about C _{6 to} C ₁₀ , and the alkoxy group is preferably about C _{1 to} C ₆ .

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.

  Moreover, as a basic compound (C), the compound represented by Formula (C3)-Formula (C11) is mentioned.

In these equations,
R ^c8 represents any of the groups described for R ^c7 .
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 for R ^c15 is preferably about C _{1 to} C ₆ , the saturated cyclic hydrocarbon group is preferably about C _{3 to} C ₆ , and the alkanoyl group is preferably C _{2 to} C _6. 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 is preferably about C _{1 to} C ₆ .
R ^c3 represents a C ₁ -C ₄ alkyl group.

  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 or 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 aqueous solutions of tetramethylammonium hydroxide, (2-hydroxyethyl) trimethylammonium hydroxide (commonly called choline), and the like.
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 or use amount are based on mass unless otherwise specified.

The weight average molecular weight of the resin is a value determined by gel permeation chromatography.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: 3 TSKgel Multipore HXL-M + guard column (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 is NMR (GX-270 type or EX-270 type; manufactured by JEOL Ltd.), mass spectrometry (LC is Agilent 1100 type, MASS is Agilent LC / MSD type or LC / MSD TOF. Type).

温度計及び攪拌装置を備えたフラスコに、モノマーＡ、モノマーＢ及びモノマーＣを、モル比５０：２５：２５の割合で仕込み、全モノマーの合計質量に対して、１．５質量倍のジオキサンを加えた。得られた混合物に、開始剤としてアゾビスイソブチロニトリルとアゾビス（２，４−ジメチルバレロニトリル）とを全モノマーの合計モル数に対して、それぞれ、１ｍｏｌ％と３ｍｏｌ％との割合で添加し、これを７７℃で約５時間加熱した。その後、反応液を、メタノールと水との容量比３：１の混合溶媒の大過剰量中に注いで、析出した樹脂を濾取した。さらに濾取された樹脂を前記と同じ比率の大過剰量の混合溶媒中に注いで、濾取する操作を２回行うことにより精製し、重量平均分子量が約８０００である樹脂Ａ１を収率６０％で得た。 Synthesis Example 1: Synthesis of Resin A1

A flask equipped with a thermometer and a stirrer is charged with monomer A, monomer B and monomer C in a molar ratio of 50:25:25, and 1.5 mass times dioxane is added to the total mass of all monomers. added. 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 was poured into a large excess of a mixed solvent of methanol and water having a volume ratio of 3: 1, and the precipitated resin was collected by filtration. Further, the resin A1 having a weight average molecular weight of about 8,000 was obtained by pouring the resin collected by filtration into a large excess amount of a mixed solvent having the same ratio as described above, and performing the filtration operation twice. %.

温度計及び攪拌装置を備えたフラスコに、モノマーＡ、モノマーＢ、モノマーＣ及びモノマーＤを、モル比３５：１２：３０：２３の割合で仕込み、全モノマーの合計質量に対して、１．５質量倍のジオキサンを加えた。得られた混合物に、開始剤としてアゾビスイソブチロニトリルとアゾビス（２，４−ジメチルバレロニトリル）とを全モノマーの合計モル数に対して、それぞれ、１ｍｏｌ％と３ｍｏｌ％との割合で添加し、これを７７℃で約５時間加熱した。その後、反応液を、メタノールと水との容量比４：１の混合溶媒の大過剰量中に注いで、析出した樹脂を濾取した。さらに濾取された樹脂を前記と同じ比率の大過剰量の混合溶媒中に注いで、濾取する操作を２回行うことにより精製し、重量平均分子量が約８０００である樹脂Ａ２を収率７０％で得た。 Synthesis Example 2: Synthesis of Resin A2

A flask equipped with a thermometer and a stirrer was charged with monomer A, monomer B, monomer C and monomer D in a molar ratio of 35: 12: 30: 23, and 1.5% relative to the total mass of all monomers. Mass times dioxane was added. 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 was poured into a large excess of a mixed solvent of methanol and water in a volume ratio of 4: 1, and the precipitated resin was collected by filtration. Further, the resin A2 having a weight average molecular weight of about 8,000 was obtained by pouring the resin collected by filtration into a large excess amount of a mixed solvent having the same ratio as described above and performing the filtration operation twice. %.

温度計及び攪拌装置を備えたフラスコに、モノマーＥ、モノマーＢ及びモノマーＣを、モル比５０：２５：２５の割合で仕込み、全モノマーの合計質量に対して、２．２質量倍のメチルイソブチルケトンを加えた。得られた混合物に、開始剤としてアゾビスイソブチロニトリルを全モノマーの合計モル数に対して、それぞれ、２．４％との割合で添加し、これを９０℃で約５時間加熱した。その後、反応液を、メタノールと水との容量比９：１の混合溶媒の大過剰量中に注いで、析出した樹脂を濾取した。さらに濾取された樹脂を前記と同じ比率の大過剰量の混合溶媒中に注いで、濾取する操作を２回行うことにより精製し、重量平均分子量が約７０００である樹脂Ａ３を収率６５％で得た。 Synthesis Example 3: Resin A3

Into a flask equipped with a thermometer and a stirrer, monomer E, monomer B and monomer C were charged in a molar ratio of 50:25:25. Methyl isobutyl was 2.2 mass times the total mass of all monomers. Ketone was added. To the obtained mixture, azobisisobutyronitrile as an initiator was added in a ratio of 2.4% with respect to the total number of moles of all monomers, and this was heated at 90 ° C. for about 5 hours. Thereafter, the reaction solution was poured into a large excess of a mixed solvent having a volume ratio of 9: 1 of methanol and water, and the precipitated resin was collected by filtration. Furthermore, the resin A3 having a weight average molecular weight of about 7000 was obtained by pouring the resin collected by filtration into a large excess amount of the mixed solvent having the same ratio as described above and performing the operation of filtering twice to obtain a resin A3 having a weight average molecular weight of about 7000. %.

Examples 1 to 9 and Comparative Example 1
As shown in Table 1, a mixture obtained by mixing and dissolving the above-described resin and the following components was filtered through a fluororesin filter having a pore size of 0.2 μm to prepare a chemically amplified photoresist composition. did.

Ｂ１−２：

Ｂ１−３：

Ｂ１−４：

Ｂ２−１：

Ｂ２−２：

Ｂ２−３：トリフェニルスルホニウムトリフルオロメタンスルホネート <Acid generator>
B1-1:

B1-2:

B1-3:

B1-4:

B2-1:

B2-2:

B2-3: Triphenylsulfonium trifluoromethanesulfonate

<Basic compound: Quencher>
C1: 2,6-Diisopropylaniline C2: Tri-n-pentylamine <Solvent>
Propylene glycol monomethyl ether acetate 250 parts 2-heptanone 20.0 parts Propylene glycol monomethyl ether 40.0 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. After coating, the obtained silicon wafer was pre-baked on a direct hot plate at the temperature shown in Table 1 for 60 seconds.
Using the ArF excimer stepper [FPA5000-AS3; manufactured by Canon Inc., NA = 0.75, σ = 0.85, 6% HTM], the exposure amount was changed stepwise on the obtained silicon wafer. Then, exposure was performed through a mask for forming a contact hole pattern (hole diameter 130 nm / pitch 210 nm).
After the exposure, the silicon wafer was subjected to post-exposure baking at a temperature shown in Table 1 for 60 seconds on a hot plate.
Further, paddle development was performed for 60 seconds with a 2.38 wt% tetramethylammonium hydroxide aqueous solution.

  A contact hole pattern formed on the developed silicon wafer is observed with a scanning electron microscope (S-4100; manufactured by Hitachi, Ltd.), and a hole pattern formed with a mask for forming a pattern with a hole diameter of 130 nm. It was confirmed that the hole diameter was 110 nm.

<Focus margin evaluation (DOF)>
For Examples 1 to 9 and Comparative Example 1, in the effective sensitivity, the focal range in which the hole diameter is 105 nm or more and 116 nm or less is set to DOF, and when the DOF is 0.10 μm or more, it is judged as good and marked as “good”. When it was less than 0.10 μm, it was judged as defective and marked with “X”.
The results are shown in Table 2.

  According to the resist composition of the present invention, a pattern having an excellent shape and a good focus margin can be formed.

Claims (9)

A resist composition comprising a resin, an acid generator (B-1) and an acid generator (B-2),
The acid generator (B-1) is an anion having a group represented by the formula (I) or a group represented by the formula (II), a group represented by the formula (I), and a formula (II). An acid generator comprising a cation that does not have any of the groups
The acid generator (B-2) includes an anion represented by the formula (III) having neither the group represented by the formula (I) nor the group represented by the formula (II); And a cation that does not have any of the group represented by formula (II).

[In the formula (I),
R ¹ , R ² and R ³ each independently represent a C ₁ -C ₆ alkyl group, a C ₃ -C ₁₈ saturated cyclic hydrocarbon group, a C ₆ -C ₁₂ aryl group or a C ₇ -C ₁₃ aralkyl group. Alternatively, R ¹ and R ² are bonded together to form a C ₅ -C ₁₂ ring. —CH ₂ — contained in the ring may be replaced by —O— or —CO—. ]

[In the formula (II),
R ⁴ and R ⁵ each independently represents a hydrogen atom or a C ₁ -C ₆ alkyl group.
R ⁶ represents a C ₁ -C ₆ alkyl group. ]

[In the formula (III),
Q ¹ and Q ² each independently represents a fluorine atom or a C _{1 to} C ₆ perfluoroalkyl group.
X ¹ represents a C _{1 to} C ₆ alkylene group, and —CH ₂ — contained in the alkylene group may be replaced by —O— or —CO—.
Y ¹ represents a C _{3 to} C ₁₈ saturated hydrocarbon group, and the hydrogen atom contained in the saturated hydrocarbon group is a hydroxyl group, a C _{1 to} C ₆ alkyl group, a C _{1 to} C ₆ hydroxyalkyl group, or C _1. -C ₆ alkoxyl _groups, C 6 _{-C 12} aryl _group, C 3 _{-C 18} saturated cyclic hydrocarbon group or _{- (CH 2) a -O-} CO- (CH 2) b -R may be substituted by In the saturated hydrocarbon group, —CH ₂ — may be replaced by —O— or —CO—. The hydrogen atom contained in the aryl group may be substituted with a C _{1 to} C ₆ alkyl group or a C _{1 to} C ₆ alkoxyl group.
a and b represent the integer of 0-4 each independently.
R _is, C 3 _{-C 18} represents a saturated cyclic hydrocarbon group or a _C 6 _{-C 12} aryl group, a hydrogen atom contained in the saturated cyclic hydrocarbon group and aryl _group, C 1 -C ₆ alkyl or _{C 1} it may be substituted by -C ₆ alkoxyl groups. ] A resist composition comprising a resin, an acid generator (B-1) and an acid generator (B-2),
The acid generator (B-1) has a group represented by the formula (I) or a group represented by the formula (II), and is represented by either the formula (IV) or the formula (V). An acid generator comprising an anion and a cation having neither a group represented by formula (I) nor a group represented by formula (II);
The acid generator (B-2) includes an anion having neither the group represented by the formula (I) nor the group represented by the formula (II), the group represented by the formula (I), and the formula (I A resist composition comprising an acid generator comprising a cation having no group represented by II).

[In the formula (I),
R ¹ , R ² and R ³ each independently represent a C ₁ -C ₆ alkyl group, a C ₃ -C ₁₈ saturated cyclic hydrocarbon group, a C ₆ -C ₁₂ aryl group or a C ₇ -C ₁₃ aralkyl group. Alternatively, R ¹ and R ² are bonded together to form a C ₅ -C ₁₂ ring. —CH ₂ — contained in the ring may be replaced by —O— or —CO—. ]

[In the formula (II),
R ⁴ and R ⁵ each independently represents a hydrogen atom or a C ₁ -C ₆ alkyl group.
R ⁶ represents a C ₁ -C ₆ alkyl group. ]

[In the formula (IV),
R ⁷ represents a group represented by the formula (I) or a group represented by the formula (II).
R ⁸ represents a hydrogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ alkoxy group.
m represents an integer of 1 to 5. ]

[In the formula (V),
Q ¹¹ and Q ¹² each independently represent a fluorine atom or a C _{1 to} C ₆ perfluoroalkyl group.
X ¹¹ represents a single bond or a C _{1 to} C ₆ alkylene group, and —CH ₂ — contained in the alkylene group may be replaced by —O— or —CO—.
Y ¹¹ represents a (n + 1) -valent C _{3 to} C ₁₈ saturated cyclic hydrocarbon group or a (n + 1) -valent C _{3 to} C ₁₈ aromatic hydrocarbon group, and the saturated cyclic hydrocarbon group and the aromatic hydrocarbon The hydrogen atom contained in the group may be substituted with a hydroxyl group or a C _{1 to} C ₆ alkyl group, and —CH ₂ — contained in the saturated cyclic hydrocarbon group is replaced with —O— or —CO—. May be.
R ⁹ represents a group represented by the formula (I) or a group represented by the formula (II).
n represents an integer of 1 to 3. ] The resist composition according to claim 2, wherein the anion of the acid generator (B-2) is an anion represented by the formula (III).

[In the formula (III),
Q ¹ and Q ² each independently represents a fluorine atom or a C _{1 to} C ₆ perfluoroalkyl group.
X ¹ represents a C _{1 to} C ₆ alkylene group, and —CH ₂ — contained in the alkylene group may be replaced by —O— or —CO—.
Y ¹ represents a C _{3 to} C ₁₈ saturated hydrocarbon group, and the hydrogen atom contained in the saturated hydrocarbon group is a hydroxyl group, a C _{1 to} C ₆ alkyl group, a C _{1 to} C ₆ hydroxyalkyl group, or C _1. -C ₆ alkoxyl _groups, C 6 _{-C 12} aryl _group, C 3 _{-C 18} saturated cyclic hydrocarbon group or _{- (CH 2) a -O-} CO- (CH 2) b -R may be substituted by In the saturated hydrocarbon group, —CH ₂ — may be replaced by —O— or —CO—. The hydrogen atom contained in the aryl group may be substituted with a C _{1 to} C ₆ alkyl group or a C _{1 to} C ₆ alkoxyl group.
a and b represent the integer of 0-4 each independently.
R _is, C 3 _{-C 18} represents a saturated cyclic hydrocarbon group or a _C 6 _{-C 12} aryl group, a hydrogen atom contained in the saturated cyclic hydrocarbon group and aryl _group, C 1 -C ₆ alkyl or _{C 1} it may be substituted by -C ₆ alkoxyl groups. ] In Formula (I), R ¹ and R ² are bonded to each other to form a C _{5 to} C ₁₂ ring, R ³ represents a C _{1 to} C ₆ alkyl group, and —CH ₂ — contained in the ring is — The resist composition according to any one of claims 1 to 3, which may be replaced by O- or -CO-. Group represented by formula (I), the resist composition according to any one of claims 1-4 is a group represented by formula (I-1).

[In formula (I-1), R ³ represents the same meaning as described above. ] The resist composition according to any one of claims 1 to 5 , wherein the content ratio of the acid generator (B-1) to the acid generator (B-2) is 1:10 to 7:10 by mass ratio. . The resin according to any one of claims 1 to 6 , wherein the resin has an acid labile group and is insoluble or hardly soluble in an alkaline aqueous solution, and the resin that has reacted with an acid is a resin that can be dissolved in an alkaline aqueous solution. Resist composition. The resist composition according to any one of claims 1-7 which contains a basic compound. (1) The process of apply | coating the resist composition in any one of Claims 1-8 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 pattern forming method including a step of developing the heated composition layer using a developing device.