Salt, resin, resist composition and method for producing resist pattern

Abstract

A salt represented by the formula (I);

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to Japanese Application No. 2014-170761 filed on Aug. 25, 2014. The entire disclosures of Japanese Application No. 2014-170761 is incorporated hereinto by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a salt, a resin, a resist composition and a method for producing resist pattern, which are used for semiconductor microfabrication.

2. Related Art

A resist composition which contains a structural unit derived from a salt represented by the following formula is described in Patent document of JP 2013-125204A.

SUMMARY OF THE INVENTION

The present invention provides following inventions of <1> to <6>.

<1> A salt represented by the formula (I);

wherein Q¹ and Q² each independently represent a fluorine atom or a C₁ to C₆ perfluoroalkyl group,

L^b1 represents a single bond or a divalent C₁ to C₂₄ saturated hydrocarbon group where a methylene group may be replaced by an oxygen atom or a carbonyl group and where a hydrogen atom may be replaced by a hydroxyl group or a fluorine atom, and

Y represents a hydrogen atom, a fluorine atom, or an optionally substituted C₃ to C₁₈ alicyclic hydrocarbon group where a methylene group may be replaced by an oxygen atom, a carbonyl group or a sulfonyl group; and

Ar represents a divalent C₆ to C₂₀ aromatic hydrocarbon group, and

Z⁺ represents an organic sulfonium cation or an organic iodonium cation.

<2> A resin including a structural unit derived from the salt according to <1>.

<3> The resin according to <2>, further including a structural unit having an acid-labile group.

<4> A resist composition including the resin according <2> or <3>.

<5> A resist composition including the salt according to <1>.

<6> A method for producing a resist pattern including steps (1) to (5);

(1) applying the resist composition according to <4> or <5> onto a substrate;

(2) drying the applied composition to form a composition layer;

(3) exposing the composition layer;

(4) heating the exposed composition layer, and

(5) developing the heated composition layer.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

“(Meth)acrylic monomer” means a monomer having a structure of “CH₂═CH—CO—” or “CH₂═C(CH₃)—CO—”, as well as “(meth)acrylate” and “(meth)acrylic acid” mean “an acrylate or methacrylate” and “an acrylic acid or methacrylic acid,” respectively. Herein, chain structure groups include those having a linear structure and those having a branched structure. The indefinite articles “a” and “an” are taken as the same meaning as “one or more”.

In the specification, the term “solid components” means components other than solvents in a resist composition.

<Salt (I)>

The salt of the present invention is represented by formula (I) (which is sometimes referred to as “salt (I)”).

wherein Q¹ and Q² each independently represent a fluorine atom or a C₁ to C₆ perfluoroalkyl group,

L^b1 represents a single bond or a divalent C₁ to C₂₄ saturated hydrocarbon group where a methylene group may be replaced by an oxygen atom or a carbonyl group and where a hydrogen atom may be replaced by a hydroxyl group or a fluorine atom, and

Y represents a hydrogen atom, a fluorine atom, or an optionally substituted C₃ to C₁₈ alicyclic hydrocarbon group where a methylene group may be replaced by an oxygen atom, a carbonyl group or a sulfonyl group; and

Ar represents a divalent C₆ to C₂₀ aromatic hydrocarbon group, and

Z⁺ represents an organic sulfonium cation or an organic iodonium cation.

Examples of the perfluoroalkyl group of Q¹ and Q² include trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoro-isopropyl, perfluorobutyl, perfluoro-sec-butyl, perfluoro-tert-butyl, perfluoropentyl and perfluorohexyl groups.

Among these, Q¹ and Q² independently are preferably trifluoromethyl or fluorine atom, and more preferably a fluorine atom.

Examples of the divalent saturated hydrocarbon group of L^b1 include;

a chain alkanediyl group such as methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl, heptadecane-1,17-diyl, ethane-1,1-diyl, propane-1,1-diyl and propane-2,2-diyl groups;

a branched chain alkanediyl group such as butane-1,3-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl and 2-methylbutane-1,4-diyl groups;

a mono-alicyclic divalent saturated hydrocarbon group such as a cycloalkanediyl group (e.g., cyclobutan-1,3-diyl, cyclopentan-1,3-diyl, cyclohexane-1,4-diyl and cyclooctan-1,5-diyl groups); and

a poly-alicyclic divalent saturated hydrocarbon group such as norbornane-1,4-diyl, norbornane-2,5-diyl, adamantane-1,5-diyl and adamantane-2,6-diyl groups.

Examples of the saturated hydrocarbon group of L^b1 in which a methylene group has been replaced by an oxygen atom or a carbonyl group include groups represented by the formula (b1-1) to the formula (b1-7) below. * and ** represent a binding site, and * represents a binding site bonded to Y.

wherein L^b2 represents a single bond or a C₁ to C₂₂ divalent saturated hydrocarbon group,

L^b3 represents a single bond or a C₁ to C₁₉ divalent saturated hydrocarbon group,

L^b4 represents a C₁ to C₂₀ divalent saturated hydrocarbon group,

provided that the total carbon number contained in the group of L^b3 and L^b4 is 20 or less;

L^b5 represents a single bond or a C₁ to C₂₂ divalent saturated hydrocarbon group;

L^b6 represents a C₁ to C₂₂ divalent saturated hydrocarbon group,

provided that the total carbon number contained in the group of L^b5 and L^b6 is 23 or less;

L^b1 represents a single bond or a C₁ to C₂₂ divalent saturated hydrocarbon group,

L^b8 represents a C₁ to C₂₂ divalent saturated hydrocarbon group,

provided that the total carbon number contained in the group of L^b1 and L^b8 is 23 or less;

L^b9 and L^b10 independently represent a C₁ to C₁₈ divalent saturated hydrocarbon group;

provided that the total carbon number contained in the group of L^b9 and L^b10 is 20 or less;

L^b11 and L^b12 independently represent a single bond or a C₁ to C₁₈ divalent saturated hydrocarbon group;

L^b13 represents a C₁ to C₁₉ divalent saturated hydrocarbon group;

provided that the total carbon number contained in the group of L^b11, L^b12 and L^b13 is 19 or less;

L^b14 and L^b15 independently represents a single bond or a C₁ to C₂₀ divalent saturated hydrocarbon group;

L^b16 represents a C₁ to C₂₁ divalent saturated hydrocarbon group;

provided that the total carbon number contained in the group of L^b14, L^b15 and L^b16 is 21 or less.

Among these, L^b1 is preferably any one of the groups represented by the formula (b1-1) to the formula (b1-4), more preferably the group represented by the formula (b1-1) or the formula (b1-2), still more preferably the group represented by the formula (b1-1), particular preferably the divalent group represented by the formula (b1-1) in which L^b2 represents a single bond or methylene group.

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

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

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

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

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

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

Examples of the group represented by the formula (b1-7) include the following ones.

Examples of the group represented by L^b1 in which group a hydrogen atom has been replaced with a fluorin atom or a hydroxy group include the following ones.

Examples of the alicyclic hydrocarbon group represented by Y include groups represented by the formula (Y1) to the formula (Y27). * represents a bond bonded to L^b1.

Among these, the alicyclic hydrocarbon group of Y is preferably any one of groups represented by the formula (Y1) to the formula (Y19), more preferably any one of groups represented by the formula (Y11), (Y14), (Y15) or (Y19), and still more preferably a group represented by the formula (Y11) or (Y14).

Examples of the substituent for the alicyclic hydrocarbon group represented by Y include a halogen atom, a hydroxyl group, a C₁-C₁₂ alkyl group, a hydroxy group-containing C₁-C₁₂ alkyl group, a C₃-C₁₆ alicyclic hydrocarbon group, a C₁-C₁₂ alkoxy group, a C₆-C₁₈ aromatic hydrocarbon group, a C₇-C₂₁ aralkyl group, a C₂-C₄ acyl group, a glycidyloxy group and —(CH₂)_j2—O—CO—R^b1— in which R^b1 represents an C₁-C₁₆ alkyl group, a C₃-C₁₆ alicyclic hydrocarbon group, or a C₆-C₁₈ aromatic hydrocarbon group, and j2 represents an integer of 0 to 4.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms.

Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl and 2-ethylhexyl groups.

Examples of the hydroxy group-containing alkyl group include hydroxymethyl and hydroxyethyl groups.

Examples of the alicyclic hydrocarbon group include monocyclic groups such as a cycloalkyl group, i.e., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl groups; and polycyclic hydrocarbon groups such as decahydronaphtyl, adamantyl and norbornyl groups as well as groups below.

Examples of the aromatic hydrocarbon group include an aryl group such as phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl, phenanthryl, 2,6-diethylphenyl and 2-methyl-6-ethylphenyl groups.

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

Examples of the alkoxyl group include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, decyloxy and dodecyloxy groups.

Examples of the acyl group include a group in which an alkyl group bonds to carbonyl group, such as acetyl, propionyl and butyryl groups.

Examples of Y preferably include a fluorine atom, a hydrogen atom and the groups below.

Y is preferably a fluorine atom or a C₃ to C₁₈ alicyclic hydrocarbon group in which a hydrogen atom may be replaced by a substituent and in which a methylene group may be replaced by an oxygen atom or a carbonyl group, more preferably a fluorine atom or an amadantyl group in which a hydrogen atom may be replaced by a substituent and in which a methylene group may be replaced by an oxygen atom or a carbonyl group, and still more preferably a fluorine atom, an amadantyl group, a hydroxyamadantyl group or an oxoamadantyl group.

Examples of the divalent aromatic hydrocarbon group include phenylene, naphthylene, biphenylene and anthracenylene group. Phenylene and naphthylene group are preferred as Ar.

Specific examples of the anion for the salt (I) include anions described below.

Examples of the cation for the salt (I) include an organic sulfonium cation and an organic iodonium cation, among these, an organic sulfonium cation is preferred, and an arylsulfonium cation is more preferred.

The cations represented by the formula (b2-1) to the formula (b2-4) are preferred for the salt (I), which are sometimes referred to as “cation (b2-1)” to “cation (b2-4)” respectively:

wherein R^b4, R^b5 and R^b6 independently represent a C₁ to C₃₀ aliphatic hydrocarbon group, a C₃ to C₃₆ alicyclic hydrocarbon group or a C₆ to C₃₆ aromatic hydrocarbon group, a hydrogen atom contained in an aliphatic hydrocarbon group may be replaced by a hydroxy group, a C₁ to C₁₂ alkoxy group, a C₃ to C₁₂ alicyclic hydrocarbon group or a C₆ to C₁₈ aromatic hydrocarbon group, a hydrogen atom contained in an alicyclic hydrocarbon group may be replaced by a halogen atom, a C₁ to C₁₈ aliphatic hydrocarbon group, a C₂ to C₄ acyl group or a glycidyloxy group, a hydrogen atom contained in an aromatic hydrocarbon group may be replaced by a halogen atom, a hydroxy group or a C₁ to C₁₂ alkoxy group, or R^b4 and R^b5 may be bonded together with a sulfur atom bonded thereto to form a sulfur-containing ring, a methylene group contained in the ring may be replaced by an oxygen atom, a sulfur atom or a carbonyl group;

R^b7 and R^b8 in each occurrence independently represent a hydroxy group, a C₁ to C₁₂ aliphatic hydrocarbon group or a C₁ to C₁₂ alkoxy group,

m2 and n2 independently represent an integer of 0 to 5;

R^b9 and R^b10 independently represent a C₁ to C₃₆ aliphatic hydrocarbon group or a C₃ to C₃₆ alicyclic hydrocarbon group, or R^b9 and R^b10 may be bonded together with a sulfur atom bonded thereto to form a sulfur-containing ring, and a methylene group contained in the ring may be replaced by an oxygen atom, sulfur atom or a carbonyl group;

R^b11 represents a hydrogen atom, a C₁ to C₃₆ aliphatic hydrocarbon group, a C₃ to C₃₆ alicyclic hydrocarbon group or a C₆ to C₁₈ aromatic hydrocarbon group;

R^b12 represents a C₁ to C₁₂ aliphatic hydrocarbon group, a C₃ to C₁₈ alicyclic hydrocarbon group and a C₆ to C₁₈ aromatic hydrocarbon group, a hydrogen atom contained in an aliphatic hydrocarbon group may be replaced by a C₆ to C₁₈ aromatic hydrocarbon group, and a hydrogen atom contained in an aromatic hydrocarbon group may be replaced by a C₁ to C₁₂ alkoxy group or a C₁ to C₁₂ alkyl carbonyloxy group;

R^b11 and R^b12 may be bonded together with —CH—CO— bonded thereto to form a ring, and a methylene group contained in the ring may be replaced by an oxygen atom, sulfur atom or a carbonyl group;

R^b13, R^b14, R^b15, R^b16, R^b17 and R^b18 in each occurrence independently represent a hydroxy group, a C₁ to C₁₂ aliphatic hydrocarbon group or a C₁ to C₁₂ alkoxy group;

L^b31 represents —S— or —O—;

o2, p2, s2 and t2 independently represent an integer of 0 to 5;

q2 or r2 independently represent an integer of 0 to 4; and

u2 represents an integer of 0 or 1.

Examples of the aliphatic group preferably include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl and 2-ethylhexyl groups. Among these, the aliphatic hydrocarbon group of R^b9 to R^b12 is preferably a C₁ to C₁₂ aliphatic hydrocarbon group.

Examples of the alicyclic hydrocarbon group preferably include monocyclic groups such as a cycloalkyl group, i.e., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl groups; and polycyclic hydrocarbon groups such as decahydronaphtyl, adamantyl and norbornyl groups as well as groups below.

Among these, the alicyclic hydrocarbon group of R^b9 to R^b12 is preferably a C₃ to C₁₈ alicyclic group, and more preferably a C₄ to C₁₂ alicyclic hydrocarbon group.

Examples of the alicyclic hydrocarbon group where a hydrogen atom may be replaced by an aliphatic hydrocarbon group include methylcyclohexyl, dimethylcyclohexyl, 2-alkyladamantane-2-yl, methylnorbornyl and isobornyl groups. In the alicyclic hydrocarbon group where a hydrogen atom may be replaced by an aliphatic hydrocarbon group, the total carbon number of the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably 20 or less.

Examples of the aromatic hydrocarbon group preferably include an aryl group such as phenyl, tolyl, xylyl, cumenyl, mesityl, p-ethylphenyl, p-tert-butylphenyl, p-cyclohexylphenyl, p-adamantylphenyl, biphenyl, naphthyl, phenanthryl, 2,6-diethylphenyl and 2-methyl-6-ethylphenyl groups.

When the aromatic hydrocarbon includes an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, a C₁ to C₁₈ aliphatic hydrocarbon group or a C₃ to C₁₈ alicyclic hydrocarbon group is preferred.

Examples of the aromatic hydrocarbon group where a hydrogen atom may be replaced by an alkoxy group include a p-methoxyphenyl group.

Examples of the aliphatic hydrocarbon group where a hydrogen atom may be replaced by an aromatic hydrocarbon group include an aralkyl group such as benzyl, phenethyl phenylpropyl, trityl, naphthylmethyl and naphthylethyl groups.

Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, and dodecyloxy groups.

Examples of the acyl group include acetyl, propionyl and butyryl groups.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms.

Examples of the alkylcarbonyloxy group include methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, isopropylcarbonyloxy, n-butylcarbonyloxy, sec-butylcarbonyloxy, tert-butyl carbonyloxy, pentylcarbonyloxy, hexylcarbonyloxy, octylcarbonyloxy and 2-ethylhexylcarobonyloxy groups.

The sulfur atom-containing ring which is formed by R^b4 and R^b5 may be a monocyclic or polycyclic one, which may be an aromatic or non-aromatic one, and which may be a saturated or unsaturated one. The ring is preferably a ring having 3 to 18 carbon atoms, and more preferably a ring having 4 to 13 carbon atoms. Examples of the sulfur atom-containing ring include a 3- to 12-membered ring, preferably a 3- to 7-membered ring, examples thereof include rings below.

Examples of the ring formed by R^b9 and R^b10 may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. The ring may be a 3- to 12-membered ring, preferably a 3- to 7-membered ring. Examples of the ring include thiolane-1-ium ring (tetrahydrothiophenium ring), thian-1-ium ring and 1,4-oxathian-4-ium ring.

Examples of the ring formed by R^b11 and R^b12 may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. The ring may be a 3- to 12-membered ring, preferably a 3- to 7-membered ring. Examples of the ring include oxocycloheptane ring, oxocyclohexane ring, oxonorbornane ring and oxoadamantane ring.

Among the cations represented by formula (b2-1) to formula (b2-4), the cation represented by formula (b2-1) is preferred.

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

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

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

The salt (a) includes salts which has any one combination of the above anion and a cation.

Specific examples of the salt (a) include the following ones.

<Method for Producing the Salt (I)>

The salt (I) can be produced by reacting a salt represented by the formula (I-a) with a salt represented by the formula (I-b) in a solvent:

wherein Q¹, Q², L^b1, Y, Ar and Z⁺ are as defined above.

Preferred examples of the solvent include chloroform and ion-exchange water.

The salt represented by the formula (I-a) can be synthesized by methods described in JP2012-194466A.

Preferred examples of the salt represented by the formula (I-b) include salts represented by the formula below, which is available on the market.

<Resin>

The resin of the present invention includes a structural unit derived from the salt (I), which is sometimes referred to as “structural unit (I)”. This resin is useful for a resist composition described below. The resin may be a resin having only the structural unit (I), and a resin having another structural unit than the structural unit (I).

Examples of another structural unit include a structural unit having an acid-labile group. Here the “acid-labile group” means a group having a leaving group which is detached by contacting with an acid resulting in forming a hydrophilic group such as a hydroxy or carboxy group.

The resin which includes the structural unit derived from the salt (I) and the structural unit having the acid-labile group is sometimes referred to as “resin (A)”).

<Resin (A)>

The resin (A) includes the structural unit (I) and a structural unit having an acid-labile group. The structural unit having an acid-labile group is sometimes referred to as “structural unit (a1)”). The structural unit (a1) is derived from a monomer having an acid-labile group (which is sometimes referred to as “monomer (a1)”). The resin (A) further preferably includes a structural unit other than the structural unit (a1). Examples of the structural unit other than the structural unit (a1) include a structural unit not having an acid-labile group (which is sometimes referred to as “structural unit (s)”).

<Structural Unit (a1)>

The structural units (a1) is derived from a monomer (a1) having an acid-labile group.

In the resin (A), the acid-labile group contained in the structural unit (a1) is preferably the following group (1) and/or the group (2).

wherein R^a1 to R^a3 independently represent a C₁ to C₈ alkyl group, a C₃ to C₂₀ alicyclic hydrocarbon group or combination thereof, or R^a1 and R^a2 may be bonded together with a carbon atom bonded thereto to form a C₃ to C₂₀ divalent alicyclic hydrocarbon group;

na represents an integer of 0 or 1;

* represents a binding site.

wherein R^a1′ and R^a2′ independently represent a hydrogen atom or a C₁ to C₁₂ hydrocarbon group, R^a3′ represents a C₁ to C₂₀ hydrocarbon group, or R^a2′ and R^a3′ may be bonded together with a carbon atom and X bonded thereto to form a divalent C₃ to C₂₀ heterocyclic group, and a methylene group contained in the hydrocarbon group or the divalent heterocyclic group may be replaced by an oxygen atom or sulfur atom;

X represents —O— or —S—;

* represents a binding site.

Examples of the alkyl group of R^a1 to R^a3 include methyl, ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl and n-octyl groups.

Examples of the alicyclic hydrocarbon group of R^a1 to R^a3 include monocyclic groups such as a cycloalkyl group, i.e., cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl groups; and polycyclic hydrocarbon groups such as decahydronaphtyl, adamantyl and norbornyl groups as well as groups below. * represents a binding site.

The alicyclic hydrocarbon group of R^a1 to R^a3 preferably has 3 to 16 carbon atoms.

Examples of groups combining the alkyl group and the alicyclic hydrocarbon group include methyl cyclohexyl, dimethyl cyclohexyl, methyl norbornyl and cyclohexylmethyl, adamantylmethyl and norbornyletyl groups.

na is preferably an integer of 0.

When R^a1 and R^a2 is bonded together to form a divalent alicyclic hydrocarbon group, examples of the group-C(R^a1)(R^a2)(R^a3) include groups below. The divalent alicyclic hydrocarbon group preferably has 3 to 12 carbon atoms. * represent a binding site to —O—.

Specific examples of the group represented by the formula (1) include, for example,

1,1-dialkylalkoxycarbonyl group (a group in which R^a1 to R^a3 are alkyl groups, preferably tert-butoxycarbonyl group, in the formula (1)),

2-alkyladamantane-2-yloxycarbonyl group (a group in which R^a1, R^a2 and a carbon atom form adamantyl group, and R^a3 is alkyl group, in the formula (1)), and

1-(adamantane-1-yl)-1-alkylalkoxycarbonyl group (a group in which R^a1 and R^a2 are alkyl group, and R^a3 is adamantyl group, in the formula (1)).

The hydrocarbon group of R^a1′ to R^a3′ includes any of an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and a group formed by combining them.

Examples of the alkyl group and the alicyclic hydrocarbon group are the same examples as described above.

Examples of the aromatic hydrocarbon group include an aryl group such as phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl, phenanthryl, 2,6-diethylphenyl and 2-methyl-6-ethylphenyl groups.

Examples of the divalent heterocyclic group formed by bonding with R^a2′ and R^a3′ include groups below.

At least one of R^a1′ and R^a2′ is preferably a hydrogen atom.

Specific examples of the group represented by the formula (2) include a group below. * represents a binding site.

The monomer (a1) is preferably a monomer having an acid-labile group and an ethylene unsaturated bond, and more preferably a (meth)acrylic monomer having the acid-labile group.

Among the (meth)acrylic monomer having an acid-labile group, a monomer having a C₅ to C₂₀ alicyclic hydrocarbon group is preferred. When a resin (A) having a structural unit derived from a monomer (a1) having a bulky structure such as the alicyclic hydrocarbon group is used for a resist composition, the resist composition having excellent resolution tends to be obtained.

Examples of a structural unit derived from the (meth)acrylic monomer having the group represented by the formula (1) preferably include structural units represented by the formula (a1-0), the formula (a1-1) and the formula (a1-2) below. These may be used as a single structural unit or as a combination of two or more structural units. The structural unit represented by the formula (a1-0), the structural unit represented by the formula (a1-1) and a structural unit represented by the formula (a1-2) are sometimes referred to as “structural unit (a1-0)”, “structural unit (a1-1)” and “structural unit (a1-2)”), respectively, and monomers deriving the structural unit (a1-0), the structural unit (a1-1) and the structural unit (a1-2) are sometimes referred to as “monomer (a1-0)”, “monomer (a1-1)” and “monomer (a1-2)”), respectively:

wherein L^a01 represents —O— or *—O—(CH₂)_k01—CO—O—,

k01 represents an integer of 1 to 7,

* represents a binding site to —CO—,

R^a01 represents a hydrogen atom or a methyl group, and

R^a02, R^a03 and R^a04 independently represent a C₁ to C₈ alkyl group, a C₃ to C₁₈ alicyclic hydrocarbon group or combination thereof.

L^a01 is preferably an —O— or *—O—(CH₂)_k01—CO—O— in which k01 is preferably an integer of 1 to 4, more preferably an integer of 1, more preferably an —O—.

Examples of the alkyl group and an alicyclic hydrocarbon group of R^a02, R^a03 and R^a04 and combination thereof are the same examples as the group described in R^a1 to R^a3 in the formula (1).

The alkyl group of R^a02, R^a03 and R^a04 is preferably a C₁ to C₆ alkyl group.

The alicyclic hydrocarbon group of R^a02, R^a03 and R^a04 is preferably a C₃ to C₈ alicyclic hydrocarbon group, more preferably a C₃ to C₆ alicyclic hydrocarbon group.

The group formed by combining the alkyl group and the alicyclic hydrocarbon group has preferably 18 or less of carbon atom. Examples of those groups include methyl cyclohexyl, dimethyl cyclohexyl and methyl norbornyl groups.

R^a02 and R^a03 is preferably a C₁ to C₆ alkyl group, more preferably a methyl or ethyl group.

R^a04 is preferably a C₁ to C₆ alkyl group or C₅ to C₁₂ alicyclic hydrocarbon group, more preferably a methyl, ethyl, cyclohexyl or adamantyl group.

wherein L^a1 and L^a2 independently represent —O— or *—O—(CH₂)_k1—CO—O—,

k1 represents an integer of 1 to 7,

* represents a binding site to —CO—,

R^a4 and R^a5 independently represent a hydrogen atom or a methyl group,

R^a6 and R^a7 independently represent a C₁ to C₈ alkyl group, a C₃ to C₁₈ alicyclic hydrocarbon group or a combination thereof,

m1 represents an integer of 0 to 14,

n1 represents an integer of 0 to 10, and

n1′ represents an integer of 0 to 3.

L^a1 and L^a2 are preferably —O— or *—O—(CH₂)_k1′—CO—O— in which k1′ represents an integer of 1 to 4 and more preferably 1, still more preferably —O—.

R^a4 and R^a5 are preferably a methyl group.

Examples of the alkyl group of R^a6 and R^a7 include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, 2-ethylhexyl and n-octyl groups.

Examples of the alicyclic hydrocarbon group of R^a6 and R^a7 include monocyclic hydrocarbon groups such as a cycloalkyl group, i.e., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl and cyclooctyl groups; and polycyclic hydrocarbon groups such as decahydronaphtyl, adamantyl, 2-alkyadamantane-2-yl, 1-(adamantane-1-yl) alkane-1-yl, norbornyl, methyl norbornyl and isobornyl groups.

Examples of group formed by combining the alkyl group and the alicyclic hydrocarbon group of R^a6 and R^a7 include an aralkyl group such as benzyl and phenethyl groups.

The alkyl group of R^a6 and R^a7 is preferably a C₁ to C₆ alkyl group.

The alicyclic hydrocarbon group of R^a6 and R^a7 is preferably a C₃ to C₈ alicyclic hydrocarbon group, more preferably a C₃ to C₆ alicyclic hydrocarbon group.

m1 is preferably an integer of 0 to 3, and more preferably 0 or 1.

n1 is preferably an integer of 0 to 3, and more preferably 0 or 1.

n1′ is preferably 0 or 1, and more preferably 1.

Examples of the monomer (a1-0) preferably include monomers represented by the formula (a1-0-1) to the formula (a1-0-12), and more preferably monomers represented by the formula (a1-0-1) to the formula (a1-0-10) below.

Examples of the structural units (a1-0) include structural units in which a methyl group corresponding to R^a01 in the structural units represented as above has been replaced by a hydrogen atom.

Examples of the monomer (a1-1) include monomers described in JP 2010-204646A. Among these, the monomers are preferably monomers represented by the formula (a1-1-1) to the formula (a1-1-8), and more preferably monomers represented by the formula (a1-1-1) to the formula (a1-1-4) below.

Examples of the monomer (a1-2) include 1-methylcyclopentane-1-yl (meth)acrylate, 1-ethylcyclopentane-1-yl (meth)acrylate, 1-methylcyclohexane-1-yl (meth)acrylate, 1-ethylcyclohexane-1-yl (meth)acrylate, 1-ethylcycloheptane-1-yl (meth)acrylate, 1-ethylcyclooctane-1-yl (meth)acrylate, 1-isopropylcyclopentane-1-yl (meth)acrylate and 1-isopropylcyclohexane-1-yl (meth)acrylate. Among these, the monomers are preferably monomers represented by the formula (a1-2-1) to the formula (a1-2-12), and more preferably monomers represented by the formula (a1-2-3), the formula (a1-2-4), the formula (a1-2-9) and the formula (a1-2-10), and still more preferably monomer represented by the formula (a1-2-3) and the formula (a1-2-9) below.

When the resin (A) contains the structural unit (a1-0) and/or the structural unit (a1-1) and/or the structural unit (a1-2), the total proportion thereof is generally 10 to 95% by mole, preferably 15 to 90% by mole, more preferably 20 to 85% by mole, with respect to the total structural units (100% by mole) of the resin (A).

Further, examples of the structural unit (a1) having a group (1) include a structural unit presented by the formula (a1-3). The structural unit represented by the formula (a1-3) is sometimes referred to as “structural unit (a1-3)”. The monomer from which the structural unit (a1-3) is derived is sometimes referred to as “monomer (a1-3)”.

wherein R^a9 represents a carboxy group, a cyano group, a —COOR^a13, a hydrogen atom or a C₁ to C₃ aliphatic hydrocarbon group that may have a hydroxy group,

R^a13 represents a C₁ to C₈ aliphatic hydrocarbon group, a C₃ to C₂₀ alicyclic hydrocarbon group or a group formed by combining thereof, a hydrogen atom contained in the aliphatic hydrocarbon group and the alicyclic hydrocarbon group may be replaced by a hydroxy group, a a methylene group contained in the aliphatic hydrocarbon group and the alicyclic hydrocarbon group may be replaced by an oxygen atom or a carbonyl group, and

R^a10, R^a11 and R^a12 independently represent a C₁ to C₈ alkyl hydrocarbon group, a C₃ to C₂₀ alicyclic hydrocarbon group or a group formed by combining them, or R^a10 and R^a11 may be bonded together with a carbon atom bonded thereto to form a C₁ to C₂₀ divalent hydrocarbon group.

Here, examples of —COOR^a13 group include a group in which a carbonyl group is bonds to the alkoxy group, such as methoxycarbonyl and ethoxycarbonyl groups.

Examples of the aliphatic hydrocarbon group that may have a hydroxy group of R^a9 include methyl, ethyl, propyl, hydroxymethy and 2-hydroxyethyl groups.

Examples of the C₁ to C₈ aliphatic hydrocarbon group of R^a13 include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, 2-ethylhexyl and n-octyl groups.

Examples of the C₃ to C₂₀ alicyclic hydrocarbon group of R^a13 include cyclopentyl, cyclopropyl, adamantyl, adamantylmetyl, 1-(adamantyl-1-yl)-methylethyl, 2-oxo-oxolane-3-yl, 2-oxo-oxolane-4-yl groups.

Examples of the alkyl group of R^a10 to R^a12 include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, 2-ethylhexyl and n-octyl groups.

Examples of the alicyclic hydrocarbon group of R^a19 to R^a12 include monocyclic hydrocarbon groups such as a cycloalkyl group, i.e., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl groups; and polycyclic hydrocarbon groups such as decahydronaphtyl, adamantyl, 2-alkyl-2-adamantyl, 1-(adamantane-1-yl) alkane-1-yl, norbornyl, methyl norbornyl and isobornyl groups.

When R^a10 and R^a11 is bonded together with a carbon atom bonded thereto to form a divalent hydrocarbon group, examples of the group-C(R^a10)(R^a11)(R^a12) include groups below.

Examples of the monomer (a1-3) include tert-butyl 5-norbornene-2-carboxylate, 1-cyclohexyl-1-methylethyl 5-norbornene-2-carboxylate, 1-methylcyclohexyl 5-norbornene-2-carboxylate, 2-methy-2-adamantane-2-yl 5-norbornene-2-carboxylate, 2-ethyl-2-adamantane-2-yl 5-norbornene-2-carboxylate, 1-(4-methycyclohexyl)-1-methylethyl 5-norbornene-2-carboxylate, 1-(4-hydroxycyclohexyl)-1-methylethyl 5-norbornene-2-carboxylate, 1-methyl-(4-oxocyclohexyl)-1-ethyl 5-norbornene-2-carboxylate, and 1-(1-adamantane-1-yl)-1-methylethyl 5-norbornene-2-carboxylate.

The resin (A) having a structural unit (a1-3) can improve the resolution of the obtained resist composition because it has a bulky structure, and also can improve a dry-etching tolerance of the obtained resist composition because of incorporated a rigid norbornene ring into a main chain of the resin (A).

When the resin (A) contains the structural unit (a1-3), the proportion thereof is generally 10% by mole to 95% by mole, preferably 15% by mole to 90% by mole, and more preferably 20% by mole to 85% by mole, with respect to the total structural units constituting the resin (A) (100% by mole).

Examples of a structural unit (a1) having a group (2) include a structural unit represented by the formula (a1-4). The structural unit is sometimes referred to as “structural unit (a1-4)”.

wherein R^a32 represents a hydrogen atom, a halogen atom or a C₁ to C₆ alkyl group that may have a halogen atom,

R^a33 in each occurrence independently represent a halogen atom, a hydroxy group, a C₁ to C₆ alkyl group, a C₁ to C₆ alkoxy group, a C₂ to C₄ acyl group, a C₂ to C₄ acyloxy group, an acryloyl group or methacryloyl group,

1a represents an integer 0 to 4,

R^a34 and R^a35 independently represent a hydrogen atom or a C₁ to C₁₂ hydrocarbon group; and

R^a36 represents a C₁ to C₂₀ hydrocarbon group, or R^a35 and R^a36 may be bonded together with a C—O bonded thereto to form a divalent C₂ to C₂₀ hydrocarbon group, and a methylene group contained in the hydrocarbon group or the divalent hydrocarbon group may be replaced by an oxygen atom or sulfur atom.

Examples of the alkyl group of R^a32 and R^a33 include methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl groups. The alkyl group is preferably a C₁ to C₄ alkyl group, and more preferably a methyl or ethyl group, and still more preferably a methyl group.

Examples of the halogen atom of R^a32 and R^a33 include fluorine, chlorine, bromine or iodine atom.

Examples of the alkyl group that may have a halogen atom include trifluoromethyl, difluoromethyl, methyl, perfluoromethyl, 1,1,1-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, ethyl, perfluoropropyl, 1,1,1,2,2-pentafluoropropyl, propyl, perfluorobutyl, 1,1,2,2,3,3,4,4-octafluorobutyl, butyl, perfluoropentyl, 1,1,1,2,2,3,3,4,4-nonafluoropentyl, n-pentyl, n-hexyl and n-perfluorohexyl groups.

Examples of an alkoxy group include methoxy, ethoxy, propoxy, butoxy, pentyloxy, and hexyloxy groups. The alkoxy group is preferably a C₁ to C₄ alkoxy group, more preferably a methoxy and ethoxy group, and still more preferably methoxy group.

Examples of the acyl group include acetyl, propanonyl and butylyl groups.

Examples of the acyloxy group include acetyloxy, propanonyloxy and butylyloxy groups.

Examples of the hydrocarbon group of R^a34 and R^a35 are the same examples as described in R^a1′ to R^a2′ in the formula (2).

Examples of hydrocarbon group of R^a36 include a C₁ to C₁₈ alkyl group, a C₃ to C₁₈ alicyclic hydrocarbon group, a C₆ to C₁₈ aromatic hydrocarbon group or a group formed by combining them.

In the formula (a1-4), R^a32 is preferably a hydrogen atom.

R^a33 is preferably a C₁ to C₄ alkoxy group, more preferably a methoxy and ethoxy groups, and still more preferably methoxy group.

1a is preferably 0 or 1, and more preferably 0.

R^a34 is preferably a hydrogen atom.

R^a35 is preferably a C₁ to C₁₂ hydrocarbon group, and more preferably a methyl or ethyl group.

The hydrocarbon group of R^a36 is preferably a C₁ to C₁₈ alkyl group, a C₃ to C₁₈ alicyclic hydrocarbon group, a C₆ to C₁₈ aromatic hydrocarbon group or a combination thereof, and more preferably a C₁ to C₁₈ alkyl group, a C₃ to C₁₈ alicyclic hydrocarbon group or a C₇ to C₁₈ aralkyl group. The alkyl group and the alicyclic hydrocarbon group of R^a36 is preferably not substituted. When the aromatic hydrocarbon group of R^a36 has a substituent, the substituent is preferably a C₆ to C₁₀ aryloxy group.

Examples of the monomer from which a structural unit (a1-4) is derived include monomers described in JP 2010-204646A. Among these, the monomers are preferably monomers represented by the formula (a1-4-1) to the formula (a1-4-7), and more preferably monomers represented by the formula (a1-4-1) to the formula (a1-4-5) below.

When the resin (A) contains the structural unit (a1-4), the proportion thereof is generally 10% by mole to 95% by mole, preferably 15% by mole to 90% by mole, more preferably 20% by mole to 85% by mole, with respect to the total structural units constituting the resin (A) (100% by mole).

Examples of a structural unit having an acid-labile group include a structural unit represented by the formula (a1-5). Such structural unit is sometimes referred to as “structural unit (a1-5)”.

wherein R^a8 represents a hydrogen atom, a halogen atom or a C₁ to C₆ alkyl group that may have a halogen atom,

Z^a1 represent a single bond or *—(CH₂)_h3—CO-L⁵⁴-,

h3 represents an integer of 1 to 4,

* represents a binding site to L⁵¹,

L⁵¹, L⁵² and L⁵³ independently represent —O— or —S—,

s1 represents an integer of 1 to 3, and

s1′ represents an integer of 0 to 3.

In the formula (a1-5), R^a8 is preferably a hydrogen atom, a methyl group or trifluoromethyl group;

L⁵¹ is preferably —O—;

L⁵² and L⁵³ are independently preferably —O— or —S—, and more preferably one is —O— and another is —S—.

s1 is preferably 1;

s1′ is preferably an integer of 0 to 2;

Z^a1 is preferably a single bond or *—CH₂—CO—O—.

Examples of a monomer from which a structural unit (a1-5) is derived include a monomer described in JP 2010-61117A. Among these, the monomers are preferably monomers represented by the formula (a1-5-1) to the formula (a1-5-4), and more preferably monomers represented by the formula (a1-5-1) to the formula (a1-5-2) below.

When the resin (A) contains the structural unit (a1-5), the proportion thereof is generally 1% by mole to 50% by mole, preferably 3% by mole to 45% by mole, and more preferably 5% by mole to 40% by mole, with respect to the total structural units (100% by mole) constituting the resin (A).

Examples of a structural unit (a1) having an acid-labile group in a resin (A) is preferably at least one, more preferably two or more structural units selected from the structural unit (a1-0), the structural unit (a1-1), the structural unit (a1-2), the structural unit (a1-5), still more preferably a combination of the structural unit (a1-1) and the structural unit (a1-2), a combination of the structural unit (a1-1) and the structural unit (a1-5), a combination of the structural unit (a1-1) and the structural unit (a1-0), a combination of the structural unit (a1-2) and the structural unit (a1-0), a combination of the structural unit (a1-5) and the structural unit (a1-0), a combination of the structural unit (a1-0), the structural unit (a1-1) and the structural unit (a1-2), a combination of the structural unit (a1-0), the structural unit (a1-1) and the structural unit (a1-5), in particular preferably a combination of the structural unit (a1-1) and the structural unit (a1-2), and a combination of the structural unit (a1-1) and the structural unit (a1-5).

<Structural Unit Having No Acid-Labile Group(s)>

The structural units (s) is derived from a monomer (which is sometimes referred to as “monomer (s)”) having no acid-labile group.

For the monomer (s) from which a structural unit (s) is derived, a known monomer having no acid-labile group can be used.

As the structural unit (s), a structural unit having a hydroxy group or a lactone ring but having no acid-labile group is preferred. When a resin containing the structural unit derived from a structural unit having hydroxy group but having no acid-labile group (such structural unit is sometimes referred to as “structural unit (a2)”) and/or a structural unit having a lactone ring but having no acid-labile group (such structural unit is sometimes referred to as “structural unit (a3)”) is used, the adhesiveness of resist to a substrate and resolution of resist pattern tend to be improved.

<Structural Unit (a2)>

The structural unit (a2) having a hydroxy group may be an alcoholic hydroxy group or a phenolic hydroxy group.

When KrF excimer laser lithography (248 nm), or high-energy irradiation such as electron beam or EUV (extreme ultraviolet) is used for the resist composition, using the structural unit having a phenolic hydroxy group as structural unit (a2) is preferred.

When ArF excimer laser lithography (193 nm) is used, using the structural unit having an alcoholic hydroxy group as the structural unit (a2) is preferred, using the structural represented by the formula (a2-1) is more preferred.

The structural unit (a2) may be used as a single structural unit or as a combination of two or more structural units.

Examples of the structural unit (a2) having a phenolic hydroxy group include the structural unit (which is sometimes referred to as “structural unit (a2-0)”) represented by the formula (a2-0).

wherein R^a30 represents a hydrogen atom, a halogen atom or a C₁ to C₆ alkyl group that may have a halogen atom,

R^a31 in each occurrence independently represents a halogen atom, a hydroxy group, a C₁ to C₆ alkyl group, a C₁ to C₆ alkoxy group, a C₂ to C₄ acyl group, a C₂ to C₄ acyloxy group, an acryloyl group or methacryloyl group, and

ma represents an integer 0 to 4.

Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, n-pentyl and n-hexyl groups.

Example of the halogen atom is a chlorine atom, a fluorine atom and bromine atom.

Examples of a C₁ to C₆ alkyl group that may have a halogen atom of R^a30 include trifluoromethyl, difluoromethyl, methyl, perfluoromethyl, 1,1,1-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, ethyl, perfluoropropyl, 1,1,1,2,2-pentafluoropropyl, propyl, perfluorobutyl, 1,1,2,2,3,3,4,4-octafluorobutyl, butyl, perfluoropentyl, 1,1,1,2,2,3,3,4,4-nonafluoropentyl, n-pentyl, n-hexyl and n-perfluorohexyl groups.

R^a30 is preferably a hydrogen atom or a C₁ to C₄ alkyl group, and more preferably a hydrogen atom, methyl or ethyl group, and still more preferably a hydrogen atom or methyl group.

Examples of a C₁ to C₆ alkoxy group of R^a31 include methoxy, ethoxy, propoxy, butoxy, pentyloxy, and hexyloxy groups. R^a31 is preferably a C₁ to C₄ alkoxy group, more preferably a methoxy and ethoxy group, and still more preferably methoxy group.

Examples of the acyl group include acetyl, propanonyl and butylyl groups.

Examples of the acyloxy group include acetyloxy, propanonyloxy and butylyloxy groups.

ma is preferably 0, 1 or 2, more preferably 0 or 1, still more preferably 0.

The structural unit (a2-0) having a phenolic hydroxy group is preferably a structural unit represented below.

Among these, a structural unit represented by the formula (a2-0-1) or the formula (a2-0-2) is preferred.

Examples of a monomer from which the structural unit (a2-0) is derived include monomers described in JP2010-204634A.

The resin (A) which contains the structural units (a2) having a phenolic hydroxy group can be produced, for example, by polymerizing a monomer where its phenolic hydroxy group has been protected with a suitable protecting group, followed by deprotection. The deprotection is carried in such a manner that an acid-labile group in the structural unit (a1) is significantly impaired. Examples of the protecting group for a phenolic hydroxy group include an acetyl group.

When the resin (A) contains the structural unit (a2-0) having the phenolic hydroxy group, the proportion thereof is generally 5% by mole to 95% by mole, preferably 10% by mole to 80% by mole, more preferably 15% by mole to 80% by mole, with respect to the total structural units (100% by mole) constituting the resin (A).

Examples of the structural unit (a2) having alcoholic hydroxy group include the structural unit (which is sometimes referred to as “structural unit (a2-1)”) represented by the formula (a2-1).

wherein L^a3 represents —O— or *—O—(CH₂)_k2—CO—O—,

k2 represents an integer of 1 to 7,

* represents a binding site to —CO—,

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, and

o1 represents an integer of 0 to 10.

In the formula (a2-1), L^a3 is preferably —O—, —O—(CH₂)_f1—CO—O—, here f1 represents an integer of 1 to 4, and more preferably —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, and more preferably an integer of 0 or 1.

Examples of the monomer from which the structural unit (a2-1) is derived include monomers described in JP 2010-204646A. Among these, the monomers are preferably monomers represented by the formula (a2-1-1) to the formula (a2-1-6), more preferably structural units represented by the formula (a2-1-1) to the formula (a2-1-4), and still more preferably structural units represented by the formula (a2-1-1) and the formula (a2-1-3) below.

Examples of monomers introducing the structural unit (a2) having the alcoholic hydroxy group include monomers described in JP 2010-204646A.

When the resin (A) contains the structural unit (a2) having the alcoholic hydroxy group, the proportion thereof is generally 1% by mole to 45% by mole, preferably 1% by mole to 40% by mole, more preferably 1% by mole to 35% by mole, and still more preferably 2% by mole to 20% by mole, with respect to the total structural units (100% by mole) constituting the resin (A).

<Structural Unit (a3)>

The lactone ring included in the structural unit (a3) may be a monocyclic compound such as β-propiolactone, γ-butyrolactone, δ-valerolactone, or a condensed ring of monocyclic lactone ring with another ring. Examples of the lactone ring preferably include γ-butyrolactone, amadantane lactone, or bridged ring with γ-butyrolactone.

Examples of the structural unit (a3) include structural units represented by any of the formula (a3-1), the formula (a3-2), the formula (a3-3) and the formula (a3-4). These structural units may be used as a single unit or as a combination of two or more units.

wherein L^a4 represents *—O— or *—O—(CH₂)_k3—CO—O—, k3 represents an integer of 1 to 7, * represents a binding site to a carbonyl group,

R^a18 represents a hydrogen atom or a methyl group,

R^a21 in each occurrence represents a C₁ to C₄ aliphatic hydrocarbon group, and

p1 represents an integer of 0 to 5,

L^a5 represents *—O— or *—O—(CH₂)_k3—CO—O—, k3 represents an integer of 1 to 7, * represents a binding site to a carbonyl group,

R^a19 represents a hydrogen atom or a methyl group,

R^a22 in each occurrence represents a carboxy group, a cyano group or a C₁ to C₄ aliphatic hydrocarbon group,

q1 represents an integer of 0 to 3,

L^a6 represents *—O— or *—O—(CH₂)_k3—CO—O—, k3 represents an integer of 1 to 7, * represents a binding site to a carbonyl group,

R^a20 represents a hydrogen atom or a methyl group,

R^a23 in each occurrence represents a carboxy group, a cyano group or a C₁ to C₄ aliphatic hydrocarbon group, and

r1 represents an integer of 0 to 3,

R^a24 represents a hydrogen atom, a halogen atom or a C₁ to C₆ alkyl group that may have a halogen atom,

L^a7 represents a single bond, *-L^a8-O—, *-L^a8-CO—O—, *-L^a8-CO—O-L^a9-CO—O—, or *-L^a8-O—CO-L^a9-O—; * represents a binding site to a carbonyl group, and

L^a8 and L^a9 independently represents a C₁ to C₆ alkanediyl group.

Examples of the aliphatic hydrocarbon group R^a21, R^a22 and R^a23 include an alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl groups.

Examples of the halogen atom of R^a24 include fluorine, chlorine, bromine or iodine atom;

Examples of the alkyl group of R^a24 include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl and n-hexyl groups, preferably a C₁ to C₄ alkyl group, more preferably a methyl or ethyl group.

Examples of the alkyl group having a halogen atom of R^a24 include trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoro-isopropyl, perfluorobutyl, perfluoro-sec-butyl, perfluoro-tert-butyl, perfluoropentyl, perfluorohexyl, tricloromethyl, tribromomethyl and triiodomethyl groups.

Examples of the alkanediyl group of L^a8 and L^a9 include methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, butane-1,3-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl and 2-methylbutane-1,4-diyl groups.

In the formulae (a3-1) to (a3-3), L^a4 to L^a6 is independently preferably —O—, *—O—(CH₂)_{k3′—CO—O—, here k}3′ represents an integer of 1 to 4, more preferably —O— or *—O—CH₂—CO—O—, and still more preferably *—O—.

R^a18 to R^a21 is preferably a methyl group.

R^a22 and R^a23 are independently preferably a carboxy group, a cyano group or a methyl group.

p1, q1 and r1 are independently preferably an integer of 0 to 2, and more preferably 0 or 1

In the formula (a3-4), R^a24 is preferably a hydrogen atom or a C₁ to C₄ alkyl group, more preferably a hydrogen atom, a methyl group or an ethyl group, and still more preferably a hydrogen atom or a methyl group.

L^a7 is preferably a single bond or *-L^a8-CO—O—, and more preferably a single bond, —CH₂—CO—O— or —C₂H₄—CO—O—.

Examples of the monomer from which the structural unit (a3) is derived include monomers described in JP 2010-204646A, monomers described in JP2000-122294A and monomers described in JP2012-41274A. Among these, the structural units are preferably structural units represented by the formula (a3-1-1) to the formula (a3-1-4), the formula (a3-2-1) to the formula (a3-2-4), the formula (a3-3-1) to the formula (a3-3-4), the formula (a3-4-1) to the formula (a3-4-12), more preferably monomers represented by the formula (a3-1-1) to the formula (a3-1-2), the formula (a3-2-3), the formula (a3-2-4), the formula (a3-4-1) and the formula (a3-4-2), and still more preferably monomers represented by the formula (a3-1-1), the formula (a3-2-3) or the formula (a3-4-2) below.

When the resin (A) contains the structural units (a3), the total proportion thereof is preferably 5% by mole to 70% by mole, more preferably 10% by mole to 65% by mole, still more preferably 10% by mole to 60% by mole, with respect to the total structural units (100% by mole) constituting the resin (A).

The proportion each of the formula (a3-1), the formula (a3-2), the formula (a3-3) and the formula (a3-4) is preferably 5% by mole to 60% by mole, more preferably 5% by mole to 50% by mole, still more preferably 10% by mole to 50% by mole, with respect to the total structural units (100% by mole) constituting the resin (A).

<Other Structural Unit (t)>

The resin (A) may include a structural unit other than the structural unit (a1) and the structural unit (s) described above (which is sometimes referred to as “structural unit (t)”). Examples of the structural unit (t) include a structural unit having a halogen atom (which is sometimes referred to as “structural unit (a4)”) other than the structural unit (a1) and the structural unit (a3), and a structural unit having a non-leaving hydrocarbon group (which is sometimes referred to as “structural unit (a5)”).

<Structural Unit (a4)>

The structural unit having a halogen atom preferably has a fluorine atom.

Examples of the structural unit (a4) include the structural units represented by the formula (a4-0).

wherein R⁵ represents a hydrogen atom or a methyl group,

L⁵ represent a single bond or a C₁ to C₄ saturated aliphatic hydrocarbon group,

L³ represents a C₁ to C₈ perfluoroalkanediyl group or a C₅ to C₁₂ perfluorocycloalkanediyl group, and

R⁶ represents a hydrogen atom or a fluorine atom.

Examples of the saturated aliphatic hydrocarbon group of L⁵ include a liner alkanediyl group such as methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl; and a branched alkanediyl group such as a group in which a liner alkanediyl group has a side chain of an alkyl group (e.g., methyl and ethyl groups), for example, ethane-1,1-diyl, propane-1,2-diyl, butane-1,3-diyl, 2-methylpropane-1,3-diyl and 2-methylpropane-1,2-diyl groups.

Examples of the perfluoroalkanediyl group of L³ include difluoromethylene, perfluoroethylene, perfluoroethyl fluoromethylene, perfluoropropane-1,3-diyl, a perfluoropropane-1,2-diyl, perfluoropropane-2,2-diyl, perfluorobutane-1,4-diyl, perfluorobutane-2,2-diyl, perfluorobutane-1,2-diyl, perfluoropentane-1,5-diyl, perfluoropentane-2,2-diyl, perfluoropentane-3,3-diyl, perfluorohexane-1,6-diyl, perfluorohexane-2,2-diyl, perfluorohexane-3,3-diyl, perfluoroheptane-1,7-diyl, perfluoroheptane-2,2-diyl, perfluoroheptane-3,4-diyl, perfluoroheptane-4,4-diyl, perfluorooctan-1,8-diyl, perfluorooctan-2,2-diyl, perfluorooctan-3,3-diyl and perfluorooctan-4,4-diyl groups

Examples of the perfluoro cycloalkanediyl group of L³ include perfluorocyclohexanediyl, perfluorocyclopentanediyl, perfluorocycloheptanediyl and perfluoroadamantanediyl groups.

L⁵ is preferably a single bond, methylene or ethylene group, and more preferably a single bond or methylene group.

L³ is preferably a C₁ to C₆ perfluoroalkanediyl group, more preferably a C₁ to C₃ perfluoroalkanediyl group.

Examples of the structural unit (a4-0) include structural units represented by the formula (a4-0-1) to the formula (a4-0-32).

Examples of the structural unit (a4) include the structural units represented by the formula (a4-1):

wherein R^a41 represents a hydrogen atom or a methyl group,

R^a42 represents an optionally substituted C₁ to C₂₀ hydrocarbon group, and a methylene group contained in the hydrocarbon group may be replaced by an oxygen atom or a carbonyl group, and

A^a41 represents an optionally substituted C₁ to C₆ alkanediyl group or a group represented by the formula (a-g1),

wherein s represents 0 or 1,

A^a42 and A^a44 independently represent an optionally substituted C₁ to C₅ aliphatic hydrocarbon group,

A^a43 represents a single bond or an optionally substituted C₁ to C₅ aliphatic hydrocarbon group, and

X^a41 and X^a42 independently represent —O—, —CO—, —CO—O— or —O—CO—,

provided that the total carbon number contained in the group of A^a42, A^a43, A^a44, X^a41 and X^a42 is 6 or less, and

at least one of A^a41 and R^a42 has a halogen atom as a substituent, and

* and ** represent a binding site, and * represents a binding site to —O—CO—R^a42.

The hydrocarbon group of R^a42 includes a chain and a cyclic aliphatic hydrocarbon groups, an aromatic hydrocarbon group and a combination thereof.

Examples of the chain aliphatic hydrocarbon group include an alkyl group such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-dodecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl and n-octadecyl groups. Examples of the cyclic aliphatic hydrocarbon group include a monocyclic hydrocarbon group, i.e., cycloalkyl group such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl groups; and polycyclic hydrocarbon groups such as decahydronaphtyl, adamantyl and norbornyl groups as well as groups below. * represents a binding site.

Examples of the aromatic hydrocarbon group include an aryl group such as phenyl, naphthyl, anthryl, biphenyl, phenanthryl and fluorenyl groups.

The hydrocarbon group of R^a42 is preferably a chain and a cyclic aliphatic hydrocarbon groups, and a combination thereof. The hydrocarbon group may have a carbon-carbon unsaturated bond, is preferably a chain and a cyclic saturated aliphatic hydrocarbon groups, and a combination thereof.

Examples of the substituent of R^a42 include a fluorine atom or a group represented by the formula (a-g3).

Examples of the halogen atom include fluorine, chlorine, bromine or iodine atom, and preferably a fluorine atom.*—X^a43-A^a45  (a-g3)

wherein X^a43 represent an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group,

A^a45 represents a C₁ to C₁₇ aliphatic hydrocarbon group that has a halogen atom, and

* represents a binding site to carbonyl group.

Examples of the aliphatic hydrocarbon group of A^a45 are the same examples as the group of R^a42.

R^a42 is preferably an aliphatic hydrocarbon group that may have a halogen atom, and more preferably an alkyl group having a halogen atom and/or an aliphatic hydrocarbon group having the group represented by the formula (a-g3).

When R^a42 is an aliphatic hydrocarbon group having a halogen atom, an aliphatic hydrocarbon group having a fluorine atom is preferred, a perfluoroalkyl group or a perfulorocycloalkyl group are more preferred, a C₁ to C₆ perfluoroalkyl group is still more preferred, a C₁ to C₃ perfluoroalkyl group is particularly preferred.

Examples of the perfluoroalkyl group include perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluoroheptyl and perfluorooctyl groups. Examples of the perfluorocycloalkyl group include perfluorocyclohexyl group.

When R^a42 is an aliphatic hydrocarbon group having the group represented by the formula (a-g3), the total carbon number contained in the aliphatic hydrocarbon group including the group represented by the formula (a-g3) is preferably 15 or less, more preferably 12 or less. The number of the group represented by the formula (a-g3) is preferably one when the group represented by the formula (a-g3) is the substituent.

The aliphatic hydrocarbon having the group represented by the formula (a-g3) is more preferably a group represented by the formula (a-g2);*-A^a46-X^a44-A^a47  (a-g2)

wherein A^a46 represents a C₁ to C₁₇ aliphatic hydrocarbon group that may have a halogen atom,

X^a44 represent a carbonyloxy group or an oxycarbonyl group,

A^a47 represents a C₁ to C₁₇ aliphatic hydrocarbon group that may have a halogen atom,

provided that the total carbon number contained in the group of A^a46, X^a44 and A^a47 is 18 or less,

at least one of A^a46 and A^a47 has a halogen atom, and

* represents a binding site to carbonyl group.

The carbon number of the aliphatic hydrocarbon group of A^a46 is preferably 1 to 6, and more preferably 1 to 3.

The carbon number of the aliphatic hydrocarbon group of A^a47 is preferably 4 to 15, and more preferably 5 to 12, and cyclohexyl and adamantyl groups are still more preferred as the aliphatic hydrocarbon group.

Preferred structure represented by the formula (a-g2), *-A^a46-X^a44-A^a47, include the following ones.

Examples of the alkanediyl group of A^a41 include a liner alkanediyl group such as methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl and hexane-1,6-diyl groups;

a branched alkanediyl group such as propane-1,2-diyl, butan-1,3-diyl, 2-methylpropane-1,2-diyl, 1-methylpropane-1,4-diyl, 2-methylbutane-1,4-diyl groups.

Examples of the substituent of the alkanediyl group of A^a41 include a hydroxy group and a C₁ to C₆ alkoxy group.

A^a41 is preferably a C₁ to C₄ alkanediyl group, more preferably a C₂ to C₄ alkanediyl group, and still more preferably ethylene group.

In the group represented by the formula (a-g1) (which is sometimes referred to as “group (a-g1)”), examples of the aliphatic hydrocarbon group of A^a42, A^a43 and A^a44 include methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, 1-methylpropane-1,3-diyl, 2-methylpropane-1,3-diyl and 2-methylpropane-1,2-diyl groups.

Examples of the substituent of the aliphatic hydrocarbon group of A^a42, A^a43 and A^a44 include a hydroxy group and a C₁ to C₆ alkoxy group.

s is preferably 0.

Examples of the group (a-g1) in which X^a42 represents an oxygen atom include the following ones. In the formula, * and ** each represent a binding site, and ** represents a binding site to —O—CO—R^a42.

Examples of the group (a-g1) in which X^a42 represents a carbonyl group include the following ones.

Examples of the group (a-g1) in which X^a42 represents a carbonyloxy group include the following ones.

Examples of the group (a-g1) in which X^a42 represents an oxycarbonyl group include the following ones.

The structural unit represented by the formula (a4-1) is preferably structural units represented by the formula (a4-2) and the formula (a4-3):

wherein R^f1 represents a hydrogen atom or a methyl group,

A^f1 represent a C₁ to C₆ alkanediyl group, and

R^f2 represents a C₁ to C₁₀ hydrocarbon group that has a fluorine atom.

Examples of the alkanediyl group of A^f1 include a chain alkanediyl group such as methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl and hexane-1,6-diyl groups;

a branched alkanediyl group such as 1-methylpropane-1,3-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, 1-methylbutane-1,4-diyl and 2-methylbutane-1,4-diyl groups.

The hydrocarbon group of R^f2 includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The aliphatic hydrocarbon group includes a chain and a cyclic groups, and a combination thereof. The aliphatic hydrocarbon group is preferably an alkyl group and an alicyclic hydrocarbon group.

Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl and 2-ethylhexyl groups.

Examples of the alicyclic hydrocarbon group include any of a monocyclic group and a polycyclic group. Examples of the monocyclic alicyclic hydrocarbon group include a cycloalkyl group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and cyclodecyl groups. Examples of the polycyclic hydrocarbon groups include decahydronaphthyl, adamantyl, 2-alkyladamantane-2-yl, 1-(adamantane-1-yl) alkane-1-yl, norbornyl, methylnorbornyl and isobornyl groups.

Examples of the hydrocarbon group having a fluorine atom of R^f2 include an alkyl group having a fluorine atom and an alicyclic hydrocarbon group having a fluorine atom.

Specific examples of an alkyl group having a fluorine atom include a fluorinated alkyl group such as difluoromethyl, trifluoromethyl, 1,1-difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, perfluoroethyl, 1,1,2,2-tetrafluoropropyl, 1,1,2,2,3,3-hexafluoropropyl, perfluoroethylmethyl, 1-(trifluoromethyl)-1,2,2,2-tetrafluoroethyl, perfluoropropyl, 1,1,2,2-tetrafluorobutyl, 1,1,2,2,3,3-hexafluorobutyl, 1,1,2,2,3,3,4,4-octafluorobutyl, perfluorobutyl, 1,1-bis(trifluoromethyl)methyl-2,2,2-trifluoroethyl, 2-(perfluoropropyl)ethyl, 1,1,2,2,3,3,4,4-octafluoropentyl, perfluoropentyl, 1,1,2,2,3,3,4,4,5,5-decafluoropentyl, 1,1-bis(trifluoromethyl)2,2,3,3,3-pentafluoropropyl, perfluoropentyl, 2-(perfluorobutyl)ethyl, 1,1,2,2,3,3,4,4,5,5-decafluorohexyl, 1,1,2,2,3,3,4,4,5,5,6,6-dodeca fluorohexyl, perfluoropentylmethyl and perfluorohexyl groups.

Examples of the alicyclic hydrocarbon group having a fluorine atom include a fluorinated cycloalkyl group such as perfluorocyclohexyl and perfluoroadamantyl groups.

In the formula (a4-2). A^f1 is preferably a C₂ to C₄ alkanediyl group, and more preferably ethylene group.

R^f2 is preferably a C₁ to C₆ fluorinated alkyl group:

wherein R^f11 represents a hydrogen atom or a methyl group,

A^f11 represent a C₁ to C₆ alkanediyl group,

A^f13 represents a C₁ to C₁₈ aliphatic hydrocarbon group that may has a fluorine atom,

X^f12 represents an oxycarbonyl group or a carbonyloxy group,

A^f14 represents a C₁ to C₁₇ aliphatic hydrocarbon group that may has a fluorine atom, and

provided that at least one of A^f13 and A^f14 represents an aliphatic hydrocarbon group having a fluorine atom.

Examples of the alkanediyl group of A^f11 are the same examples as the alkanediyl group of A^f1.

Examples of the aliphatic hydrocarbon group of A^f13 include any of a divalent chain or cyclic hydrocarbon group, or a combination thereof. The aliphatic hydrocarbon group may have a carbon-carbon unsaturated bond, and is preferably a saturated aliphatic hydrocarbon group.

The aliphatic hydrocarbon group that may has a fluorine atom of A^f13 is the saturated aliphatic hydrocarbon group that may has a fluorine atom, and preferably a perfuloroalkandiyl group.

Examples of the divalent chain aliphatic hydrocarbon that may have a fluorine atom include an alkanediyl group such as methylene, ethylene, propanediyl, butanediyl and pentanediyl groups; a perfluoroalkanediyl group such as difluoromethylene, perfluoroethylene, perfluoropropanediyl, perfluorobutanediyl and perfluoropentanediyl groups.

The divalent cyclic aliphatic hydrocarbon group that may have a fluorine atom is any of monocyclic or polycyclic group.

Examples monocyclic aliphatic hydrocarbon group include cyclohexanediyl and perfluorocyclohexanediyl groups.

Examples polycyclic aliphatic hydrocarbon group include adamantanediyl, norbornanediyl, and perfluoroadamantanediyl groups.

Examples of the aliphatic hydrocarbon group of A^f14 include any of a chain or a cyclic hydrocarbon group, or a combination thereof. The aliphatic hydrocarbon group may have a carbon-carbon unsaturated bond, and is preferably a saturated aliphatic hydrocarbon group.

The aliphatic hydrocarbon group that may has a fluorine atom of A^f14 is preferably the saturated aliphatic hydrocarbon group that may have a fluorine atom.

Examples of the chain aliphatic hydrocarbon group that may have a halogen atom include trifluoromethyl, difluoromethyl, methyl, perfluoromethyl, 1,1,1-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, ethyl, perfluoropropyl, 1,1,1,2,2-pentafluoropropyl, propyl, perfluorobutyl, 1,1,2,2,3,3,4,4-octafluorobutyl, butyl, perfluoropentyl, 1,1,1,2,2,3,3,4,4-nonafluoropentyl, pentyl, hexyl, perfluorohexyl, hepthyl, perfluoroheptyl, octyl and perfluorooctyl groups.

The cyclic aliphatic hydrocarbon group that may have a halogen atom is any of monocyclic or polycyclic group. Examples of the group containing the monocyclic aliphatic hydrocarbon group include cyclopropylmethyl, cyclopropyl, cyclobutylmethyl, cyclopentyl, cyclohexyl and perfluorocyclohexyl groups. Examples of the group containing the polycyclic aliphatic hydrocarbon group include adamantyl, adamantylmethyl, norbornyl, norbornylmethyl, perfluoroadamantyl and perfluoroadamantylmethyl groups

In the formula (a4-3), A^f11 is preferably ethylene group.

The aliphatic hydrocarbon group of Aⁿ³ is preferably a C₁ to C₆ aliphatic hydrocarbon group, more preferably a C₂ to C₃ aliphatic hydrocarbon group.

The aliphatic hydrocarbon group of A^f14 is preferably a C₃ to C₁₂ aliphatic hydrocarbon group, more preferably a C₃ to C₁₀ aliphatic hydrocarbon group. Among these, A^f14 is preferably a group containing a C₃ to C₁₂ alicyclic hydrocarbon group, more preferably cyclopropylmethyl, cyclopentyl, cyclohexyl, norbornyl and adamantyl group.

Examples of the structural unit (a4-2) include structural units represented by the formula (a4-1-1) to the formula (a4-1-22).

Examples of the structural unit (a4-3) include structural units presented by the formula (a4-1′-1) to the formula (A4-1′-22).

Examples of the structural unit (a4) include a structural unit presented by the formula (a4-4):

wherein R^f21 represents a hydrogen atom or a methyl group,

A^f21 represents —(CH₂)_j1—, —(CH₂)_j2—O—(CH₂)_j3— or —(CH₂)_j4—CO—O—(CH₂)_j5—,

j1 to j5 independently represents an integer of 1 to 6, and

R^f22 represents a C₁ to C₁₀ hydrocarbon group having a fluorine atom.

Examples of the hydrocarbon group having a fluorine atom of R^f22 are the same examples as the hydrocarbon group described in R^f2 in the formula (a4-2). R^f22 is preferably a C₁ to C₁₀ alkyl having a fluorine atom or a C₃ to C₁₀ alicyclic hydrocarbon group having a fluorine atom, more preferably a C₁ to C₁₀ alkyl having a fluorine atom, and still more preferably a C₁ to C₆ alkyl having a fluorine atom.

In the formula (a4-4), A^f21 is preferably —(CH₂)_j1—, more preferably methylene or ethylene group, and still more preferably methylene group.

Examples of the structural unit represented by the formula (a4-4) include the following ones.

When the resin (A) contains the structural unit (a4), the proportion thereof is generally 1 to 20% by mole, preferably 2 to 15% by mole, more preferably 3 to 10% by mole, with respect to the total structural units (100% by mole) of the resin (A).

<Structural Unit (a5)>

Examples of the non-leaving hydrocarbon group in the structural unit (a5) include a chain, a branched or a cyclic hydrocarbon group. Among these, the structural unit (a5) is preferably a structural unit containing an alicyclic hydrocarbon group.

The structural unit (a5) is, for example, a structural unit represented by the formula (a5-1):

wherein R⁵¹ represents a hydrogen atom or a methyl group,

R⁵² represents a C₃ to C₁₈ alicyclic hydrocarbon group where a hydrogen atom may be replaced by a C₁ to C₈ aliphatic hydrocarbon group or a hydroxy group, provided that a hydrogen atom contained in the carbon atom bonded to L⁵¹ is not replaced by the C₁ to C₈ aliphatic hydrocarbon group, and

L⁵¹ represents a single bond or a C₁ to C₁₈ divalent saturated hydrocarbon group where a methylene group may be replaced by an oxygen atom or a carbonyl group.

Examples of the alicyclic hydrocarbon group of R⁵² include any one of a monocyclic group or a polycyclic group. Examples of the monocyclic alicyclic hydrocarbon group include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl groups. Examples of the polycyclic hydrocarbon group include adamantyl and norbornyl groups.

Examples of the C₁ to C₈ aliphatic hydrocarbon group include an alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, 2-ethylhexyl and n-octyl groups.

Examples of the alicyclic hydrocarbon group having a substituent include 3-hydroxyadamantyl and 3-methyladamantyl.

R⁵² is preferably an unsubstituted C₃ to C₁₈ alicyclic hydrocarbon group, and more preferably adamantyl, norbornyl and cyclohexyl groups.

Examples of the divalent saturated hydrocarbon group of L⁵¹ include a divalent aliphatic saturated hydrocarbon group and a divalent alicyclic saturated hydrocarbon group, and a divalent aliphatic saturated hydrocarbon group is preferred.

Examples of the divalent aliphatic saturated hydrocarbon group include an alkanediyl such as methylene, ethylene, propanediyl, butanediyl and pentanediyl.

Examples of the divalent alicyclic saturated hydrocarbon group include any of a monocyclic group and a polycyclic group. Examples of the monocyclic alicyclic saturated hydrocarbon groups include cycloalkanediyl such as cyclopentanediyl and cyclohexanediyl groups. Examples of the polycyclic saturated hydrocarbon groups include adamantanediyl and norbornanediyl groups.

Examples of the group in which a methylene group contained in the saturated hydrocarbon group is replaced by an oxygen atom or a carbonyl group include groups represented by the formula (L1-1) to the formula (L1-4). In the formula (L1-1) to the formula (L1-4), * represents a binding site to an oxygen atom.

wherein X^X1 represents an oxycarbonyl group or a carbonyloxy group,

L^X1 represents a C₁ to C₁₆ divalent saturated aliphatic hydrocarbon group,

L^X2 represents a single bond or a C₁ to C₁₅ divalent saturated hydrocarbon group,

provided that the total carbon number contained in the group of L^X1 and L^X2 is 16 or less

L^X3 represents a single bond or a C₁ to C₁₇ divalent saturated aliphatic hydrocarbon group,

L^X4 represents a single bond or a C₁ to C₁₆ divalent saturated hydrocarbon group,

provided that the total carbon number contained in the group of L^X3 and L^X4 is 17 or less,

L^X5 represents a C₁ to C₁₅ divalent saturated aliphatic hydrocarbon group,

L^X6 and L^X7 independently represents a single bond or a C₁ to C₁₄ divalent saturated hydrocarbon group,

provided that the total carbon number contained in the group of L^X5, L^X6 and L^X7 is 15 or less;

L^X8 and L^X9 independently represents a single bond or a C₁ to C₁₂ divalent saturated hydrocarbon group,

W^X1 represents a C₃ to C₁₅ divalent saturated alicyclic hydrocarbon group, provided that the total carbon number contained in the group of L^X8, L^X9 and W^X1 is 15 or less.

L^X1 is preferably a C₁ to C₈ divalent saturated aliphatic hydrocarbon group, and more preferably methylene or ethylene group.

L^X2 is preferably a single bond or a C₁ to C₈ divalent saturated aliphatic hydrocarbon group, and more preferably a single bond.

L^X3 is preferably a C₁ to C₈ divalent saturated aliphatic hydrocarbon group.

L^X4 is preferably a single bond or a C₁ to C₈ divalent saturated aliphatic hydrocarbon group.

L^X5 is preferably a C₁ to C₈ divalent saturated aliphatic hydrocarbon group, and more preferably methylene or ethylene group.

L^X6 is preferably a single bond or a C₁ to C₈ divalent saturated aliphatic hydrocarbon group, and more preferably methylene or ethylene group.

L^X7 is preferably a single bond or a C₁ to C₈ divalent saturated aliphatic hydrocarbon group.

L^X8 is preferably a single bond or a C₁ to C₈ divalent saturated aliphatic hydrocarbon group, and more preferably a single bond or methylene group.

L^X9 is preferably a single bond or a C₁ to C₈ divalent saturated aliphatic hydrocarbon group, and more preferably a single bond or methylene group.

W^X1 is preferably a C₃ to C₁₀ divalent saturated alicyclic hydrocarbon group, and more preferably cyclohexanediyl or adamantanediyl group.

Examples of the group represented by the formula (L1-1) include the following ones.

Examples of the group represented by the formula (L1-2) include the following ones.

Examples of the group represented by the formula (L1-3) include the following ones.

Examples of the group represented by the formula (L1-4) include the following ones.

L⁵¹ is preferably a single bond, methylene group, ethylene group or the groups represented by the formula (L1-1), and more preferably a single bond or the groups represented by the formula (L1-1).

Examples of the structural unit (a5-1) include the following ones.

When the resin (A) contains the structural unit (a5), the proportion thereof is generally 1 to 30% by mole, preferably 2 to 20% by mole, more preferably 3 to 15% by mole, with respect to the total structural units (100% by mole) of the resin (A).

The resin (A) may include a structural unit other than structural units described above. Examples of the structural unit include a known structural unit.

The resin (A) preferably is a resin having the structural unit (I), the structural unit (a1) and the structural unit (s), that is, a copolymer of the salt (I), the monomer (a1) and the monomer (s).

When the resin (A) is the resin having the structural unit (I), the structural unit (a1) and the structural unit (s), the proportion thereof is preferably

the structural unit (I): 1 to 10% by mole, more preferably 2 to 8% by mole,

the structural unit (a1): 15 to 74% by mole, more preferably 25 to 65% by mole, and

the structural unit (s): 25 to 84% by mole, more preferably 27 to 73% by mole, with respect to the resin (A) (100% by mole).

The structural unit (a1) is preferably at least one of the structural unit (a1-1) and the structural unit (a1-2) (preferably the structural unit having a cyclohexyl group or a cyclopentyl group), and more preferably is the structural unit (a1-1).

The structural unit (s) is preferably at least one of the structural unit (a2) or the structural unit (a3). The structural unit (a2) is preferably the structural unit represented by the formula (a2-1). The structural unit (a3) is preferably at least one of a structural unit including the structural units (a3-1-1) to (a3-1-4), the structural units (a3-2-1) to (a3-2-4) and the structural units (a3-4-1) to (a3-4-2).

The proportion of the structural unit derived from the monomer having an adamantyl group (in particular, the structural unit (a1-1)) in the resin (A) is preferably 15% by mole or more with respect to the structural units (a1). As the mole ratio of the structural unit derived from the monomer having an adamantyl group increases within this range, the dry etching resistance of the resulting resist improves.

The resin (A) can be produced by a known polymerization method, for example, radical polymerization method, using the salt (I) and monomer (a1). The proportion of the structural unit in the resin (A) can be adjusted by changing the amount of monomers used for polymerization.

The weight average molecular weight of the resin (A) is preferably 2,000 or more (more preferably 2,500 or more, and still more preferably 3,000 or more), and 50,000 or less (more preferably 30,000 or less, and still more preferably 15,000 or less).

The weight average molecular weight is a value determined by gel permeation chromatography using polystyrene as the standard product. The detailed condition of this analysis is described in Examples.

<Resist Composition>

The resist composition according to one aspect of the disclosure includes the resin having the structural unit derived from the salt (I). The resin is preferably the resin (A) which includes the structural unit having an acid-labile group in addition to the structural unit derived from the salt (I). The resist composition may further includes the salt (I) as an origomer of the salt (I).

Further, the resist composition according to another aspect of the disclosure includes the salt (I).

The resist composition may another resin than the resin of the present disclosure, i.e., the resin which includes the structural unit derived from the salt (I).

The resist composition generally includes an acid generator known in the art of the disclosure. The acid generator for the resist composition is sometimes referred to as “acid generator (B)”.

Further, the resist composition preferably includes a solvent which is sometimes referred to as “solvent (E)”. The resist composition preferably includes a quencher which is sometimes referred to as “quencher (C)”.

Examples of the quencher (C) include a salt which generates an acid weaker in acidity than an acid generated from the acid generator, such as a weak acid inner salt which is sometimes referred to as “weak acid inner salt (D)”.

<Resin Other than Resin (A)>

The resist composition of the present invention may further include another resin than the resin of the present disclosure. The another resin includes no structural unit (I), and examples of the resin include a resin having the structural unit (a1) and the structural unit (s) which resin is sometimes referred to as “resin (A1)”, a resin having the structural unit (a4) which resin is sometimes referred to as “resin (X)” and a resin having only the structural unit (s).

The resin other than the resin of the present disclosure is preferably the resin (A1). In the resin (A1), the proportion of the structural unit (a1) is preferably 1 to 80% by mole, more preferably 1 to 75% by mole, and still more preferably 3 to 70% by mole with respect to the total structural units (100% by mole) constituting the resin (A1). In the resin (A1), the structural unit (a1) is preferably at least one of the structural unit (a1-1) and the structural unit (a1-2) (preferably the structural unit having a cyclohexyl group or a cyclopentyl group).

Examples of the structural unit (s) in the resin (A1) preferably include at least one of the structural unit (a2) and the structural unit (a3). The structural unit (a2) is preferably the structural unit represented by the formula (a2-1). The structural unit (a3) is preferably at least one of a structural unit including the structural unit (a3-1) and the structural unit (a3-2).

The weight average molecular weight of the resin (A1) is preferably 2,500 or more (more preferably 3,000 or more, and still more preferably 4,000 or more), and 50,000 or less (more preferably 30,000 or less, and still more preferably 15,000 or less). The method of measuring of the weight average molecular weight of the resin (A1) is the same as the resin (A).

When the resist composition includes the resin (A1), the proportion thereof is preferably 5 to 80% by mass with respect to the total resin (100% by mass) in the resist composition.

The salt (I) is also useful for resist compositions. A resist composition including the salt (I) falls within the scope of the disclosure. The resist composition including the salt (I) may further includes the resin (A1), the resin of the present disclosure, such as the resin (A), or both of them.

The resin other than the resin of the present disclosure is also preferably the resin (X). In the resin (X), the proportion of the structural unit (a4) is preferably 40% by mole or more, and more preferably 45% by mole or more, and still more preferably 50% by mole or more with respect to the total structural units (100% by mole) of the resin (X).

Examples of the structural unit which the resin (X) may further include the structural unit (a2), the structural unit (a3) and other structural unit derived from a known monomer.

The weight average molecular weight of the resin (X) is preferably 8,000 or more (more preferably 10,000 or more), and 80,000 or less (more preferably 60,000 or less). The method of measuring of the weight average molecular weight of the resin (X) is the same as the resin (A).

When the resist composition includes the resin (X), the proportion thereof is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, and still more preferably 1 to 40 parts by mass, in particular preferably 2 to 30 parts by mass, with respect to the resin of the present disclosure such as the resin (A) (100 parts by mass).

The total proportion of the resin of the present disclosure and the resin other than the resin (A) is preferably 80% by mass to 99% by mass, and more preferably 90% by mass to 99% by mass, with respect to the total solid components of the resist composition. The solid proportion of the resist composition can be measured with a known analytical method such as liquid chromatography and gas chromatography.

<Acid Generator (B)>

The acid generator (B) may be an ionic acid generator or a non-ionic acid generator. The acid generator (B) may be used any an ionic acid generator and a non-ionic acid generator. Examples of the nonionic compounds for the acid generator include organic halogenated compounds; sulfonate esters, e.g. 2-nitrobenzylester, aromatic sulfonates, oximesulfonate, N-sulfonyloxyimide, sulfonyloxyketone, and diazonaphtoquione 4-sulfonate; sulfones, e.g., disulfone, ketosulfone, and sulfonium diazomethane. The ionic compounds for the acid generator include onium salts having an onium cation, e.g., diazonium salts, phosphonium salts, sulfonium salts and iodonium salts. Examples of the anions of onium salt include a sulfonic acid anion, a sulfonylimide anion, sulfonylmethide anion.

As the acid generator, the compounds giving an acid by radiation can be used, which are mentioned in JP63-26653A1, JP55-164824A1, JP62-69263A1, JP63-146038A1, JP63-163452A1, JP62-153853A1, JP63-146029A1, U.S. Pat. No. 3,779,778B1, U.S. Pat. No. 3,849,137B1, DE3914407 and EP126,712A1. The acid generator for the photoresist composition can be produced by the method described in the above-mentioned documents.

The acid generator is preferably a fluorine-containing compound, more preferably salt represented by the formula (B1) (which is sometimes referred to as “acid generator (B1)”):

wherein Q¹ and Q² respectively represent a fluorine atom or a C₁ to C₆ perfluoroalkyl group,

L^b1 represents a divalent C₁ to C₂₄ saturated hydrocarbon group where a methylene group may be replaced by an oxygen atom or a carbonyl group and where a hydrogen atom may be replaced by a hydroxyl group or fluorine atom, and

Y represents an optionally substituted C₃ to C₁₈ alicyclic hydrocarbon group where a methylene group may be replaced by an oxygen atom, a carbonyl group or a sulfonyl group, and

Z⁺ represents an organic cation.

Examples of the perfluoroalkyl group of Q¹ and Q² include trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoro-isopropyl, perfluorobutyl, perfluoro-sec-butyl, perfluoro-tert-butyl, perfluoropentyl and perfluorohexyl groups.

Q¹ and Q² independently are preferably trifluoromethyl or fluorine atom, and both of Q¹ and Q² are preferably a fluorine atom.

Examples of the divalent saturated hydrocarbon group of L^b1 include any of a chain or a branched alkanediyl group, a divalent mono- or a poly-alicyclic saturated hydrocarbon group, and a combination thereof.

Specific examples of the chain alkanediyl group include methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl, heptadecane-1,17-diyl groups.

Specific examples of the branched chain alkanediyl group include ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-2,2-diyl, pentane-1,4-diyl, pentane-2,4-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl and 2-methylbutane-1,4-diyl groups.

Specific examples of the mono-alicyclic saturated hydrocarbon group include a cycloalkanediyl group such as cyclobutan-1,3-diyl, cyclopentan-1,3-diyl, cyclohexane-1,4-diyl and cyclooctan-1,5-diyl groups.

Specific examples of the poly-alicyclic saturated hydrocarbon group include norbornane-1,4-diyl, norbornane-2,5-diyl, adamantane-1,5-diyl and adamantane-2,6-diyl groups.

Examples of the saturated hydrocarbon group of L^b1 in which a methylene group has been replaced by oxygen atom or a carbonyl group include groups represented by the formula (b1-1) to the formula (b1-3) below:

wherein L^b2 represents a single bond or a C₁ to C₂₂ divalent saturated hydrocarbon group where a hydrogen atom may be replaced by a fluorine atom;

L^b3 represents a single bond or a C₁ to C₂₂ divalent saturated hydrocarbon group where a hydrogen atom may be replaced by a fluorine atom or a hydroxy group, and a methylene group may be replaced by an oxygen atom or a carbonyl group;

provided that the total carbon number contained in the group of L^b2 and L^b3 is 22 or less;

L^b4 represents a single bond or a C₁ to C₂₂ divalent saturated hydrocarbon group where a hydrogen atom may be replaced by a fluorine atom;

L^b5 represents a single bond or a C₁ to C₂₂ divalent saturated hydrocarbon group where a hydrogen atom may be replaced by a fluorine atom or a hydroxy group, and a methylene group may be replaced by an oxygen atom or a carbonyl group;

provided that the total carbon number contained in the group of L^b4 and L^b5 is 22 or less;

L^b6 represents a single bond or a C₁ to C₂₃ divalent saturated hydrocarbon group where a hydrogen atom may be replaced by a fluorine atom or a hydroxy group;

L^b7 represents a single bond or a C₁ to C₂₃ divalent saturated hydrocarbon group where a hydrogen atom may be replaced by a fluorine atom or a hydroxy group, and a methylene group may be replaced by an oxygen atom or a carbonyl group;

provided that the total carbon number contained in the group of L^b6 and L^b7 is 23 or less, and

* represents a binding site to —Y.

In the formula (b1-1) to the formula (b1-3), when a methylene group contained in a saturated hydrocarbon group has been replaced by an oxygen atom and/or a carbonyl group, the number of carbon atoms in the saturated hydrocarbon group includes that of the replaced carbon atoms.

Examples of the divalent saturated hydrocarbon group are the same examples as the divalent saturated hydrocarbon group of L^b1.

L^b2 is preferably a single bond.

L^b3 is preferably a C₁ to C₄ divalent saturated hydrocarbon group.

L^b4 is preferably a C₁ to C₈ divalent saturated hydrocarbon group where a hydrogen atom may be replaced by a fluorine atom.

L^b5 is preferably a single bond or a C₁ to C₈ divalent saturated hydrocarbon group.

L^b6 is preferably a single bond or a C₁ to C₄ divalent saturated hydrocarbon group where a hydrogen atom may be replaced by a fluorine atom.

L^b1 is preferably a single bond or a C₁ to C₁₈ divalent saturated hydrocarbon group where a hydrogen atom may be replaced by a fluorine atom or a hydroxy group, and where a methylene group may be replaced by an oxygen atom or a carbonyl group.

Among these, the group represented by the formula (b1-1) or the formula (b1-3) is preferred.

Examples of the divalent group represented by the formula (b1-1) include groups represented by the formula (b1-4) to the formula (b1-8) described below:

wherein L^b8 represents a single bond or a C₁ to C₂₂ divalent saturated hydrocarbon group where a hydrogen atom may be replaced by a fluorine atom or a hydroxy group;

L^b9 represents a C₁ to C₂₀ divalent saturated hydrocarbon group;

L^b10 represents a single bond or a C₁ to C₁₉ divalent saturated hydrocarbon group where a hydrogen atom may be replaced by a fluorine atom or a hydroxy group;

provided that the total carbon number contained in the group of L^b9 and L^b10 is 20 or less;

L^b11 represents a C₁ to C₂₁ divalent saturated hydrocarbon group;

L^b12 represents a single bond or a C₁ to C₂₀ divalent saturated hydrocarbon group where a hydrogen atom may be replaced by a fluorine atom or a hydroxy group;

provided that the total carbon number contained in the group of L^b11 and L^b12 is 21 or less,

L^b13 represents a C₁ to C₁₉ divalent saturated hydrocarbon group;

L^b14 represents a single bond or a C₁ to C₁₈ divalent saturated hydrocarbon group;

L^b15 represents a single bond or a C₁ to C₁₈ divalent saturated hydrocarbon group where a hydrogen atom may be replaced by a fluorine atom or a hydroxy group;

provided that the total carbon number contained in the group of L^b13, L^b14 and L^b15 is 19 or less;

L^b16 represents a C₁ to C₁₈ divalent saturated hydrocarbon group;

L^b17 represents a C₁ to C₁₈ divalent saturated hydrocarbon group;

L^b18 represents a single bond or a C₁ to C₁₇ divalent saturated hydrocarbon group where a hydrogen atom may be replaced by a fluorine atom or a hydroxy group;

provided that the total carbon number contained in the group of L^b16, L^b17 and L^b18 is 19 or less.

L^b8 is preferably a C₁ to C₄ divalent saturated hydrocarbon group.

L^b9 is preferably a C₁ to C₈ divalent saturated hydrocarbon group.

L^b10 is preferably a single bond or a C₁ to C₁₉ divalent saturated hydrocarbon group, and more preferably a single bond or a C₁ to C₈ divalent saturated hydrocarbon group.

L^b11 is preferably a C₁ to C₈ divalent saturated hydrocarbon group.

L^b12 is preferably a single bond or a C₁ to C₈ divalent saturated hydrocarbon group.

L^b13 is preferably a C₁ to C₁₂ divalent saturated hydrocarbon group.

L^b14 is preferably a single bond or a C₁ to C₆ divalent saturated hydrocarbon group.

L¹⁵ is preferably a single bond or a C₁ to C₁₈ divalent saturated hydrocarbon group, and more preferably a single bond or a C₁ to C₈ divalent saturated hydrocarbon group.

L^b16 is preferably a C₁ to C₁₂ divalent saturated hydrocarbon group.

L^b17 is preferably a C₁ to C₆ divalent saturated hydrocarbon group.

L^b18 is preferably a single bond or a C₁ to C₁₇ divalent saturated hydrocarbon group, and more preferably a single bond or a C₁ to C₄ divalent saturated hydrocarbon group.

Examples of the divalent group represented by the formula (b1-3) include groups represented by the formula (b1-9) to the formula (b1-11) described below:

wherein L^b19 represents a single bond or a C₁ to C₂₃ divalent saturated hydrocarbon group where a hydrogen atom may be replaced by a fluorine atom;

L^b20 represent a single bond or a C₁ to C₂₃ divalent saturated hydrocarbon group where a hydrogen atom may be replaced by a fluorine atom, a hydroxy group or an acyloxy group, and a methylene group contained in an acyloxy group may be replaced by an oxygen atom or a carbonyl group, and a hydrogen atom contained in an acyloxy group may be replaced by a hydroxy group,

provided that the total carbon number contained in the group of L^b19 and L^b20 is 23 or less;

L^b21 represents a single bond or a C₁ to C₂₁ divalent saturated hydrocarbon group where a hydrogen atom may be replaced by a fluorine atom;

L^b22 represents a single bond or a C₁ to C₂₁ divalent saturated hydrocarbon group;

L^b23 represents a single bond or a C₁ to C₂₁ divalent saturated hydrocarbon group where a hydrogen atom may be replaced by a fluorine atom, a hydroxy group or an acyloxy group, and a methylene group contained in an acyloxy group may be replaced by an oxygen atom or a carbonyl group, and a hydrogen atom contained in an acyloxy group may be replaced by a hydroxy group,

provided that the total carbon number contained in the group of L^b21, L^b22 and L^b23 is 21 or less;

L^b24 represents a single bond or a C₁ to C₂₀ divalent saturated hydrocarbon group where a hydrogen atom may be replaced by a fluorine atom;

L^b25 represents a single bond or a C₁ to C₂₁ divalent saturated hydrocarbon group;

L^b26 represents a single bond or a C₁ to C₂₀ divalent saturated hydrocarbon group where a hydrogen atom may be replaced by a fluorine atom, a hydroxy group or an acyloxy group, and a methylene group contained in an acyloxy group may be replaced by an oxygen atom or a carbonyl group, and a hydrogen atom contained in an acyloxy group may be replaced by a hydroxy group,

provided that the total carbon number contained in the group of L^b24, L^b25 and L^b26 is 21 or less.

In formula (b1-9) to formula (b1-11), when a hydrogen atom has been replaced by an acyloxy group, the carbon number of the saturated hydrocarbon group corresponds to the number of the carbon atom, CO and O in addition to the carbon number of the saturated hydrocarbon group.

For formula (b1-9) to formula (b1-11), examples of the divalent saturated hydrocarbon group include an alkanediyl and a monocyclic or polycyclic divalent saturated hydrocarbon group, and a combination of two or more such groups.

Examples of the acyloxy group include acetyloxy, propionyloxy, butyryloxy, cyclohexyl carbonyloxy and adamantyl carbonyloxy groups.

Examples of the acyloxy group having a substituent include oxoadamantyl carbonyloxy, hydroxyadamantyl carbonyloxy, oxocyclohexyl carbonyloxy and hydroxycyclohexyl carbonyloxy groups.

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

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

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

Examples of the group represented by the formula (b1-7) include the following ones.

Examples of the group represented by the formula (b1-8) include the following ones.

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

Examples of the group represented by the formula (b1-9) include the following ones.

Examples of the group represented by the formula (b1-10) include the following ones.

Examples of the group represented by the formula (b1-11) include the following ones.

Examples of the monovalent alicyclic hydrocarbon group of Y include groups represented by the formula (Y1) to the formula (Y11).

Examples of the monovalent alicyclic hydrocarbon group of Y in which a methylene group has been replaced by an oxygen atom, a carbonyl group or a sulfonyl group include groups represented by the formula (Y12) to the formula (Y27).

Among these, the alicyclic hydrocarbon group is preferably any one of groups represented by the formula (Y1) to the formula (Y19), more preferably any one of groups represented by the formula (Y11), (Y14), (Y15) or (Y19), and still more preferably group represented by the formula (Y11) or (Y14).

Examples of the substituent for the alicyclic group represented by Y include a halogen atom, a hydroxyl group, a C₁ to C₁₂ alkyl group, a hydroxy group-containing C₁ to C₁₂ alkyl group, a C₃ to C₁₆ monovalent alicyclic hydrocarbon group, a C₁ to C₁₂ alkoxy group, a C₆ to C₁₈ monovalent aromatic hydrocarbon group, a C₇ to C₂₁ aralkyl group, a C₂ to C₄ acyl group, a glycidyloxy group and —(CH₂)_j2—O—CO—R^b1— in which R^b1 represents an C₁ to C₁₆ alkyl group, a C₃ to C₁₆ monovalent alicyclic hydrocarbon group, or a C₆ to C₁₈ monovalent aromatic hydrocarbon group, and j2 represents an integer of 0 to 4.

Examples of the hydroxy group-containing alkyl group include hydroxymethyl and hydroxyethyl groups

Examples of the alkoxyl group include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, decyloxy and dodecyloxy groups.

Examples of the monovalent aromatic hydrocarbon group include an aryl group such as phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl, phenanthryl, 2,6-diethylphenyl and 2-methyl-6-ethylphenyl groups.

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

Examples of the acyl group include acetyl, propionyl and butyryl groups.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms.

Examples of Y include the groups below. * represents a binding site to L^b1.

Y is preferably a C₃ to C₁₈ monovalent alicyclic hydrocarbon group which may have a substituent, more preferably an adamantyl group which may have a substituent and one or more methylene group contained in the adamantyl group may be replaced with an oxygen atom, a carbonyl group or a sufonyl group, and still more preferably an adamantyl group, a hydroxyadamantyl group or an oxoadamantyl group.

The sulfonic acid anion in the salt represented by the formula (B1) is preferably an anions represented by the formula (B1-A-1) to the formula (B1-A-33), and more preferably an anions represented by the formula (B1-A-1) to the formula (B1-A-4), the formula (B1-A-9), the formula (B1-A-10), the formula (B1-A-24) to the formula (B1-A-33), below.

In the formula (B1-A-1) to the formula (B1-A-33), Rⁱ² to Rⁱ⁷ independently represent, for example, a C₁ to C₄ alkyl group, and preferably methyl or ethyl group, R¹⁸ represent, for example, a C₁ to C₁₂ aliphatic hydrocarbon group, preferably a C₁ to C₄ alkyl group, a C₅ to C₁₂ monovalent alicyclic hydrocarbon group or a group formed by a combination thereof, more preferably a methyl, ethyl group, cyclohexyl group or adamantyl group. L⁴ represents a single bond or a C₁ to C₄ alkanediyl group. Q¹ and Q² represent the same meaning as defined above.

Specific examples of the sulfonic acid anion in the salt represented by the formula (B1) include anions mentioned in JP2010-204646A1.

Among these, preferred examples of the sulfonic acid anion for the salt represented by the formula (B1) include anions represented by the formulae (B1a-1) to (B1a-15).

Among them, preferred examples of the sulfonic acid anion include anions represented by the formulae (B1a-1) to (B1a-3) and (B1a-7) to (B1a-15).

Examples of the organic cation represented by Z⁺ include an organic onium cation such as an organic sulfonium cation, an organic iodonium cation, an organic ammonium cation, a benzothiazolium cation and an organic phosphonium cation, and an organic sulfonium cation and an organic iodonium cation are preferred, and an arylsulfonium cation is more preferred.

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

wherein R^b4, R^b5 and R^b6 independently represent a C₁ to C₃₀ aliphatic hydrocarbon group, a C₃ to C₃₆ alicyclic hydrocarbon group or a C₆ to C₃₆ aromatic hydrocarbon group, a hydrogen atom contained in an aliphatic hydrocarbon group may be replaced by a hydroxy group, a C₁ to C₁₂ alkoxy group, a C₃ to C₁₂ alicyclic hydrocarbon group or a C₆ to C₁₈ aromatic hydrocarbon group, a hydrogen atom contained in an alicyclic hydrocarbon group may be replaced by a halogen atom, a C₁ to C₁₈ aliphatic hydrocarbon group, a C₂ to C₄ acyl group or a glycidyloxy group, a hydrogen atom contained in an aromatic hydrocarbon group may be replaced by a halogen atom, a hydroxy group or a C₁ to C₁₂ alkoxy group, or R^b4 and R^b5 may be bonded together with a sulfur atom bonded thereto to form a sulfur-containing ring, a methylene group contained in the ring may be replaced by an oxygen atom, a sulfur atom or a carbonyl group;

R^b7 and R^b8 in each occurrence independently represent a hydroxy group, a C₁ to C₁₂ aliphatic hydrocarbon group or a C₁ to C₁₂ alkoxy group,

m2 and n2 independently represent an integer of 0 to 5;

R^b9 and R^b10 independently represent a C₁ to C₃₆ aliphatic hydrocarbon group or a C₃ to C₃₆ alicyclic hydrocarbon group, or R^b9 and R^b10 may be bonded together with a sulfur atom bonded thereto to form a sulfur-containing ring, and a methylene group contained in the ring may be replaced by an oxygen atom, sulfur atom or a carbonyl group;

R^b11 represents a hydrogen atom, a C₁ to C₃₆ aliphatic hydrocarbon group, a C₃ to C₃₆ alicyclic hydrocarbon group or a C₆ to C₁₈ aromatic hydrocarbon group;

R^b12 represents a C₁ to C₁₂ aliphatic hydrocarbon group, a C₃ to C₁₈ alicyclic hydrocarbon group and a C₆ to C₁₈ aromatic hydrocarbon group, a hydrogen atom contained in an aliphatic hydrocarbon group may be replaced by a C₆ to C₁₈ aromatic hydrocarbon group, and a hydrogen atom contained in an aromatic hydrocarbon group may be replaced by a C₁ to C₁₂ alkoxy group or a C₁ to C₁₂ alkyl carbonyloxy group;

R^b11 and R^b12 may be bonded together with —CH—CO— bonded thereto to form a ring, and a methylene group contained in the ring may be replaced by an oxygen atom, sulfur atom or a carbonyl group;

R^b13, R^b14, R^b15, R^b16, R^b17 and R^b18 in each occurrence independently represent a hydroxy group, a C₁ to C₁₂ aliphatic hydrocarbon group or a C₁ to C₁₂ alkoxy group;

L^b11 represents —S— or —O—;

o2, p2, s2 and t2 independently represent an integer of 0 to 5;

q2 or r2 independently represent an integer of 0 to 4; and

u2 represents an integer of 0 or 1.

Examples of the aliphatic group preferably include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl and 2-ethylhexyl groups. Among these, the aliphatic hydrocarbon group of R^b9 to R^b12 is preferably a C₁ to C₁₂ aliphatic hydrocarbon group.

Examples of the alicyclic hydrocarbon group preferably include monocyclic groups such as a cycloalkyl group, i.e., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl groups; and polycyclic hydrocarbon groups such as decahydronaphtyl, adamantyl and norbornyl groups as well as groups below.

Among these, the alicyclic hydrocarbon group of R^b9 to R^b12 is preferably a C₃ to C₁₈ alicyclic group, and more preferably a C₄ to C₁₂ alicyclic hydrocarbon group.

Examples of the alicyclic hydrocarbon group where a hydrogen atom may be replaced by an aliphatic hydrocarbon group include methylcyclohexyl, dimethylcyclohexyl, 2-alkyladamantane-2-yl, methylnorbornyl and isobornyl groups. In the alicyclic hydrocarbon group where a hydrogen atom may be replaced by an aliphatic hydrocarbon group, the total carbon number of the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably 20 or less.

Examples of the aromatic hydrocarbon group preferably include an aryl group such as phenyl, tolyl, xylyl, cumenyl, mesityl, p-ethylphenyl, p-tert-butylphenyl, p-cyclohexylphenyl, p-adamantylphenyl, biphenyl, naphthyl, phenanthryl, 2,6-diethylphenyl and 2-methyl-6-ethylphenyl groups.

When the aromatic hydrocarbon includes an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, a C₁ to C₁₈ aliphatic hydrocarbon group or a C₃ to C₁₈ alicyclic hydrocarbon group is preferred.

Examples of the aromatic hydrocarbon group where a hydrogen atom may be replaced by an alkoxy group include a p-methoxyphenyl group.

Examples of the aliphatic hydrocarbon group where a hydrogen atom may be replaced by an aromatic hydrocarbon group include an aralkyl group such as benzyl, phenethyl phenylpropyl, trityl, naphthylmethyl and naphthylethyl groups.

Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, and dodecyloxy groups.

Examples of the acyl group include acetyl, propionyl and butyryl groups.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms.

Examples of the alkylcarbonyloxy group include methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, isopropylcarbonyloxy, n-butylcarbonyloxy, sec-butylcarbonyloxy, tert-butyl carbonyloxy, pentylcarbonyloxy, hexylcarbonyloxy, octylcarbonyloxy and 2-ethylhexylcarobonyloxy groups.

The sulfur atom-containing ring which is formed by R^b4 and R^b5 may be a monocyclic or polycyclic one, which may be an aromatic or non-aromatic one, and which may be a saturated or unsaturated one. The ring is preferably a ring having 3 to 18 carbon atoms, and more preferably a ring having 4 to 13 carbon atoms. Examples of the sulfur atom-containing ring include a 3- to 12-membered ring, preferably a 3- to 7-membered ring, examples thereof include rings below.

Examples of the ring formed by R^b9 and R^b10 may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. The ring may be a 3- to 12-membered ring, preferably a 3- to 7-membered ring. Examples of the ring include thiolane-1-ium ring (tetrahydrothiophenium ring), thian-1-ium ring and 1,4-oxathian-4-ium ring.

Examples of the ring formed by R^b11 and R^b12 may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. The ring may be a 3- to 12-membered ring, preferably a 3- to 7-membered ring. Examples of the ring include oxocycloheptane ring, oxocyclohexane ring, oxonorbornane ring and oxoadamantane ring.

Among the cations represented by the formula (b2-1) to the formula (b2-4), the cation represented by the formula (b2-1) is preferred, the cation represented by the formula (b2-1-1) is more preferred, and triphenyl sulfonium cation (v2=w2=x2=0 in the formula (b2-1-1)), diphenyl sulfonium cation (v2=w2=0, x2=1, and R^b21 is a methyl group in the formula (b2-1-1)), and tritolyl sulfonium cation (v2=w2=x2=1, R^b19, R^b20 and R^b21 are a methyl group in the formula (b2-1-1)) are still more preferred:

wherein R^b19, R^b20 and R^b21 in each occurrence independently represent a halogen atom, a hydroxy group, a C₁ to C₁₈ aliphatic hydrocarbon group, a C₃ to C₁₈ alicyclic hydrocarbon group or a C₁ to C₁₂ alkoxy group, or two of R^b19, R^b20 and R^b21 may be bonded together to form a sulfur-containing ring.

In the formula (b2-1-1), the sulfur-containing ring formed by two of R^b19, R^b20 and R^b21 may be monocyclic or polycyclic ring. The ring may be aromatic or non-aromatic ring. The ring may be saturated or unsaturated ring. The ring may have a further more sulfur atom and/or an oxygen atom.

The alkyl group of R^b19, R^b20 and R^b21 is preferably a C₁ to C₁₂ aliphatic hydrocarbon group. The alicyclic hydrocarbon group of R^b19, R^b20 and R^b21 is preferably a C₄ to C₁₈ alicyclic hydrocarbon group,

R^b19, R^b20 and R^b21 each independently preferably represent a halogen atom (and more preferably fluorine atom), a hydroxy group, a C₁ to C₁₂ aliphatic hydrocarbon group or a C₁ to C₁₂ alkoxy group; or two of R^b19, R^b20 and R^b21 preferably are bonded together to form a sulfur-containing ring, and

v2, w2 and x2 independently represent preferably 0 or 1.

Specific examples of the organic cations represented by the formula (b2-1) to the formula (b2-4) and the formula (b2-1-1) include, for example, compounds described in JP2010-204646A.

The acid generator (B1) is generally a compound which consists of the above sulfonate anion with an organic cation. The above sulfonic acid anion and the organic cation may optionally be combined. Preferred combination is a combination of any of the anion represented by the formula (B1a-1) to the formula (B1a-3), the formula (B1a-7) to the formula (B1a-15) and the cation represented by the formula (b2-1-1) or the formula (b2-3).

Preferred acid generators (B1) are represented by the formula (B1-1) to the formula (B1-30). Among these, the formulae (B1-1), (B1-2), (B1-3), (B1-5), (B1-6), (B1-7), (B1-11), (B1-12), (B1-13), (B1-14), (B1-17), (B1-20), (B1-21), (B1-23), (B1-24), (B1-25), (B1-26) and (B1-29) which contain arylsulfonium cation are preferred.

The proportion of the acid generator (B1) is preferably 30% by mass or more, and 100% by mass or less, more preferably 50% by mass or more, and 100% by mass or less, and still more preferably substantially 100% by weight with respect to 100% by mass of total acid generator (B).

In the resist composition of the present invention, the proportion of the acid generator (B) is preferably 1 parts by mass or more and more preferably 3 parts by mass or more, and preferably 30 parts by mass or less and more preferably 25 parts by mass or less with respect to 100 parts by mass of the resin (A).

In the resist composition of the present invention, the acid generator (B) may be used as a single salt or as a combination of two or more of salts.

<Solvent (E)>

The proportion of a solvent (E) is generally 90% by mass or more, preferably 92% by mass or more, and more preferably 94% by mass or more, and also preferably 99% by mass or less, and more preferably 99.9% by mass or less. The proportion of the solvent (E) can be measured with a known analytical method such as liquid chromatography and gas chromatography.

Examples of the solvent (E) include glycol ether esters such as ethylcellosolve acetate, methylcellosolve acetate and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; esters such as ethyl lactate, butyl acetate, amyl acetate and ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone; and cyclic esters such as γ-butyrolactone. These solvents may be used as a single solvent or as a mixture of two or more solvents.

<Quencher (C)>

The resist composition of the present invention may contain a quencher such as a basic nitrogen-containing organic compound and a salt which generates an acid weaker in acidity than an acid generated from the acid generator.

The proportion of the quencher is preferably 0.01% by mass to 5% by mass with respect to the total solid components of the resist composition.

Examples of the basic nitrogen-containing organic compound include an amine and ammonium salts. The amine may be an aliphatic amine or an aromatic amine. The aliphatic amine includes any of a primary amine, secondary amine and tertiary amine.

Specific examples of the amine include 1-naphtylamine, 2-naphtylamine, aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexylmethylamine, tris[2-(2-methoxy ethoxy)ethyl]amine, triisopropanolamine, ethylene diamine, tetramethylene diamine, hexamethylene diamine, 4,4′-diamino-1,2-diphenylethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-diamino-3,3′-diethyldiphenylmethane, 2,2′-methylenebisaniline, imidazole, 4-methylimidazole, pyridine, 4-methylpyridine, 1,2-di(2-pyridyl)ethane, 1,2-di(4-pyridyl)ethane, 1,2-di(2-pyridyl)ethene, 1,2-di(4-pyridyl)ethene, 1,3-di(4-pyridyl)propane, 1,2-di(4-pyridyloxy)ethane, di(2-pyridyl)ketone, 4,4′-dipyridyl sulfide, 4,4′-dipyridyl disulfide, 2,2′-dipyridylamine, 2,2′-dipicolylamine and bipyridine. Among these, diisopropylaniline is preferred, particularly 2,6-diisopropylaniline is more preferred.

Specific examples of the ammonium salt include tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethyl ammonium hydroxide, 3-(trifluoromethyl)phenyltrimethylammonium hydroxide, tetra-n-butyl ammonium salicylate and choline.

<Weak Acid Salt>

The salt generating an acid which is lower in acidity than an acid generated from the acid generator (B) is sometimes referred to as “weak acid salt”. The “acidity” can be represented by acid dissociation constant, pKa, of an acid generated from a weak acid salt. Examples of the weak acid salt include a salt generating an acid of pKa represents generally more than −3, preferably −1 to 7, and more preferably 0 to 5.

Specific examples of the weak acid salt include the following salts, the salt of formula (D), and salts as disclosed in JP2012-229206A1, JP2012-6908A1, JP2012-72109A1, JP2011-39502A1 and JP2011-191745A1, preferably the salt of formula (D).

In the formula (D), R^D1 and R^D2 in each occurrence independently represent a C₁ to C₁₂ hydrocarbon group, a C₁ to C₆ alkoxyl group, a C₂ to C₇ acyl group, a C₂ to C₇ acyloxy group, a C₂ to C₇ alkoxycarbonyl group, a nitro group or a halogen atom;

m′ and n′ each independently represent an integer of 0 to 4.

Examples of the hydrocarbon group of R^D1 and R^D2 include any of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and a combination thereof.

Examples of the aliphatic hydrocarbon group include an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl and nonyl groups.

The alicyclic hydrocarbon group is any one of monocyclic or polycyclic hydrocarbon group, and saturated or unsaturated hydrocarbon group. Examples thereof include a cycloalkyl group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclononyl and cyclododecyl groups; adamantyl and norbornyl groups. The alicyclic hydrocarbon group is preferably saturated hydrocarbon group.

Examples of the aromatic hydrocarbon group include an aryl group such as phenyl, 1-naphthyl, 2-naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-ethylphenyl, 4-propylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, anthryl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl, phenanthryl, 2,6-diethylphenyl and 2-methyl-6-ethylphenyl groups.

Examples of the combination thereof include an alkyl-cycloalkyl, a cycloalkyl-alkyl, aralkyl (e.g., phenylmethyl, 1-phenylethyl, 2-phenylethyl, 1-phenyl-1-propyl, 1-phenyl-2-propyl, 2-phenyl-2-propyl, 3-phenyl-1-propyl, 4-phenyl-1-butyl, 5-phenyl-1-pentyl and 6-phenyl-1-hexyl groups) groups.

Examples of the alkoxyl group include methoxy and ethoxy groups.

Examples of the acyl group include acetyl, propanonyl, benzoyl and cyclohexanecarbonyl groups.

Examples of the acyloxy group include a group in which oxy group (—O—) bonds to an acyl group.

Examples of the alkoxycarbonyl group include a group in which the carbonyl group (—CO—) bonds to the alkoxy group.

Example of the halogen atom is a chlorine atom, a fluorine atom and bromine atom.

In the formula (D), R^D1 and R^D2 in each occurrence independently preferably represent a C₁ to C₈ alkyl group, a C₃ to C₁₀ cycloalkyl group, a C₁ to C₆ alkoxyl group, a C₂ to C₄ acyl group, a C₂ to C₄ acyloxy group, a C₂ to C₄ alkoxycarbonyl group, a nitro group or a halogen atom.

m′ and n′ independently preferably represent an integer of 0 to 3, more preferably an integer of 0 to 2, and more preferably 0.

Specific examples of the salt of the formula (D) include compounds below.

The salt of the formula (D) can be produced by a method described in “Tetrahedron Vol. 45, No. 19, p6281-6296”. Also, commercially available compounds can be used as the salt of the formula (D).

In the resist composition of the present invention, the proportion of the salt which generates an acid weaker in acidity than an acid generated from the acid generator, for example, the salt of the formula (D) is preferably 0.01% by mass to 5% by mass, more preferably 0.01% by mass to 4% by mass, and still more preferably 0.01% by mass to 3% by mass with respect to total solid components of the resist composition.

<Other Ingredient>

The resist composition can also include other ingredient (which is sometimes referred to as “other ingredient (F)”). Examples of the other ingredient (F) include various additives such as sensitizers, dissolution inhibitors, surfactants, stabilizers, and dyes, as needed.

<Preparing the Resist Composition>

The present resist composition can be prepared by mixing the resin (A), the compound (a), the acid generator (B), the resin other than the resin (A), the quencher, the solvent (E) and the other ingredient (F), as needed. There is no particular limitation on the order of mixing. The mixing may be performed in an arbitrary order. The temperature of mixing may be adjusted to an appropriate temperature within the range of 10 to 40° C., depending on the kinds of the resin and solubility in the solvent (E) of the resin. The time of mixing may be adjusted to an appropriate time within the range of 0.5 to 24 hours, depending on the mixing temperature. There is no particular limitation to the tool for mixing. An agitation mixing may be adopted.

After mixing the above ingredients, the present resist compositions can be prepared by filtering the mixture through a filter having about 0.003 to 0.2 μm pore diameter.

<Method for Producing Resist Pattern>

The method for producing a resist pattern of the present invention includes the steps of:

(1) applying the resist composition of the present invention onto a substrate;

(2) drying the applied composition to form a composition layer;

(3) exposing the composition layer;

(4) heating the exposed composition layer, and

(5) developing the heated composition layer.

Applying the resist composition onto the substrate can generally be carried out through the use of a resist application device, such as a spin coater known in the field of semiconductor microfabrication technique. Examples of the substrate include inorganic substrates such as silicon wafer. The substrate may be washed, and an organic antireflection film may be formed on the substrate by use of a commercially available antireflection composition, before the application of the resist composition.

The solvent evaporates from the resist composition and a composition layer with the solvent removed is formed. Drying the applied composition layer, for example, can be carried out using a heating device such as a hotplate (so-called “prebake”), a decompression device, or a combination thereof. The temperature is preferably within the range of 50 to 200° C. The time for heating is preferably 10 to 180 seconds. The pressure is preferably within the range of 1 to 1.0×10⁵ Pa.

The composition layer thus obtained is generally exposed using an exposure apparatus or a liquid immersion exposure apparatus. The exposure is generally carried out using with various types of exposure light source, such as irradiation with ultraviolet lasers, i.e., KrF excimer laser (wavelength: 248 nm), ArF excimer laser (wavelength: 193 nm), F₂ excimer laser (wavelength: 157 nm), irradiation with harmonic laser light of far-ultraviolet or vacuum ultra violet wavelength-converted laser light from a solid-state laser source (YAG or semiconductor laser or the like), or irradiation with electron beam or EUV or the like. In the specification, such exposure to radiation is sometimes referred to be collectively called as exposure. The exposure is generally carried out through a mask that corresponds to the desired pattern. When electron beam is used as the exposure light source, direct writing without using a mask can be carried out.

After exposure, the composition layer is subjected to a heat treatment (so-called “post-exposure bake”) to promote the deprotection reaction. The heat treatment can be carried out using a heating device such as a hotplate. The heating temperature is generally in the range of 50 to 200 degree C., preferably in the range of 70 to 150 degree C.

The developing of the baked composition film is usually carried out with a developer using a development apparatus. Developing can be conducted in the manner of dipping method, paddle method, spray method and dynamic dispensing method. Temperature for developing is generally 5 to 60 degree C. The time for developing is preferably 5 to 300 seconds.

The photoresist pattern obtained from the photoresist composition may be a positive one or a negative one by selecting suitable developer.

The development for obtaining a positive photoresist pattern is usually carried out with an alkaline developer. The alkaline developer to be used may be any one of various alkaline aqueous solution used in the art. Generally, an aqueous solution of tetramethylammonium hydroxide or (2-hydroxyethyl)trimethylammonium hydroxide (commonly known as “choline”) is often used. The surfactant may be contained in the alkaline developer.

After development, the resist pattern formed is preferably washed with ultrapure water, and the residual water remained on the resist film or on the substrate is preferably removed therefrom.

The development for obtaining a negative photoresist pattern is usually carried out with a developer containing an organic solvent. The organic solvent to be used may be any one of various organic solvents used in the art, examples of which include ketone solvents such as 2-hexanone, 2-heptanone; glycol ether ester solvents such as propylene glycol monomethyl ether acetate; ester solvents such as the butyl acetate; glycol ether solvents such as the propylene glycol monomethyl ether; amide solvents such as N,N-dimethylacetamide; aromatic hydrocarbon solvents such as anisole.

In the developer containing an organic solvent, the amount of organic solvents is preferably 90% by mass to 100% by mass, more preferably 95% by mass to 100% by mass of the developer. The developer still more preferably consists essentially of organic solvents.

Among these, the developer containing an organic solvent preferably contains butyl acetate and/or 2-heptanone. In the developer containing an organic solvent, the total amount of butyl acetate and 2-heptanone is preferably 50% by mass to 100% by mass of the developer, more preferably 90% by mass to 100% by mass of the developer. The developer still more preferably consists essentially of butyl acetate and/or 2-heptanone.

Developers containing an organic solvent may contain a surfactant. Also, the developer containing an organic solvent may include a little water.

The developing with a developer containing an organic solvent can be finished by replacing the developer by another solvent.

After development, the photoresist pattern formed is preferably washed with a rinse agent. Such rinse agent is not unlimited provided that it does not detract a photoresist pattern. Examples of the agent include solvents which contain organic solvents other than the above-mentioned developers, such as alcohol agents or ester agents.

After washing, the residual rinse agent remained on the substrate or photoresist film is preferably removed therefrom.

<Application>

The resist composition of the present invention is useful for excimer laser lithography such as with ArF, KrF, electron beam (EB) exposure lithography or extreme-ultraviolet (EUV) exposure lithography, and is more useful for electron beam (EB) exposure lithography, ArF excimer laser exposure lithography and extreme-ultraviolet (EUV) exposure lithography.

The resist composition of the present invention can be used in semiconductor microfabrication.

EXAMPLES

The present invention will be described more specifically by way of examples, which are not construed to limit the scope of the present invention.

All percentages and parts expressing the content or amounts used in the Examples and Comparative Examples are based on mass, unless otherwise specified.

The weight average molecular weight is a value determined by gel permeation chromatography.

Column: TSK gel Multipore HXL-M×3+guardcolumn (Tosoh Co. Ltd.)

Eluant: tetrahydrofuran

Flow rate: 1.0 mL/min

Detecting device: RI detector

Column temperature: 40° C.

Injection amount: 100 μL

Standard material for calculating molecular weight: standard polysthylene (Tosoh Co. ltd.)

Structures of compounds were determined by mass spectrometry (Liquid Chromatography: 1100 Type, manufactured by AGILENT TECHNOLOGIES LTD., Mass Spectrometry: LC/MSD Type, manufactured by AGILENT TECHNOLOGIES LTD.). The value of the peak in the mass spectrometry is referred to as “MASS”.

Example 1

Synthesis of the Salt Represented by the Formula (I-1)

A salt represented by the formula (I-1-b) was synthesized by the method described in JP2012-194466A.

Into a reactor, 25 parts of the salt represented by the formula (I-1-a), 29.19 parts of the salt represented by the formula (I-1-b), 175 parts of chloroform and 87.5 parts of ion exchanged water were charged and stirred at 23 degree C. for 2 hours. Then, the mixture was left still to thereby separate an organic phase therefrom. To the obtained organic layer, 87.5 parts of ion exchanged water was added, and the obtained mixture was washed with water. The washing step with water was conducted five times. The obtained chloroform layer was concentrated, whereby giving 33.54 parts of the salt represented by the formula (I-1).

MASS (ESI(+)Spectrum):M⁺ 263.1

MASS (ESI(−)Spectrum):M⁻ 314.0

Example 2

Synthesis of the Salt Represented by the Formula (I-2)

Into a reactor, 5 parts of compound represented by formula (I-2-a), 1 part of N,N-dimethylformamide and 50 parts of n-heptane were charged and stirred at 23 degree C. for 30 minutes. Then, 4.51 parts of thionyl chloride were dropped thereinto at 23 degree C. for 30 minutes, and the obtained mixture was stirred at 75 degree C. for two hours. The obtained reaction solution was cooled into 23 degree C., followed by separating n-heptane layer. 50 parts of 5% of aqueous sodium bicarbonate solution was added to the obtained organic layer, and stirred at 23 degree C. for 30 minutes. Then, the mixture was left still to thereby separate an organic phase. To the obtained organic layer, 50 parts of ion exchanged water was added, and stirred at 23 degree C. for 30 minutes, followed by separating an organic layer to wash with water. The obtained organic layer was concentrated, whereby giving 1.88 parts of the salt represented by the formula (I-2-a).

Into a reactor, 1.91 parts of compound represented by formula (I-2-c) and 10 parts of tetrahydrofran were charged and stirred at 23 degree C. for 30 minutes. The obtained reaction solution was cooled into 0 degree C. To the obtained mixture, 0.17 parts of ammoia was added, and stirred at 0 degree C. for 2 hours, and then stirred at 23 degree C. for 30 minutes. Then, 0.36 parts of hydrochloric acid was added to the obtained mixture and stirred, whereby giving the solution containing the compound represented by the formula (I-2-d).

To the obtained solution containing the compound represented by the formula (I-2-d), 25 parts of methylene chloride was added, and stirred at 23 degree C. for 30 minutes. The obtained reaction solution was cooled into 5 degree C. Then, 1.82 parts of triethylamine was dropped thereinto for 20 minutes, and 1.83 parts of the compound represented by the formula (I-2-b) thereto. The obtained mixture solution was stirred at 23 degree C. for 5 hours. Then, 100 parts of ion exchanged water was added thereto and stirred at 23 degree C. for 30 minutes, followed by separating an organic layer to wash with water. The obtained organic layer was concentrated, whereby giving 3.12 parts of the salt represented by the formula (I-2-e).

Into a reactor, 2.85 parts of the compound represented by the formula (I-2-e), 2.50 parts of the compound represented by the formula (I-2-f), 17.5 parts of chloroform and 8.75 parts of ion exchanged water were charged and stirred at 23 degree C. for 2 hours, followed by separating an organic layer to wash with water. To the obtained organic layer, 8.75 parts of ion exchanged water was added, and washed with water. The washing step with water was conducted five times. Then the obtained chloroform layer was concentrated, whereby giving 3.17 parts of the salt represented by the formula (I-2).

MASS (ESI(+)Spectrum):M⁺ 263.1

MASS (ESI(−)Spectrum):M⁻ 354.0

Example 3

Synthesis of the Salt Represented by the Formula (I-3)

Into a reactor, 1.50 parts of the salt represented by the formula (I-2), 10 parts of ion exchanged water and 10 parts of acetonitrile were charged and stirred at 23 degree C. for about 30 minutes. The resulting reactant was cooled into 5 degree C. 2 parts of 30% aqueous sodium hydroxide solution was dropped and the obtained mixture was stirred at 80 degree C. for 3 hours. After cooling the mixture, neutralization of it was conducted with 1 part of the concentrated hydrochloric acid. Then the obtained mixture was concentrated, whereby giving the mixture containing the salt represented by the formula (I-3-a).

To the mixture containing the salt represented by the formula (I-3-a), 0.44 parts of the salt represented by the formula (I-3-b) and 20 parts of dichloroethane were added, and 0.3 parts of concentrated sulfuric acid was added thereto, and the mixture was heated to reflux for 20 hours. Then the reaction mixture was concentrated, 30 parts of t-butylmethlether was added to the obtained residue and stirred at 23 degree C. for about 1 hour, followed by filtrating, whereby giving 0.48 parts of the salt represented by the formula (I-3).

MASS (ESI(+)Spectrum):M⁺ 263.1

MASS (ESI(−)Spectrum):M⁻ 488.1

Synthesis Examples of Resins

The monomers used for the synthesis of resins are shown below. These monomers are referred to as “monomer (X)” where “(X)” is the symbol of the formula representing the structure of each monomer.

Example 4

Synthesis of Resin A1

Monomer (a1-1-3), monomer (a1-2-9), monomer (a2-1-3), monomer (a3-2-1), monomer (a3-1-1) and monomer (I-1) were mixed together with the mole ratio of monomer (a1-1-3), monomer (a1-2-9), monomer (a2-1-3), monomer (a3-2-1), monomer (a3-1-1) and monomer (I-1)=28:15:5:7:42:3, and methylethylketone was added thereto in the amount equal to 1.5 times by mass of the total amount of monomers to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators to the solution in the amounts of 1.2% by mole and 3.6% by mole respectively with respect to the total amount of monomers, and the resultant mixture was heated for about 5 hours at 75° C. Then, the obtained solution of a resin was poured into a large amount of n-heptane to precipitate a resin. The obtained resin was filtrated. Then, the obtained resin was poured into a mixed solvent of n-heptane and isopropanol (the ratio of n-heptane and isopropanol was 8/2 by mass) to precipitate the resin. The obtained resin was filtrated to obtain the copolymer having a weight average molecular weight of about 5500 in 45% yield. This resin, which had the structural units of the following formulae, was referred to as Resin A1.

Example 5

Synthesis of Resin A2

Monomer (a1-1-3), monomer (a1-2-7), monomer (a2-1-1), monomer (ax-1), monomer (a3-1-1) and monomer (I-1) were mixed together with the mole ratio of monomer (a1-1-3), monomer (a1-2-7), monomer (a2-1-1), monomer (ax-1), monomer (a3-1-1) and monomer (I-1)=28:12.5:6:18:30:5.5, and methylethylketone was added thereto in the amount equal to 1.5 times by mass of the total amount of monomers to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators to the solution in the amounts of 0.6% by mole and 1.8% by mole respectively with respect to the total amount of monomers, and the resultant mixture was heated for about 5 hours at 73° C. Then, the obtained solution of a resin was poured into a large amount of n-heptane to precipitate a resin. The obtained resin was filtrated. Then, the obtained resin was poured into a mixed solvent of n-heptane and isopropanol (the ratio of n-heptane and isopropanol was 8/2 by mass) to precipitate the resin. The obtained resin was filtrated to obtain the copolymer having a weight average molecular weight of about 16000 in 42% yield. This resin, which had the structural units of the following formulae, was referred to as Resin A2.

Example 6

Synthesis of Resin A3

Monomer (a1-1-3), monomer (a1-2-9), monomer (a2-1-3), monomer (a3-2-1), monomer (a3-1-1) and monomer (1-2) were mixed together with the mole ratio of monomer (a1-1-3), monomer (a1-2-9), monomer (a2-1-3), monomer (a3-2-1), monomer (a3-1-1) and monomer (I-2)=28:15:5:7:42:3, and methylethylketone was added thereto in the amount equal to 1.5 times by mass of the total amount of monomers to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators to the solution in the amounts of 1.2% by mole and 3.6% by mole respectively with respect to the total amount of monomers, and the resultant mixture was heated for about 5 hours at 75° C. Then, the obtained solution of resin was poured into a large amount of n-heptane to precipitate a resin. The obtained resin was filtrated. Then, the obtained resin was poured into a mixed solvent of n-heptane and isopropanol (the ratio of n-heptane and isopropanol was 8/2 by mass) to precipitate the resin. The obtained resin was filtrated to the copolymer having a weight average molecular weight of about 5800 in 48% yield. This resin, which had the structural units of the following formulae, was referred to as Resin A3.

Example 7

Synthesis of Resin A4

Monomer (a1-1-3), monomer (a1-2-9), monomer (a2-1-3), monomer (a3-2-1), monomer (a3-1-1) and monomer (I-2) were mixed together with the mole ratio of monomer (a1-1-3), monomer (a1-2-9), monomer (a2-1-3), monomer (a3-2-1), monomer (a3-1-1) and monomer (I-2)=28:15:5:7:42:3, and methylethylketone was added thereto in the amount equal to 1.5 times by mass of the total amount of monomers to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators to the solution in the amounts of 1.2% by mole and 3.6% by mole respectively with respect to the total amount of monomers, and the resultant mixture was heated for about 5 hours at 75° C. Then, the obtained solution of a resin was poured into a large amount of n-heptane to precipitate a resin. The obtained resin was filtrated. Then, the obtained resin was poured into a mixed solvent of n-heptane and isopropanol (the ratio of n-heptane and isopropanol was 8/2 by mass) to precipitate the resin. The obtained resin was filtrated to obtain the copolymer having a weight average molecular weight of about 5600 in 51% yield. This resin, which had the structural units of the following formulae, was referred to as Resin A4.

Synthesis Example 1

Synthesis of Resin AX1

Monomer (a1-1-3), monomer (a1-2-7), monomer (a2-1-1), monomer (ax-1), monomer (a3-1-1) and monomer (IX-1) were mixed together with the mole ratio of monomer (a1-1-3), monomer (a1-2-7), monomer (a2-1-1), monomer (ax-1), monomer (a3-1-1) and monomer (IX-1)=28:12.5:6:18:30:5.5, and methylethylketone was added thereto in the amount equal to 1.5 times by mass of the total amount of monomers to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators to the solution in the amounts of 0.6% by mole and 1.8% by mole respectively with respect to the total amount of monomers, and the resultant mixture was heated for about 5 hours at 73° C. Then, the obtained solution of a resin was poured into a large amount of n-heptane to precipitate a resin. The obtained resin was filtrated. Then, the obtained resin was poured into a mixed solvent of n-heptane and isopropanol (the ratio of n-heptane and isopropanol was 8/2 by mass) to precipitate the resin. The obtained resin was filtrated to obtain the copolymer having a weight average molecular weight of about 16000 in 58% yield. This resin, which had the structural units of the following formulae, was referred to Resins AX1.

Synthesis Example 2

Synthesis of Resin AX2

Monomer (a1-1-2), monomer (a2-1-1), monomer (a3-1-1) and monomer (IX-2) were mixed together with the mole ratio of monomer (a1-1-2), monomer (a2-1-1), monomer (a3-1-1) and monomer (IX-2)=40:25:25:10, and methylethylketone was added thereto in the amount equal to 1.5 times by mass of the total amount of monomers to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators to the solution in the amounts of 1.2% by mole and 3.6% by mole respectively with respect to the total amount of monomers, and the resultant mixture was heated for about 5 hours at 75° C. Then, the obtained reaction mixture was poured into a large amount of a mixed solvent of methanol and water (the ratio of methanol and water was 4/1 by mass) to precipitate a resin. The obtained resin was filtrated. The obtained resin is dissoleved in another methylethylketone and the obtained solution was poured into a large amount of a mixed solvent of methanol and water (4/1 ratio by mass) to precipitate the resin. The operation was conducted twice, to obtain the copolymer having a weight average molecular weight of about 6900, in 62% yield. This resin, which had the structural units of the following formulae, was referred to Resin as AX2.

(Preparing Resist Composition)

Resist compositions were prepared by mixing and dissolving each of the components shown in Table 1, and then filtrating through a fluororesin filter having 0.2 μm pore diameter.

TABLE 1
	Resin	Acid Generator	Qencher (C)	PB/PEB
Resist Comp.	(parts)	(B) (parts)	(parts)	(° C./° C.)
Composition 1	A1 = 10	B1-21 = 3	C1 = 0.1	100/100
Composition 2	A1 = 10	—	C1 = 0.1	100/100
Composition 3	A2 = 10	B1-21 = 3	C1 = 0.1	100/100
Composition 4	A2 = 10	—	C1 = 0.1	100/100
Composition 5	A3 = 10	B1-21 = 3	C1 = 0.1	100/100
Composition 6	A4 = 10	B1-21 = 3	C1 = 0.1	100/100
Comparative	AX1 = 10	B1-21 = 3	C1 = 0.1	100/100
Composition 1
Comparative	AX2 = 10	—	C1 = 0.1	100/100
Composition 2

<Resin>

Resins: Resins A1 to A4 and AX1 to AX2, prepared by Synthesis Examples of Resins

<Acid Generator (B)>

B1-21: Salt represented by the following formula, prepared by synthesis according to JP2011-126869A.

<Quencher (C)>

C1: Compound represented by the following formula, prepared by synthesis according to JP2011-39502A.

<Solvent for Resist Compositions>

Propyleneglycolmonomethylether acetate 400 parts
Propyleneglycolmonomethylether   150 parts
γ-butyrolactone                  5 parts

(Producing Resist Pattern: EB Direst Writing)

6-inch silicon wafers were treated with hexamethyldisilazane on a direct hot plate for 60 seconds at 90° C.

On one of the treated wafers, one of the resist composition was then applied by spin coating in such a manner that the thickness of the resulting film became 40 nm.

The obtained wafer was then pre-baked for 60 sec on a direct hot plate at the temperature given in the “PB” column in Table 1.

On the wafers on which the resist film had thus been formed, the film was then exposed with changing exposure quantity stepwise by direct writing using an electron beam lithography machine (“HL-800D”, 50 keV, by Hitachi, Ltd.) to thereby form line and space patterns.

After the exposure, post-exposure baking was carried out for 60 seconds at the temperature given in the “PEB” column in Table 1.

Then, puddle development was carried out with 2.38 wt % aqueous tetramethylammonium hydroxide solution for 60 seconds to obtain resist patterns.

(Pattern Collapse (PCM) Evaluation)

The pattern collapse margin was calculated according to the formula below on the obtained resist patterns:Pattern Collapse Margin (%)=(E₂−E₁)/E₁×100,

wherein

E₁ represents a minimum exposure quantity at which line and space patterns with 60 nm width were formed, and

E₂ represents a minimum exposure quantity at which the pattern collapse arose resulting from making the same patterns by exposure at exposure quantity higher than E1.

Table 2 illustrates the results.

The higher the value of the pattern collapse margin is, the patter collapse is less likely to occur even when the exposure is conducted with high exposure quantity.

	TABLE 2
	Resist Composition	PCM (%)
	Ex. 8	Composition 1	42
	Ex. 9	Composition 2	31
	Ex. 10	Composition 3	31
	Ex. 11	Composition 4	24
	Ex. 12	Composition 5	47
	Ex. 13	Composition 6	53
	Comparative Ex. 1	Comparative Composition 1	21
	Comparative Ex. 2	Comparative Composition 2	13

(Producing Resist Pattern: EUV Exposure)

4-inch silicon wafers were treated with hexamethyldisilazane on a direct hot plate for 60 seconds at 90° C.

On one of the treated wafers, one of the resist compositions was then applied by spin coating in such a manner that the thickness of the resulting film became 35 nm.

The obtained wafer was then pre-baked for 60 sec on a direct hot plate at the temperature given in the “PB” column in Table 1.

On the wafers on which the resist film had thus been formed, the film was then exposed with changing exposure quantity stepwise using an EUV lithography machine to thereby form line and space patterns.

After the exposure, post-exposure baking was carried out for 60 seconds at the temperature given in the “PEB” column in Table 1.

Then, puddle development was carried out with 2.38 wt % aqueous tetramethylammonium hydroxide solution for 60 seconds to obtain resist patterns.

(Pattern Collapse (PCM) Evaluation)

The pattern collapse margin was calculated in the same manner as above except for making line and space patterns with 20 nm width for the evaluation. Table 3 illustrates the results of the evaluation.

	TABLE 3
	Resist Composition	PCM (%)
	Ex. 14	Composition 1	38
	Ex. 15	Composition 6	47

The resin which includes the structural unit derived from the salt (I) of the disclosure or the salt (I) is useful for the resist composition which shows good pattern collapse margin. The resist composition can be used for semiconductor microfabrication.

Claims

1. A resin comprising a structural unit derived from a salt represented by formula (I):

2. The resin according to claim 1, further comprising a structural unit having an acid-labile group.

3. A resist composition comprising the resin according to claim 1.

4. A method for producing a resist pattern comprising steps (1) to (5); (1) applying the resist composition according to claim 3 onto a substrate;(2) drying the applied composition to form a composition layer;(3) exposing the composition layer;(4) heating the exposed composition layer, and(5) developing the heated composition layer.