Resist composition, resist pattern formation method, compound, acid generator, acid diffusion control agent, and polymer compound

Abstract

The present invention provides a resist composition, a resist pattern formation method, a compound used in the resist composition, an acid generator, an acid diffusion control agent, and a polymer compound that achieve high sensitivity, enhance lithography characteristics such as roughness reduction, and suppress the occurrence of defects. [Solution] A resist composition is used that generates acid upon exposure and whose solubility in a developer solution changes due to the action of the acid, and which contains a compound comprising a cation represented by the general formula (c0). In the formula, R 01 and R 02 Each of these independently represents an optionally substituted aryl group, an optionally substituted alkyl group, or an optionally substituted alkenyl group. 01 and R 02 These may bond with each other to form a ring together with the sulfur atom in the formula. 03 represents a substituent. TIFF2026110235000171.tif46170

Description

Technical Field

[0001] The present invention relates to a resist composition, a method for forming a resist pattern, a compound, an acid generator, an acid diffusion controller, and a polymer compound.

Background Art

[0002] In recent years, in the production of semiconductor devices and liquid crystal display devices, pattern miniaturization has been rapidly progressing due to the advancement of lithography technology. As a miniaturization technique, generally, the wavelength of the exposure light source is shortened (the energy is increased).

[0003] Resist materials are required to have lithography characteristics such as sensitivity to these exposure light sources and resolution capable of reproducing patterns with fine dimensions. As a resist material that satisfies such requirements, a chemically amplified resist composition containing a base material component whose solubility in a developer changes due to the action of an acid and an acid generator component that generates an acid upon exposure has been conventionally used.

[0004] For example, Patent Document 1 discloses a positive resist composition using a triphenylsulfonium cation containing a benzene ring having an electron-withdrawing group.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] As resist patterns become smaller, for example, EUV and EB lithography aim to form fine patterns of several tens of nanometers. With this miniaturization of resist patterns, improving specific lithography characteristics such as sensitivity, roughness, and resolution has become a challenge. However, these lithography characteristics are usually in a trade-off relationship; improving one characteristic tends to degrade others. Therefore, resist compositions are required to improve sensitivity, roughness, and resolution without creating any trade-offs. Furthermore, improvements in defects are also required.

[0007] The present invention has been made in view of the above circumstances, and aims to provide a resist composition that can be made highly sensitive, improve lithography characteristics such as roughness reduction, and suppress the occurrence of defects; a method for forming a resist pattern using the resist composition; a compound used in the resist composition; an acid generator; an acid diffusion control agent; and a polymer compound. [Means for solving the problem]

[0008] To solve the above problems, the present invention employs the following configuration. In other words, a first aspect of the present invention is a resist composition that generates acid upon exposure and whose solubility in a developer changes due to the action of the acid, and which contains a compound comprising a cation represented by the following general formula (c0).

[0009] [ka] [In the formula, R 01 and R 02 Each of these independently represents an optionally substituted aryl group, an optionally substituted alkyl group, or an optionally substituted alkenyl group. 01 and R 02 These may bond with each other to form a ring together with the sulfur atom in the formula. 03 represents a substituent. k is an integer between 0 and 3.

[0010] The second aspect of the present invention is a resist pattern forming method including a step of forming a resist film using the resist composition according to the first aspect, a step of exposing the resist film, and a step of developing the exposed resist film to form a resist pattern.

[0011] The third aspect of the present invention is a compound containing a cation represented by the following general formula (c0).

[0012] [Chemical formula] [In the formula, R 01 and R 02 each independently represent an aryl group which may have a substituent, an alkyl group which may have a substituent, or an alkenyl group which may have a substituent. R 01 and R 02 may be bonded to each other to form a ring together with the sulfur atom in the formula. R 03 represents a substituent. k is an integer from 0 to 3.]

[0013] The fourth aspect of the present invention is an acid generator containing a compound represented by the following general formula (b0).

[0014] [Chemical formula] [In the formula, Mc + is a cation represented by the following general formula (c0). Xb - is at least one anion selected from the group consisting of anions represented by the following general formula (b-an-1), general formula (b-an-2), and general formula (b-an-3).]

[0015] [Chemical formula] [In the formula, R 01 and R 02Each of these independently represents an optionally substituted aryl group, an optionally substituted alkyl group, or an optionally substituted alkenyl group. 01 and R 02 These may bond with each other to form a ring together with the sulfur atom in the formula. 03 represents a substituent. k is an integer between 0 and 3. R 101 and R 104 ~R 108 Each of these is independently a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents. 104 and R 105 These may bond to each other to form a ring structure. 102 This is a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom. 101 This is a divalent linking group or single bond containing an oxygen atom. 101 ~V 103 Each of these is independently an alkylene group, a fluorinated alkylene group, or a single bond. However, Y 101 and V 101 It is impossible for them to be single bonds at the same time. 101 and L 102 Each of these is independently either an oxygen atom or a single bond. 103 ~L 105 These are, independently, -CO-, -SO2-, or single bonds.

[0016] A fifth aspect of the present invention is an acid diffusion control agent comprising a compound represented by the following general formula (d0).

[0017] [ka] [In the formula, Mc + Xd is a cation represented by the following general formula (c0). - This is at least one anion selected from the group consisting of anions represented by any of the following general formulas (d1-an-1), (d1-an-2), and (d1-an-3).

[0018] [ka] [In the formula, R 01 and R 02 Each of these independently represents an optionally substituted aryl group, an optionally substituted alkyl group, or an optionally substituted alkenyl group. 01 and R 02 These may bond with each other to form a ring together with the sulfur atom in the formula. 03 represents a substituent. k is an integer between 0 and 3. Rd 1 ~Rd 4 Each of these is independently an optionally substituted cyclic group, an optionally substituted linear alkyl group, or an optionally substituted linear alkenyl group. However, Rd in formula (d1-an-2) 2 In this example, assume that no fluorine atom is bonded to the carbon atom adjacent to the sulfur atom. 1 This is a divalent linking group or a single bond.

[0019] A sixth aspect of the present invention is a polymer compound having a structural unit derived from a compound represented by the following general formula (a0-m).

[0020] [ka] [In the formula, W 0 This represents a polymerizable group-containing group. 0 Rx represents a divalent linking group. - This is an anionic group. + This is a cation represented by the following general formula (c0).

[0021] [ka] [In the formula, R 01 and R 02 Each of these independently represents an optionally substituted aryl group, an optionally substituted alkyl group, or an optionally substituted alkenyl group. 01 and R02 These may bond with each other to form a ring together with the sulfur atom in the formula. 03 represents a substituent. k is an integer between 0 and 3. [Effects of the Invention]

[0022] According to the present invention, it is possible to provide a resist composition that can be made highly sensitive, improve lithography characteristics such as roughness reduction, and suppress the occurrence of defects, a method for forming a resist pattern using the resist composition, a compound used in the resist composition, an acid generator, an acid diffusion control agent, and a polymer compound. [Modes for carrying out the invention]

[0023] In this specification and in the claims, "aliphatic" is defined as a concept relative to aromatic, meaning a group, compound, etc., that does not possess aromaticity. Unless otherwise specified, "alkyl group" includes linear, branched, and cyclic monovalent saturated hydrocarbon groups. The same applies to alkyl groups within alkoxy groups. Unless otherwise specified, the term "alkylene group" includes linear, branched, and cyclic divalent saturated hydrocarbon groups. Examples of "halogen atoms" include fluorine, chlorine, bromine, and iodine atoms. "Constituent unit" refers to the monomer unit (monomer unit) that makes up a polymer compound (resin, polymer, copolymer). When it is stated that a group "may have substituents," this includes both cases where a hydrogen atom (-H) is substituted with a monovalent group and cases where a methylene group (-CH2-) is substituted with a divalent group. "Exposure" is a concept that includes all forms of radiation exposure.

[0024] An "acid-degradable group" is a group that has acid-degradability, meaning that at least some of the bonds in its structure can be cleaved by the action of an acid. Examples of acid-degradable groups whose polarity increases upon the action of an acid include groups that decompose upon the action of an acid to produce polar groups. Examples of polar groups include carboxyl groups, hydroxyl groups, amino groups, and sulfo groups (-SO3H). More specifically, examples of acid-degradable groups include groups in which the aforementioned polar group is protected by an acid-dissociable group (for example, a group in which the hydrogen atom of an OH-containing polar group is protected by an acid-dissociable group).

[0025] The term "acid-dissociable group" refers to both (i) a group that has acid-dissociability, in which the bond between the acid-dissociable group and an adjacent atom can be cleaved by the action of an acid, and (ii) a group in which, after some of the bonds are cleaved by the action of an acid, a decarboxylation reaction occurs, further causing the bond between the acid-dissociable group and an adjacent atom to be cleaved. The acid-dissociable group constituting the acid-degradable group must be less polar than the polar group generated by its dissociation. This means that when the acid-dissociable group dissociates due to the action of acid, a polar group with higher polarity is generated, increasing the polarity. As a result, the overall polarity of component (A1) increases. This increase in polarity relatively changes the solubility in the developer; solubility increases when the developer is an alkaline developer, and decreases when the developer is an organic developer.

[0026] A "base component" is an organic compound that has film-forming ability. Organic compounds used as base components are broadly classified into nonpolymers and polymers. Nonpolymers typically have a molecular weight of 500 or more and less than 4000. Hereinafter, "low molecular weight compound" refers to a nonpolymer with a molecular weight of 500 or more and less than 4000. Polymers typically have a molecular weight of 1000 or more. Hereinafter, "resin," "high molecular weight compound," or "polymer" refers to a polymer with a molecular weight of 1000 or more. The molecular weight of polymers shall be the weight-average molecular weight on a polystyrene basis calculated by GPC (gel permeation chromatography).

[0027] "Induced structural units" refer to structural units formed by the cleavage of multiple bonds between carbon atoms, such as ethylenic double bonds. "Acrylic acid ester" may have a substituent that replaces the hydrogen atom bonded to the α-carbon atom. αx ) is an atom or group other than a hydrogen atom. Also, substituents (R αx Itaconic acid diesters in which the substituent (R) is substituted with substituents containing an ester bond, or substituents (R αx This also includes α-hydroxyacrylic esters in which the α group is substituted with a hydroxyalkyl group or a group that modifies the hydroxyl group thereof. Unless otherwise specified, the α-carbon atom of the acrylic acid ester refers to the carbon atom to which the carbonyl group of acrylic acid is bonded. Hereafter, acrylic acid esters in which the hydrogen atom bonded to the α-carbon atom is replaced by a substituent are sometimes referred to as α-substituted acrylic acid esters.

[0028] The term "derivative" refers to a compound in which the α-position hydrogen atom of the target compound is substituted with another substituent such as an alkyl group or alkyl halide, as well as derivatives thereof. Examples of such derivatives include those in which the hydrogen atom of the hydroxyl group of the target compound (which may have the α-position hydrogen atom substituted with a substituent) is substituted with an organic group; and those in which a substituent other than a hydroxyl group is bonded to the target compound (which may have the α-position hydrogen atom substituted with a substituent). Unless otherwise specified, the α-position refers to the first carbon atom adjacent to the functional group. As substituents that substitute the hydrogen atom at the α-position of hydroxystyrene, R αx Similar examples include the above.

[0029] In this specification and in the claims, depending on the structure represented by the chemical formula, an asymmetric carbon may be present, and enantioisomers or diastereomers may exist. In such cases, a single chemical formula will represent all of these isomers. These isomers may be used individually or as a mixture.

[0030] (Resist composition) The resist composition of this embodiment generates acid upon exposure, and its solubility in the developer changes due to the action of the acid. Such a resist composition contains a compound (hereinafter also referred to as "compound (C)") that includes a cation (C0) represented by the general formula (c0).

[0031] The resist composition of this embodiment may contain, as described later, a base component (A) (hereinafter also referred to as "component (A)") whose solubility in the developer solution changes due to the action of an acid, an acid generating agent component (B) (hereinafter also referred to as "component (B)") that generates acid upon exposure, and an acid diffusion controlling agent component (D) (hereinafter also referred to as "component (D)") that traps the acid generated upon exposure (i.e., controls the diffusion of the acid). Compound (C) may be, for example, component (A), component (B), or component (D).

[0032] <Compounds containing cations (C0) (C)> The resist composition of this embodiment contains a compound (C) comprising a cation (C0) represented by the following general formula (c0).

[0033] [ka] [In the formula, R 01 and R 02 Each of these independently represents an optionally substituted aryl group, an optionally substituted alkyl group, or an optionally substituted alkenyl group. 01 and R 02 These may bond with each other to form a ring together with the sulfur atom in the formula. 03 represents a substituent. k is an integer between 0 and 3.

[0034] Compound (C) may contain an anion moiety that is paired with the cation (C0). If compound (C) is component (A), then, as will be described later, the anionic portion in compound (C) may be, for example, the anionic portion of the constituent unit (a0). If compound (C) is component (B), then, as will be described later, the anionic portion in compound (C) may be an anion represented by, for example, any of the general formulas (b-an-1), (b-an-2), and (b-an-3) described later. If compound (C) is component (D), then, as will be described later, the anionic portion of compound (C) may be an anion represented by, for example, any of the general formulas (d1-an-1), (d1-an-2), and (d1-an-3).

[0035] ≪R 01 and R 02 : Aryl group which may have substituents≫ R 01 and R 02 In this context, the aryl group is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. Examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced by heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of aromatic heterocycles include pyridine rings and thiophene rings. R 01 and R 02 Specifically, examples of aryl groups in this context include a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group); and a group obtained by removing one hydrogen atom from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.).

[0036] R 01 and R 02 Examples of substituents that the aryl group in this compound may have include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, cyano groups, carbonyl groups, nitro groups, sulfonyl groups, amino groups, aryl groups, and groups represented by the following general formulas (ca-r-1) to (ca-r-7).

[0037] • Alkyl substituent Examples of alkyl groups include linear, branched, or cyclic monovalent saturated hydrocarbon groups. The linear alkyl group has 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, and particularly preferably 1 to 5 carbon atoms. The branched alkyl group preferably has 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specifically, examples include isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 1,1-diethylpropyl group, 2,2-dimethylbutyl group, etc., with isopropyl group being preferred. The cyclic monovalent saturated hydrocarbon group may be either a polycyclic or monocyclic group. As a monocyclic aliphatic hydrocarbon group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferred. The monocycloalkane is preferably one having 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. As the polycyclic aliphatic hydrocarbon group, a group obtained by removing one hydrogen atom from a polycycloalkane is preferred, and as the polycycloalkane, those having 7 to 12 carbon atoms are preferred, specifically adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 Examples include decane and tetracyclododecane.

[0038] Alkyl groups may be partially substituted with halogen atoms or heteroatom-containing groups. For example, some of the hydrogen atoms constituting an alkyl group may be substituted with halogen atoms or heteroatom-containing groups. Also, some of the carbon atoms constituting an alkyl group (such as a methylene group) may be substituted with heteroatom-containing groups. Examples of heteroatoms used here include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of heteroatom-containing groups include (-O-), -C(=O)-O-, -OC(=O)-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -S-, -S(=O)2-, -S(=O)2-O-, etc.

[0039] • Alkoxy group as a substituent As for the alkoxy group, an alkoxy group having 1 to 5 carbon atoms is preferred, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group are more preferred, and a methoxy group and an ethoxy group are even more preferred.

[0040] • Halogen atoms as substituents As the halogen atom, iodine or fluorine atoms are preferred.

[0041] • Alkyl halogenated substituents The alkyl halide may be a group in which some or all of the hydrogen atoms of the alkyl group described above are substituted with halogen atoms. Fluorine atoms are particularly preferred as the halogen atoms.

[0042] • Aryl group as a substituent As an aryl group as a substituent, R 01 and R 02 The aryl groups mentioned above are examples of aryl groups in this context.

[0043] [ka] [In the formula, R' 201Each of these is independently a hydrogen atom, an optionally substituted cyclic group, an optionally substituted linear alkyl group, or an optionally substituted linear alkenyl group.

[0044] Cyclic groups that may have substituents: The cyclic group is preferably a cyclic hydrocarbon group, which may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity. Furthermore, the aliphatic hydrocarbon group may be saturated or unsaturated, but is usually preferred to be saturated.

[0045] R' 201 The aromatic hydrocarbon group in this context is a hydrocarbon group having an aromatic ring. The number of carbon atoms in the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, this number of carbon atoms does not include the number of carbon atoms in substituents. R' 201 Specific examples of aromatic rings in aromatic hydrocarbon groups include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic heterocycles in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, nitrogen atoms, etc. R' 201 Specific examples of aromatic hydrocarbon groups in this context include groups obtained by removing one hydrogen atom from the aromatic ring (aryl groups: e.g., phenyl group, naphthyl group, etc.), and groups in which one of the hydrogen atoms of the aromatic ring is replaced by an alkylene group (e.g., arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms in the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0046] R' 201 In this context, cyclic aliphatic hydrocarbon groups include aliphatic hydrocarbon groups that contain a ring in their structure. Examples of aliphatic hydrocarbon groups containing a ring in this structure include alicyclic hydrocarbon groups (groups from which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. A preferred monocyclic alicyclic hydrocarbon group is a group obtained by removing one or more hydrogen atoms from a monocycloalkane. The monocycloalkane is preferably one having 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. A preferred polycyclic alicyclic hydrocarbon group is a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 30 carbon atoms. Among these, adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 Polycycloalkanes having a cross-linked ring polycyclic skeleton such as decane and tetracyclododecane; polycycloalkanes having a fused ring polycyclic skeleton such as a cyclic group having a steroid skeleton are more preferred.

[0047] Among them, R' 201 The cyclic aliphatic hydrocarbon group in is preferably a monocycloalkane or polycycloalkane from which one or more hydrogen atoms have been removed, more preferably a polycycloalkane from which one hydrogen atom has been removed, with adamantyl and norbornyl groups being particularly preferred, and the adamantyl group being the most preferred.

[0048] The linear or branched aliphatic hydrocarbon group, which may be bonded to the alicyclic hydrocarbon group, preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms. As for the linear aliphatic hydrocarbon group, linear alkylene groups are preferred, specifically the methylene group [-CH2-], ethylene group [-(CH2)2-], trimethylene group [-(CH2)3-], tetramethylene group [-(CH2)4-], pentamethylene group [-(CH2)5-], etc. Preferred branched aliphatic hydrocarbon groups include branched alkylene groups, specifically alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkylalkylene groups such as alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. In the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0049] Also, R' 201 The cyclic hydrocarbon group in this formula may contain heteroatoms, such as heterocycles. Specifically, examples include lactone-containing cyclic groups represented by the following general formulas (a2-r-1) to (a2-r-7), -SO2--containing cyclic groups represented by the following general formulas (b5-r-1) to (b5-r-4), and other heterocyclic groups represented by the following chemical formulas (r-hr-1) to (r-hr-16).

[0050] The lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-7) below will be explained.

[0051] [ka] [In the formula, Ra' 21 Each of these is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR'', -OC(=O)R'', a hydroxyalkyl group, or a cyano group; R'' is a hydrogen atom, an alkyl group, or a lactone-containing cyclic group; A'' is an alkylene group having 1 to 5 carbon atoms, which may contain an oxygen atom (-O-) or a sulfur atom (-S-), an oxygen atom, or a sulfur atom, where n' is an integer from 0 to 2, and m' is 0 or 1. * indicates a bond (the same applies below).

[0052] In the general formulas (a2-r-1) to (a2-r-7), Ra' 21 The alkyl group in is preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group is preferably linear or branched. Specifically, examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, etc. Among these, the methyl group or ethyl group is preferred, and the methyl group is particularly preferred. Ra' 21 The alkoxy group in is preferably an alkoxy group having 1 to 6 carbon atoms. The alkoxy group is preferably linear or branched. Specifically, the Ra' 21 Examples of alkyl groups in this context include groups formed by linking an alkyl group with an oxygen atom (-O-). Ra' 21 In this mixture, a fluorine atom is preferred as the halogen atom. Ra' 21 The halogenated alkyl group in is the Ra' 21 Examples include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with the halogen atoms. Fluorinated alkyl groups are preferred as the halogenated alkyl group, and perfluoroalkyl groups are particularly preferred.

[0053] Ra'21 In -COOR” and -OC(=O)R”, R” is each a hydrogen atom, an alkyl group, or a lactone-containing cyclic group. The alkyl group for R” may be linear, branched, or cyclic, and preferably has 1 to 15 carbon atoms. When R” is a linear or branched alkyl group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably a methyl group or an ethyl group. When R” is a cyclic alkyl group, it preferably has 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, a group obtained by removing one or more hydrogen atoms from a monocycloalkane which may or may not be substituted with a fluorine atom or a fluorinated alkyl group; a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as bicycloalkane, tricycloalkane, tetracycloalkane, etc. can be exemplified. More specifically, a group obtained by removing one or more hydrogen atoms from a monocycloalkane such as cyclopentane, cyclohexane, etc.; adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 decane, a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as tetracyclododecane, etc. can be mentioned. Examples of the lactone-containing cyclic group for R” include the same groups as those represented by the general formulas (a2-r-1) to (a2-r-7) respectively. Ra’ 21 The hydroxyalkyl group for Ra’ preferably has 1 to 6 carbon atoms, and specifically, a group in which at least one hydrogen atom of the alkyl group in Ra’ 21 is substituted with a hydroxyl group can be mentioned.

[0054] Ra’ 21 Among the above, Ra’ is preferably each independently a hydrogen atom or a cyano group.

[0055] In the general formulas (a2-r-2), (a2-r-3), and (a2-r-5) above, the alkylene group having 1 to 5 carbon atoms in A'' is preferably a linear or branched alkylene group, such as a methylene group, ethylene group, n-propylene group, isopropylene group, etc. If the alkylene group contains an oxygen atom or a sulfur atom, specific examples include a group in which -O- or -S- is interposed at the end or between carbon atoms of the alkylene group, such as -O-CH2-, -CH2-O-CH2-, -S-CH2-, -CH2-S-CH2-, etc. As A'', an alkylene group having 1 to 5 carbon atoms or -O- is preferred, an alkylene group having 1 to 5 carbon atoms is more preferred, and a methylene group is most preferred.

[0056] The following are specific examples of the groups represented by the general formulas (a²-r-1) to (a²-r-7).

[0057] [ka]

[0058] [ka]

[0059] The following describes the -SO2-containing cyclic groups represented by the general formulas (b5-r-1) to (b5-r-4).

[0060] [ka] [In the formula, Rb' 51 Each of the following is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR'', -OC(=O)R'', a hydroxyalkyl group, or a cyano group; R'' is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, or a -SO2--containing cyclic group; B'' is an alkylene group having 1 to 5 carbon atoms, which may contain an oxygen atom or a sulfur atom, an oxygen atom, or a sulfur atom, and n' is an integer from 0 to 2. * indicates a bond.

[0061] In the above general formulas (b5-r-1) to (b5-r-2), B'' is an alkylene group having 1 to 5 carbon atoms, which may contain an oxygen atom or a sulfur atom, or an oxygen atom or a sulfur atom. B'' is preferably an alkylene group or -O- having 1 to 5 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and even more preferably a methylene group.

[0062] In the above general formulas (b5-r-1) to (b5-r-4), Rb' 51 Each of these is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR'', -OC(=O)R'', a hydroxyalkyl group, or a cyano group, and among these, each is preferably independently a hydrogen atom or a cyano group.

[0063] Specific examples of the groups represented by the general formulas (b5-r-1) to (b5-r-4) are given below. In the formulas, "Ac" indicates an acetyl group.

[0064] [ka]

[0065] [ka]

[0066] [ka]

[0067] The heterocyclic groups represented by chemical formulas (r-hr-1) to (r-hr-16) are as follows:

[0068] [ka]

[0069] R'201 Examples of substituents on the cyclic group include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, and nitro groups. As alkyl groups used as substituents, alkyl groups having 1 to 5 carbon atoms are preferred, with methyl, ethyl, propyl, n-butyl, and tert-butyl groups being the most preferred. As the substituent, an alkoxy group having 1 to 5 carbon atoms is preferred, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group are more preferred, and a methoxy group and an ethoxy group are most preferred. As the halogen atom used as a substituent, a fluorine atom is preferred. Examples of alkyl halides used as substituents include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, and tert-butyl groups, in which some or all of the hydrogen atoms are substituted with the halogen atoms. A carbonyl group as a substituent is a group that substitutes for a methylene group (-CH2-) that constitutes a cyclic hydrocarbon group.

[0070] Chain-like alkyl groups that may have substituents: R' 201 The chain-like alkyl group may be either linear or branched. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specifically, examples include 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, and 4-methylpentyl group.

[0071] A chain alkenyl group which may have a substituent: R’ 201 The chain alkenyl group of 201 may be either linear or branched, preferably having 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, even more preferably 2 to 4 carbon atoms, and particularly preferably 3 carbon atoms. Examples of the linear alkenyl group include a vinyl group, a propenyl group (allyl group), a butenyl group, etc. Examples of the branched alkenyl group include a 1-methylvinyl group, a 2-methylvinyl group, a 1-methylpropenyl group, a 2-methylpropenyl group, etc. Among the above, the chain alkenyl group is preferably a linear alkenyl group, more preferably a vinyl group or a propenyl group, and particularly preferably a vinyl group.

[0072] R’ 201 Examples of the substituent in the chain alkyl group or alkenyl group of 201 include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and the cyclic group in the above R’ 201 etc.

[0073] R’ 201 The cyclic group which may have a substituent, the chain alkyl group which may have a substituent, or the chain alkenyl group which may have a substituent, in addition to those described above, as the cyclic group which may have a substituent or the chain alkyl group which may have a substituent, also includes those similar to the acid dissociable group represented by the following formula (a1-r-2).

[0074] Among them, R’ 201 is preferably a cyclic group which may have a substituent, and more preferably a cyclic hydrocarbon group which may have a substituent. More specifically, for example, a phenyl group, a naphthyl group, a group obtained by removing one or more hydrogen atoms from a polycycloalkane; a lactone-containing cyclic group represented by the general formulas (a2-r-1) to (a2-r-7) respectively; a -SO2-containing cyclic group represented by the general formulas (b5-r-1) to (b5-r-4) respectively, etc. are preferable.

[0075] R 01 and R 02 The aryl group in this compound is preferably an aromatic hydrocarbon ring, more preferably benzene or naphthalene, and even more preferably benzene.

[0076] R 01 and R 02 The substituents that the aryl group in this compound may have are preferably alkoxy groups, halogen atoms, or alkyl halides; more preferably methoxy groups, iodine atoms, fluorine atoms, or trifluorimethyl groups; even more preferably methoxy groups or iodine atoms; and it is particularly preferable that the methoxy group and iodine atom are bonded to the same aryl group.

[0077] ≪R 01 and R 02 :alkyl groups that may have substituents≫ R 01 and R 02 Examples of alkyl groups in this context include linear, branched, or cyclic monovalent saturated hydrocarbon groups. The linear alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and even more preferably 1 to 10 carbon atoms. The branched alkyl group preferably has 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specifically, examples include isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 1,1-diethylpropyl group, 2,2-dimethylbutyl group, etc., with isopropyl group being preferred. The cyclic monovalent saturated hydrocarbon group may be either a polycyclic or monocyclic group. As a monocyclic aliphatic hydrocarbon group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferred. The monocycloalkane is preferably one having 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. As the polycyclic aliphatic hydrocarbon group, a group obtained by removing one hydrogen atom from a polycycloalkane is preferred, and as the polycycloalkane, those having 7 to 12 carbon atoms are preferred, specifically adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 Examples include decane and tetracyclododecane.

[0078] R 01 and R 02 Some or all of the hydrogen atoms in the alkyl group may be substituted with a monovalent group containing a heteroatom. Examples of such monovalent groups include halogen atoms, nitro groups, amino groups, hydroxyl groups, carboxyl groups, nitrile groups, thiol groups, and the like. 2 If the group is a chain-like hydrocarbon group, the methylene group of the chain-like hydrocarbon group may be substituted with a divalent group containing a heteroatom. Examples of such divalent groups include carbonyl groups, -O-, -C(=O)-O-, -OC(=O)-, amide groups, and imino groups.

[0079] ≪R 01 and R 02 :Alkenyl group which may have substituents≫ R 01 and R 02 The alkenyl group in this compound may be linear or branched, and preferably has 2 to 30 carbon atoms, more preferably 2 to 20, and even more preferably 2 to 10.

[0080] R 01 and R 02 Examples of substituents on the alkenyl group include alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, nitro groups, and amino groups.

[0081] ≪R 03 ≫ In the above general formula (c0), R 03Examples of substituents include alkyl groups, alkoxy groups, acyl groups, alkyl halides, hydroxyl groups, amino groups, cyano groups, halogen atoms, and nitro groups. The alkyl groups, alkoxy groups, acyl groups, and alkyl halides used as substituents may be linear or branched. Examples of alkyl groups, alkoxy groups, acyl groups, and alkyl halides include those having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 or 2 carbon atoms.

[0082] In the general formula (c0) above, k is preferably an integer between 0 and 2, more preferably 0 or 1, and even more preferably 0.

[0083] In the above general formula (c0), R 01 and R 02 When these atoms bond to each other and form a ring with the sulfur atom in the formula, heteroatoms such as sulfur atoms, oxygen atoms, nitrogen atoms, carbonyl groups, -SO-, -SO2-, -SO3-, -COO-, -CONH- or -N(R) N )-(the R N is an alkyl group having 1 to 5 carbon atoms. ) may be bonded via functional groups such as ). The formed ring preferably has 3 to 10 members, and particularly preferably 5 to 7 members, including the sulfur atom in its ring skeleton. Specific examples of the formed ring include, for example, a thiophene ring, a thiazole ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthlene ring, a phenoxatiyne ring, a tetrahydrothiophenium ring, and a tetrahydrothiopyranium ring.

[0084] Specific examples of cations (C0) are shown below, but are not limited to these.

[0085] [ka]

[0086] [ka]

[0087] [ka]

[0088] [ka]

[0089] [ka]

[0090] [ka]

[0091] [ka]

[0092] [ka]

[0093] <Base material component (A)> In the resist composition of this embodiment, it is preferable to use a component (A) that contains a resin component (A1) (hereinafter also referred to as "component (A1)") whose solubility in the developer solution changes due to the action of an acid. By using component (A1), the polarity of the substrate component changes before and after exposure, so that good development contrast can be obtained not only in the alkaline development process but also in the solvent development process. (A) Component (A1) may be used in combination with other high-molecular-weight compounds and / or low-molecular-weight compounds.

[0094] In the resist composition of this embodiment, component (A) may be used alone or in combination of two or more types.

[0095] (A1) About the ingredients Component (A1) is a resin component whose solubility in the developer changes due to the action of acid. (A1) Component is preferably one that has a constituent unit (a1) containing an acid-degradable group whose polarity increases due to the action of an acid. Component (A1) may have other constituent units in addition to the constituent unit (a1) as needed.

[0096] ≪Component Unit (a1)≫ The constituent unit (a1) is a constituent unit that contains an acid-degradable group whose polarity increases upon the action of an acid.

[0097] Examples of acid-dissociable groups include those previously proposed as acid-dissociable groups for base resins used in chemically amplified resist compositions. Specifically, the following types of acid-dissociable groups have been proposed for base resins used in chemically amplified resist compositions: "acetal-type acid-dissociable groups," "tertiary alkyl ester-type acid-dissociable groups," "tertiary alkyloxycarbonyl acid-dissociable groups," and "secondary alkyloxycarbonyl acid-dissociable groups."

[0098] Acetal type acid dissociable group: Examples of acid-dissociable groups that protect a carboxyl group or a hydroxyl group among the aforementioned polar groups include the acid-dissociable group represented by the following general formula (a1-r-1) (hereinafter sometimes referred to as an "acetal-type acid-dissociable group").

[0099] [ka] [In the formula, Ra' 1 , Ra' 2 is a hydrogen atom or an alkyl group. 3 Ra' is a hydrocarbon group. 3 Ra' 1 , Ra' 2 It may combine with any of the following to form a ring.

[0100] In formula (a1-r-1), Ra' 1 and Ra' 2 Preferably, at least one of them is a hydrogen atom, and more preferably, both are hydrogen atoms. Ra' 1 Or Ra' 2 If the alkyl group is an alkyl group, the alkyl group can be the same as those listed in the description of the α-substituted acrylic acid ester above as substituents that may be bonded to the carbon atom at the α position, and an alkyl group having 1 to 5 carbon atoms is preferred. Specifically, linear or branched alkyl groups are preferred. More specifically, examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc., with methyl group or ethyl group being more preferred, and methyl group being particularly preferred.

[0101] In formula (a1-r-1), Ra' 3 Examples of hydrocarbon groups include linear or branched alkyl groups, or cyclic hydrocarbon groups. The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms. Specifically, examples include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, etc. Among these, methyl group, ethyl group, or n-butyl group is preferred, and methyl group or ethyl group is more preferred.

[0102] The branched alkyl group preferably has 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specifically, examples include isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 1,1-diethylpropyl group, 2,2-dimethylbutyl group, etc., with isopropyl group being preferred.

[0103] Ra' 3When the hydrocarbon group is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group. As a monocyclic aliphatic hydrocarbon group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferred. The monocycloalkane is preferably one having 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. As the polycyclic aliphatic hydrocarbon group, a group obtained by removing one hydrogen atom from a polycycloalkane is preferred, and as the polycycloalkane, those having 7 to 12 carbon atoms are preferred, specifically adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 Examples include decane and tetracyclododecane.

[0104] Ra' 3 When the cyclic hydrocarbon group becomes an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. Examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced by heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of aromatic heterocycles include pyridine rings and thiophene rings. Ra' 3Specific examples of aromatic hydrocarbon groups in this context include: a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group); a group obtained by removing one hydrogen atom from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and a group in which one of the hydrogen atoms of the aromatic hydrocarbon ring or aromatic heterocycle is substituted with an alkylene group (e.g., arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms in the alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocycle is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0105] Ra' 3 The cyclic hydrocarbon group in may have substituents. Examples of substituents include -R P1 ,-R P2 -OR P1 ,-R P2 -CO-R P1 ,-R P2 -CO-OR P1 ,-R P2 -O-CO-R P1 ,-R P2 -OH, -R P2 -CN or -R P2 -COOH (These substituents are collectively referred to as "Ra" below) x5 It is also called "[...]." Examples include [...]. Here, R P1 This is a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms, a monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms. Also, R P2 This refers to a single bond, a divalent chain saturated hydrocarbon group having 1 to 10 carbon atoms, a divalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms. However, R P1 and R P2Some or all of the hydrogen atoms in the chain-like saturated hydrocarbon group, aliphatic cyclic saturated hydrocarbon group, and aromatic hydrocarbon group may be substituted with fluorine atoms. The aliphatic cyclic hydrocarbon group may have one or more of the substituents individually, or it may have one or more of each of the substituents. Examples of monovalent, chain-like saturated hydrocarbon groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl groups. Examples of monovalent aliphatic cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms include monocyclic aliphatic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and cyclododecyl groups; and polycyclic aliphatic saturated hydrocarbon groups such as bicyclo[2.2.2]octanyl, tricyclo[5.2.1.02,6]decanyl, tricyclo[3.3.1.13,7]decanyl, tetracyclo[6.2.1.13,6.02,7]dodecanyl, and adamantyl groups. Examples of monovalent aromatic hydrocarbon groups with 6 to 30 carbon atoms include groups obtained by removing one hydrogen atom from an aromatic hydrocarbon ring, such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene.

[0106] Ra' 3 However, Ra' 1 , Ra' 2 When the cyclic group is bonded to any of the above to form a ring, the cyclic group is preferably a 4- to 7-membered ring, and more preferably a 4- to 6-membered ring. Specific examples of the cyclic group include a tetrahydropyranyl group and a tetrahydrofuranyl group.

[0107] Tertiary alkyl ester type acid-dissociating group: Among the polar groups mentioned above, an example of an acid-dissociating group that protects a carboxyl group is the acid-dissociating group represented by the following general formula (a1-r-2). Furthermore, among the acid-dissociable groups represented by the following formula (a1-r-2), those composed of alkyl groups may, for convenience, be referred to below as "tertiary alkyl ester type acid-dissociable groups."

[0108] [ka] [In the formula, Ra' 4 ~Ra' 6 Each of these is a hydrocarbon group, Ra' 5 , Ra' 6 They may be joined to each other to form a ring.

[0109] Ra' 4 Examples of hydrocarbon groups include linear or branched alkyl groups, linear or cyclic alkenyl groups, or cyclic hydrocarbon groups. Ra' 4 In the above, linear or branched alkyl groups, cyclic hydrocarbon groups (monocyclic aliphatic hydrocarbon groups, polycyclic aliphatic hydrocarbon groups, aromatic hydrocarbon groups) are defined as Ra' 3 Similar examples include the above. Ra' 4 The linear or cyclic alkenyl group in this is preferably an alkenyl group having 2 to 10 carbon atoms. Ra' 5 , Ra' 6 The hydrocarbon group is the aforementioned Ra' 3 Similar examples include the above.

[0110] Ra' 5 and Ra' 6 When these groups bond to each other to form a ring, the following groups are preferred: the group represented by the general formula (a1-r2-1), the group represented by the general formula (a1-r2-2), and the group represented by the general formula (a1-r2-3). Meanwhile, Ra' 4 ~Ra' 6 When these are independent hydrocarbon groups that are not bonded to each other, the groups represented by the following general formula (a1-r2-4) are preferred.

[0111] [ka] [In formula (a1-r2-1), Ra' 10 This represents a linear or branched alkyl group having 1 to 12 carbon atoms, which may be partially substituted with halogen atoms or heteroatom-containing groups. 11 Ra' 10 This indicates a group that forms an aliphatic cyclic group with a bonded carbon atom. In formula (a1-r2-2), Ya is a carbon atom. Xa is a group that forms a cyclic hydrocarbon group with Ya. Some or all of the hydrogen atoms in this cyclic hydrocarbon group may be substituted. 101 ~Ra 103 Each of these is independently a hydrogen atom, a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms, or a monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms. Some or all of the hydrogen atoms in these linear saturated hydrocarbon groups and aliphatic cyclic saturated hydrocarbon groups may be substituted. 101 ~Ra 103 Two or more of these may be bonded to each other to form a cyclic structure. In formula (a1-r2-3), Yaa is a carbon atom. Xaa is a group that forms an aliphatic cyclic group together with Yaa. Ra 104 is an aromatic hydrocarbon group which may have substituents. In formula (a1-r2-4), Ra' 12 and Ra' 13 Each of these is independently a monovalent, chain-like saturated hydrocarbon group having 1 to 10 carbon atoms. Some or all of the hydrogen atoms in this chain-like saturated hydrocarbon group may be substituted. 14 is a hydrocarbon group that may have substituents. * indicates a bond (the same applies hereafter).

[0112] In the above equation (a1-r2-1), Ra' 10 This is a linear or branched alkyl group having 1 to 12 carbon atoms, which may be partially substituted with halogen atoms or heteroatom-containing groups.

[0113] Ra' 10In this context, the linear alkyl group has 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, and particularly preferably 1 to 5 carbon atoms. Ra' 10 In this, the branched alkyl group is the Ra' 3 Similar examples include the above.

[0114] Ra' 10 In this case, the alkyl group may be partially substituted with a halogen atom or a heteroatom-containing group. For example, some of the hydrogen atoms constituting the alkyl group may be substituted with a halogen atom or a heteroatom-containing group. Also, some of the carbon atoms constituting the alkyl group (such as a methylene group) may be substituted with a heteroatom-containing group. Examples of heteroatoms used here include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of heteroatom-containing groups include (-O-), -C(=O)-O-, -OC(=O)-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -S-, -S(=O)2-, -S(=O)2-O-, etc.

[0115] In formula (a1-r2-1), Ra' 11 (Ra' 10 The aliphatic cyclic group formed with the bonded carbon atom is Ra' in formula (a1-r-1). 3 The aliphatic hydrocarbon groups (alicyclic hydrocarbon groups) listed above, which are monocyclic or polycyclic groups, are preferred. Among these, monocyclic alicyclic hydrocarbon groups are preferred, and specifically, cyclopentyl groups and cyclohexyl groups are more preferred.

[0116] In formula (a1-r2-2), the cyclic hydrocarbon group formed by Xa together with Ya is Ra' in formula (a1-r-1). 3 Examples include groups obtained by further removing one or more hydrogen atoms from a cyclic monovalent hydrocarbon group (aliphatic hydrocarbon group). The cyclic hydrocarbon group formed by Xa and Ya may have substituents. Examples of such substituents include the above-mentioned Ra' 3Examples include substituents similar to those that may be present on the cyclic hydrocarbon group in the above. In formula (a1-r2-2), Ra 101 ~Ra 103 Examples of monovalent chain-like saturated hydrocarbon groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl groups. Ra 101 ~Ra 103 Examples of monovalent aliphatic cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms include monocyclic aliphatic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and cyclododecyl groups; bicyclo[2.2.2]octanyl, tricyclo[5.2.1.0 2,6 ]decanyl group, tricyclo[3.3.1.1 3,7 ]decanyl group, tetracyclo[6.2.1.1 3,6 .0 2,7 Examples include polycyclic aliphatic saturated hydrocarbon groups such as dodecanyl groups and adamantyl groups. Ra 101 ~Ra 103 Of these, from the viewpoint of ease of synthesis, hydrogen atoms and monovalent chain saturated hydrocarbon groups having 1 to 10 carbon atoms are preferred, and among these, hydrogen atoms, methyl groups, and ethyl groups are more preferred, with hydrogen atoms being particularly preferred.

[0117] The above Ra 101 ~Ra 103 Examples of substituents on a chain-like saturated hydrocarbon group or an aliphatic cyclic saturated hydrocarbon group represented by the above-mentioned Ra x5 Similar bases can be cited.

[0118] Ra 101 ~Ra 103Groups containing a carbon-carbon double bond formed by two or more of these groups bonding to each other to form a cyclic structure include, for example, cyclopentenyl group, cyclohexenyl group, methylcyclopentenyl group, methylcyclohexenyl group, cyclopentylideneethenyl group, and cyclohexyllideneethenyl group. Among these, cyclopentenyl group, cyclohexenyl group, and cyclopentylideneethenyl group are preferred from the viewpoint of ease of synthesis.

[0119] In formula (a1-r2-3), the aliphatic cyclic group formed by Xaa together with Yaa is Ra' in formula (a1-r-1). 3 The aliphatic hydrocarbon groups listed above, which are monocyclic or polycyclic groups, are preferred. In formula (a1-r2-3), Ra 104 Aromatic hydrocarbon groups in this context include groups obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring with 5 to 30 carbon atoms. Among them, Ra 104 The group is preferably an aromatic hydrocarbon ring having 6 to 15 carbon atoms with one or more hydrogen atoms removed; more preferably a group from benzene, naphthalene, anthracene, or phenanthrene with one or more hydrogen atoms removed; even more preferably a group from benzene, naphthalene, or anthracene with one or more hydrogen atoms removed; particularly preferably a group from benzene or naphthalene with one or more hydrogen atoms removed; and most preferably a group from benzene with one or more hydrogen atoms removed.

[0120] Ra in equation (a1-r2-3) 104 Examples of substituents that may be present include methyl groups, ethyl groups, propyl groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups (such as methoxy groups, ethoxy groups, propoxy groups, butoxy groups, etc.), and alkyloxycarbonyl groups.

[0121] In formula (a1-r2-4), Ra' 12 and Ra' 13 Each of these is independently a monovalent, chain-like saturated hydrocarbon group having 1 to 10 carbon atoms. 12 and Ra' 13In this context, the monovalent chain-like saturated hydrocarbon group having 1 to 10 carbon atoms is the above-mentioned Ra 101 ~Ra 103 Examples include monovalent chain-like saturated hydrocarbon groups having 1 to 10 carbon atoms. Some or all of the hydrogen atoms in this chain-like saturated hydrocarbon group may be substituted. Ra' 12 and Ra' 13 Among these, alkyl groups having 1 to 5 carbon atoms are preferred, alkyl groups having 1 to 5 carbon atoms are more preferred, methyl groups and ethyl groups are even more preferred, and methyl groups are particularly preferred. The above Ra' 12 and Ra' 13 When a chain-like saturated hydrocarbon group represented by is substituted, the substituent may be, for example, the above-mentioned Ra x5 Similar bases can be cited.

[0122] In formula (a1-r2-4), Ra' 14 Ra' is a hydrocarbon group that may have substituents. 14 Examples of hydrocarbon groups in this context include linear or branched alkyl groups, or cyclic hydrocarbon groups.

[0123] Ra' 14 The linear alkyl group in this compound preferably has 1 to 5 carbon atoms, more preferably 1 to 4, and even more preferably 1 or 2. Specifically, examples include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, etc. Among these, methyl group, ethyl group, or n-butyl group is preferred, and methyl group or ethyl group is more preferred.

[0124] Ra' 14 The branched alkyl group in this compound preferably has 3 to 10 carbon atoms, and more preferably 3 to 5. Specifically, examples include isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 1,1-diethylpropyl group, 2,2-dimethylbutyl group, etc., with isopropyl group being preferred.

[0125] Ra'14 When the hydrocarbon group is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group. As a monocyclic aliphatic hydrocarbon group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferred. The monocycloalkane is preferably one having 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. As the polycyclic aliphatic hydrocarbon group, a group obtained by removing one hydrogen atom from a polycycloalkane is preferred, and as the polycycloalkane, those having 7 to 12 carbon atoms are preferred, specifically adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 Examples include decane and tetracyclododecane.

[0126] Ra' 14 As for aromatic hydrocarbon groups in this context, Ra 104 Examples include those similar to aromatic hydrocarbon groups in [the text]. Among them, Ra' 14 The group is preferably an aromatic hydrocarbon ring having 6 to 15 carbon atoms with one or more hydrogen atoms removed; more preferably a group from benzene, naphthalene, anthracene, or phenanthrene with one or more hydrogen atoms removed; even more preferably a group from benzene, naphthalene, or anthracene with one or more hydrogen atoms removed; particularly preferably a group from naphthalene or anthracene with one or more hydrogen atoms removed; and most preferably a group from naphthalene with one or more hydrogen atoms removed. Ra' 14 A substituent that may be present is Ra 104 Examples of substituents that may be present include those similar to those that the molecule may have.

[0127] Ra' in equation (a1-r2-4) 14 If is a naphthyl group, the position where it bonds with the tertiary carbon atom in formula (a1-r2-4) may be either position 1 or position 2 of the naphthyl group. Ra' in equation (a1-r2-4) 14If is an anthyl group, the position where it bonds with the tertiary carbon atom in formula (a1-r2-4) may be position 1, 2, or 9 of the anthyl group.

[0128] Specific examples of the group represented by the above formula (a1-r2-1) are given below.

[0129] [ka]

[0130] [ka]

[0131] [ka]

[0132] Specific examples of the group represented by the above formula (a1-r2-2) are given below.

[0133] [ka]

[0134] [ka]

[0135] [ka]

[0136] Specific examples of the group represented by the above formula (a1-r2-3) are given below.

[0137] [ka]

[0138] Specific examples of the group represented by the above formula (a1-r2-4) are given below.

[0139] [ka]

[0140] Tertiary alkyloxycarbonyl acid dissociable group: Among the aforementioned polar groups, an example of an acid-dissociating group that protects a hydroxyl group is the acid-dissociating group represented by the following general formula (a1-r-3) (hereinafter sometimes referred to as a "tertiary alkyloxycarbonyl acid dissociating group" for convenience).

[0141] [ka] [In the formula, Ra' 7 ~Ra' 9 These are each alkyl groups.

[0142] In formula (a1-r-3), Ra' 7 ~Ra' 9 Each of these is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. Furthermore, the total number of carbon atoms in each alkyl group is preferably 3 to 7, more preferably 3 to 5, and most preferably 3 to 4.

[0143] Secondary alkyl ester type acid-dissociating group: Among the polar groups mentioned above, an example of an acid-dissociating group that protects a carboxyl group is the acid-dissociating group represented by the following general formula (a1-r-4).

[0144] [ka] [In the formula, Ra' 10 Ra' is a hydrocarbon group. 11a and Ra' 11b Each of these is independently a hydrogen atom, a halogen atom, or an alkyl group. 12is a hydrogen atom or a hydrocarbon group. 10 and Ra' 11a Or Ra' 11b These elements may be joined together to form a ring. 11a Or Ra' 11b And, Ra' 12 These elements may be joined together to form a ring.

[0145] In the formula, Ra' 10 and Ra' 12 The hydrocarbon group in this is the Ra' 3 Similar examples include the above. In the formula, Ra' 11a and Ra' 11b The alkyl group in is the aforementioned Ra' 1 Examples include alkyl groups similar to those in the above. In the formula, Ra' 10 and Ra' 12 The hydrocarbon group in, and Ra' 11a and Ra' 11b The alkyl group in may have substituents. For example, the above-mentioned Ra is an example of such substituent. x5 These are some examples.

[0146] Ra' 10 and Ra' 11a Or Ra' 11b These elements may be bonded to each other to form a ring. This ring may be polycyclic or monocyclic, and may be an alicyclic or aromatic ring. The alicyclic and aromatic rings may also contain heteroatoms.

[0147] Ra' 10 and Ra' 11a Or Ra' 11b The rings formed by the bonding of these elements are preferably monocycloalkenes, rings in which some of the carbon atoms of a monocycloalkene are substituted with heteroatoms (oxygen atoms, sulfur atoms, etc.), monocycloalkadienes, cycloalkenes having 3 to 6 carbon atoms, and cyclopentene or cyclohexene.

[0148] Ra' 10 and Ra' 11a Or Ra' 11b The ring formed by the bonding of these elements may be a fused ring. Specific examples of such fused rings include indane.

[0149] Ra' 10 and Ra' 11a Or Ra' 11b The ring formed by the bonding of these elements may have substituents. For example, the above-mentioned Ra x5 These are some examples.

[0150] Ra' 11a Or Ra' 11b And, Ra' 12 These elements may be bonded together to form a ring, and the ring may be Ra' 10 and Ra' 11a Or Ra' 11b Examples include rings formed by the bonding of these elements together.

[0151] Specific examples of the group represented by the above formula (a1-r-4) are given below.

[0152] [ka]

[0153] Examples of constituent units (a1) include constituent units derived from acrylic acid esters in which the hydrogen atom bonded to the α-carbon atom may be substituted with a substituent, constituent units derived from acrylamide, constituent units derived from hydroxystyrene or hydroxystyrene derivatives in which at least a portion of the hydrogen atoms in the hydroxyl group of a constituent unit are protected by a substituent containing the acid-degradable group, and constituent units derived from vinyl benzoic acid or vinyl benzoic acid derivatives in which at least a portion of the hydrogen atoms in the -C(=O)-OH group are protected by a substituent containing the acid-degradable group.

[0154] As for the constituent unit (a1), among the above, a constituent unit derived from an acrylic acid ester in which the hydrogen atom bonded to the α-carbon atom may be substituted with a substituent is preferred. A preferred example of such a constituent unit (a1) is a constituent unit represented by the following general formulas (a1-1), (a1-2), or (a1-3).

[0155] [ka] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halogen having 1 to 5 carbon atoms. Va 1 n is a divalent hydrocarbon group which may have an ether bond. a1 is an integer between 0 and 2. 1 This is an acid-dissociable group represented by the general formula (a1-r-1), (a1-r-2), or (a1-r-4) above. 1 is n a2 It is a +1 valent hydrocarbon group. a2 is an integer between 1 and 3. 2 This is an acid-dissociable group represented by the general formula (a1-r-1) or (a1-r-3) above. 001 It is a single bond or a divalent linking group. 01 It is a single bond or a divalent linking group. Rax 01 Rz is an acid-dissociable group represented by the general formula (a1-r-1), (a1-r-2), or (a1-r-4) above. 01 [q is an alkyl group, halogen atom, alkyl halide, hydroxyl group, or alkoxy group. q is an integer between 0 and 3. n is a non-negative integer, where n ≤ q × 2 + 4.]

[0156] In formulas (a1-1) to (a1-3), the alkyl group of R having 1 to 5 carbon atoms is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, specifically including methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl groups. The halogenated alkyl group having 1 to 5 carbon atoms is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. Fluorine atoms are particularly preferred as the halogen atoms. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, with a hydrogen atom or a methyl group being the most preferred due to their industrial availability.

[0157] In the above formula (a1-1), Va 1 The divalent hydrocarbon group in this expression may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0158] Va 1 The aliphatic hydrocarbon group as a divalent hydrocarbon group in this compound may be saturated or unsaturated, but is usually preferred to be saturated. More specifically, examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups containing a ring in their structure.

[0159] The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As for the linear aliphatic hydrocarbon group, linear alkylene groups are preferred, specifically the methylene group [-CH2-], ethylene group [-(CH2)2-], trimethylene group [-(CH2)3-], tetramethylene group [-(CH2)4-], pentamethylene group [-(CH2)5-], etc. The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. Preferred branched aliphatic hydrocarbon groups include branched alkylene groups, specifically alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkylalkylene groups such as alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. In the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0160] Examples of aliphatic hydrocarbon groups containing a ring in the aforementioned structure include alicyclic hydrocarbon groups (groups obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include those similar to the linear or branched aliphatic hydrocarbon group described above. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be polycyclic or monocyclic. A preferred monocyclic alicyclic hydrocarbon group is a group obtained by removing two hydrogen atoms from a monocycloalkane. The monocycloalkane is preferably one having 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. A preferred polycyclic alicyclic hydrocarbon group is a group obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 Examples include decane and tetracyclododecane.

[0161] Va 1 In this context, an aromatic hydrocarbon group as a divalent hydrocarbon group is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 12. However, this number of carbon atoms does not include the number of carbon atoms in substituents. Specific examples of aromatic rings in aromatic hydrocarbon groups include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced by heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of the aromatic hydrocarbon group include a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring (arylene group); and a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring (aryl group) in which one hydrogen atom is replaced by an alkylene group (for example, a group obtained by removing one more hydrogen atom from the aryl group in an arylalkyl group such as a benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms in the alkylene group (alkyl chain in an arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0162] In the above formula (a1-1), Ra 1 The acid-dissociable group is preferably represented by the general formula (a1-r-2) or (a1-r-4) described above, and among these, the group represented by the general formula (a1-r2-1) or the acid-dissociable group represented by the general formula (a1-r-4) is more preferred.

[0163] In the above formula (a1-2), Wa 1 n in a2 The +1 valent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity, and may be saturated or unsaturated, but is usually preferred to be saturated. Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in its structure, or a group that is a combination of a linear or branched aliphatic hydrocarbon group and an aliphatic hydrocarbon group containing a ring in its structure. The aforementioned n a2 The +1 valent is preferably 2 to 4 valent, and more preferably 2 or 3 valent. In the above formula (a1-2), Ra 2 The acid-dissociable group represented by the general formula (a1-r-1) above is preferred.

[0164] In the above formula (a1-3), Ya 001 The divalent linking group in this is not particularly limited, but suitable examples include divalent hydrocarbon groups which may have substituents, and divalent linking groups which contain heteroatoms. Ya 001 The alkylene group is preferably an ester bond [-C(=O)-O-, -OC(=O)-], an ether bond (-O-), a linear or branched alkylene group, an aromatic hydrocarbon group, or a combination thereof, or a single bond. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms. Among these, Ya 001The combination of an ester bond [-C(=O)-O-, -OC(=O)-] and a linear alkylene group is more preferable, and a single bond is even more preferable.

[0165] In the above formula (a1-3), Ya 01 The divalent linking group in this is not particularly limited, but suitable examples include divalent hydrocarbon groups which may have substituents, and divalent linking groups which contain heteroatoms. Ya 01 Among the above, it is preferable that the ester bond [-C(=O)-O-, -OC(=O)-], ether bond (-O-), linear or branched alkylene group, aromatic hydrocarbon group or a combination thereof, or single bond. Among these, Ya 01 The combination of an ester bond [-C(=O)-O-, -OC(=O)-] and a linear alkylene group is more preferable, and a single bond is even more preferable.

[0166] In the above formula (a1-3), Rax 01 The acid-dissociable group is preferably represented by the general formula (a1-r-2) or (a1-r-4) described above, and among these, the acid-dissociable group represented by the general formula (a1-r-2) is more preferred, and the group represented by the general formula (a1-r2-1) is even more preferred.

[0167] In the above equation (a1-3), Rz 01 The alkyl group, alkyl halide, and alkoxy group in the above preferably have 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, even more preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms. The alkyl group, alkyl halide, and alkoxy group may be linear or branched. Rz 01 In this case, an iodine atom is preferred as the halogen atom. Rz 01 In the alkyl halide, the halogen atom is preferably a fluorine atom, an iodine atom, or a bromine atom, with a fluorine atom being more preferred. Rz01 The group is preferably an alkoxy group or a hydroxyl group, with a hydroxyl group being more preferred.

[0168] In the above formula (a1-3), q is an integer between 0 and 3. When q is 0, it is a benzene structure; when q is 1, it is a naphthalene structure; when q is 2, it is an anthracene structure; and when q is 3, it is a tetracene structure. In the above formula (a1-3), n is an integer greater than or equal to 0, preferably between 0 and 5, more preferably between 0 and 3, and even more preferably 1 or 2. When n is an integer greater than or equal to 2, Rz is 2 or greater. 01 They may be the same or different from one another. In the above formula (a1-3), n ≤ q × 2 + 4. For example, if q is 1 and the structure is naphthalene, then all six hydrogen atoms in the naphthalene may be substituted with hydroxyl groups. Also, in the naphthalene, Ya 001 、-Ya 01 -C(=O)-O-Ra 01 The substitution positions of the group and the hydroxyl group are not particularly limited.

[0169] The following are specific examples of constituent units (a1). In each of the following equations, R α This represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0170] [ka]

[0171] [ka]

[0172] [ka]

[0173] [ka]

[0174] [ka]

[0175] [ka]

[0176] [ka]

[0177] [ka]

[0178] [ka]

[0179] In each of the following equations, R α Rz represents a hydrogen atom, a methyl group, or a trifluoromethyl group. Rz represents a hydrogen atom, an alkyl group, a halogen atom, an alkyl halide, a hydroxyl group, or an alkoxy group.

[0180] [ka]

[0181] [ka]

[0182] [ka]

[0183] [ka]

[0184] [ka]

[0185] The constituent units (a1) of component (A1) may be one type or two or more types. As for the constituent unit (a1), the constituent unit represented by formula (a1-1) or the constituent unit represented by formula (a1-3) is more preferable because it is easier to improve the characteristics (sensitivity, shape, etc.) in electron beam or EUV lithography. In particular, it is suitable for EB or EUV applications as it can enhance reactivity, and therefore has an acid-dissociating group (Ra 1 Rax 01 Preferably, each of these groups is an acid-dissociable group represented by the above general formula (a1-r2-1), (a1-r2-3), (a1-r2-4), or (a1-r-4), and among these, it is particularly preferable to select a cyclic group.

[0186] Alternatively, the constituent unit (a1) may include a constituent unit represented by the following general formula (a1-1-1).

[0187] [ka] [In the formula, Ra 1 " is an acid-dissociable group represented by the general formula (a1-r2-1), (a1-r2-3), (a1-r2-4), or (a1-r-4). * indicates a bond.

[0188] In the above formula (a1-1-1), R, Va 1 and n a1 R, Va in the above formula (a1-1) 1 and n a1 It is similar to that.

[0189] The acid-dissociable groups represented by the general formulas (a1-r2-1), (a1-r2-3), (a1-r2-4), or (a1-r-4) are described above. In particular, it is preferable to select those in which the acid-dissociable group is a cyclic group, as this enhances reactivity for EB or EUV applications.

[0190] The proportion of constituent units (a1) in component (A1) is preferably 5 to 80 mol%, more preferably 10 to 75 mol%, even more preferably 30 to 70 mol%, and particularly preferably 40 to 70 mol%, relative to the total amount (100 mol%) of all constituent units that make up component (A1). By setting the proportion of the constituent unit (a1) to be above the lower limit of the preferred range described above, lithography characteristics such as sensitivity, resolution, and CDU improvement are enhanced. On the other hand, if it is below the upper limit of the preferred range described above, a balance can be achieved with other constituent units, resulting in good lithography characteristics across various fields.

[0191] <<Other constituent units>> Component (A1) may have other constituent units in addition to the constituent unit (a1) described above, as needed. Other constituent units include, for example, the constituent unit (a10) represented by the general formula (a10-1) described below; the constituent unit (a2) containing a lactone-containing cyclic group; the constituent unit (a5) that generates acid upon exposure; the constituent unit (a6) that has acid diffusion controllability; and the constituent unit (a8) derived from the compound represented by the general formula (a8-1) described below.

[0192] Unit of composition (a10): The constituent unit (a10) is a constituent unit represented by the following general formula (a10-1).

[0193] [ka] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halogen having 1 to 5 carbon atoms. x1 Wa is a single bond or a divalent linking group. x1n is an aromatic hydrocarbon group which may have substituents. ax1 [ is an integer greater than or equal to 1.]

[0194] In formula (a10-1), R is the same as R in general formula (a1-1). R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and a hydrogen atom or a methyl group is particularly preferred due to their industrial availability.

[0195] In the above formula (a10-1), Ya x1 It is a single bond or a divalent linking group. In the above chemical formula, Ya x1 The divalent linking group in this is not particularly limited, but suitable examples include divalent hydrocarbon groups which may have substituents, and divalent linking groups which contain heteroatoms.

[0196] • Divalent hydrocarbon groups which may have substituents: The divalent hydrocarbon group, which may have substituents, may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0197] Aliphatic hydrocarbon groups An aliphatic hydrocarbon group refers to a hydrocarbon group that does not possess aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, but is usually preferable to be saturated. Examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups containing a ring in their structure.

[0198] ...linear or branched aliphatic hydrocarbon groups The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As for the linear aliphatic hydrocarbon group, linear alkylene groups are preferred, specifically the methylene group [-CH2-], ethylene group [-(CH2)2-], trimethylene group [-(CH2)3-], tetramethylene group [-(CH2)4-], pentamethylene group [-(CH2)5-], etc. The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. Preferred branched aliphatic hydrocarbon groups include branched alkylene groups, specifically alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkylalkylene groups such as alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. In the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0199] The linear or branched aliphatic hydrocarbon group may or may not have substituents. Examples of substituents include fluorine atoms, fluorinated alkyl groups having 1 to 5 carbon atoms substituted with fluorine atoms, and carbonyl groups.

[0200] ...Aliphatic hydrocarbon groups containing a ring in their structure Examples of aliphatic hydrocarbon groups containing a ring in the structure include cyclic aliphatic hydrocarbon groups that may contain substituents containing heteroatoms in the ring structure (groups obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), groups in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which the cyclic aliphatic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group are the same as those described above. The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. A preferred monocyclic alicyclic hydrocarbon group is a group obtained by removing two hydrogen atoms from a monocycloalkane. The monocycloalkane is preferably one having 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. A preferred polycyclic alicyclic hydrocarbon group is a group obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 Examples include decane and tetracyclododecane.

[0201] The cyclic aliphatic hydrocarbon group may or may not have substituents. Examples of substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, and carbonyl groups. The alkyl group used as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group. As the alkoxy group used as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferred, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group are more preferred, and a methoxy group and an ethoxy group are even more preferred. A fluorine atom is preferred as the halogen atom used as the substituent. Examples of halogenated alkyl groups as substituents include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with halogen atoms. A cyclic aliphatic hydrocarbon group may have some of the carbon atoms constituting its ring structure replaced by substituents containing heteroatoms. Preferred substituents containing heteroatoms are -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0202] Aromatic hydrocarbon groups The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. However, this number of carbon atoms does not include the number of carbon atoms in substituents. Examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced by heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of aromatic heterocycles include pyridine rings and thiophene rings. Specific examples of aromatic hydrocarbon groups include groups obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); groups obtained by removing two hydrogen atoms from aromatic compounds containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and groups in which one hydrogen atom of an aryl group or heteroaryl group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group) is substituted with an alkylene group (e.g., groups obtained by removing one more hydrogen atom from an aryl group in an arylalkyl group such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms in the alkylene group bonded to the aryl group or heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0203] The aromatic hydrocarbon group may have its hydrogen atoms substituted with substituents. For example, the hydrogen atoms bonded to the aromatic ring in the aromatic hydrocarbon group may be substituted with substituents. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, and the like. The alkyl group used as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group. Examples of the substituents include alkoxy groups, halogen atoms, and alkyl halides that substitute for hydrogen atoms on the cyclic aliphatic hydrocarbon group.

[0204] • Divalent linking groups containing heteroatoms: Examples of divalent linking groups containing heteroatoms include -O-, -C(=O)-O-, -OC(=O)-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)- (H may be substituted with substituents such as alkyl groups or acyl groups), -S-, -S(=O)2-, -S(=O)2-O-, and the general formula -Y 21 -OY22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 -,-[Y 21 -C(=O)-O] m” -Y 22 -, -Y 21 -OC(=O)-Y 22 - or -Y 21 -S(=O)2-OY 22 - is represented by the base [wherein Y 21 and Y 22 Each of these is a divalent hydrocarbon group which may independently have substituents, O is an oxygen atom, and m'' is an integer from 1 to 3. When the divalent linking group containing the heteroatom is -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, or -NH-C(=NH)-, the H may be substituted with substituents such as alkyl groups or acyl groups. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and particularly preferably 1 to 5. General formula-Y 21 -OY 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 -,-[Y 21 -C(=O)-O] m” -Y 22 -, -Y 21 -OC(=O)-Y 22 - or -Y 21 -S(=O)2-OY 22 - Middle, Y 21 and Y 22 Each of these is independently a divalent hydrocarbon group which may have substituents. Examples of such divalent hydrocarbon groups are the same as those described above. Y 21 Preferably, the group is a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, even more preferably a linear alkylene group having 1 to 5 carbon atoms, and particularly preferably a methylene group or an ethylene group. Y 22The group is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group, or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group. Formula - [Y 21 -C(=O)-O] m” -Y 22 In the base represented by -, m'' is an integer from 1 to 3, preferably 1 or 2, and more preferably 1. That is, in the formula -[Y 21 -C(=O)-O] m” -Y 22 As a base represented by -, formula -Y 21 -C(=O)-OY 22 Groups represented by - are particularly preferred. Among them, the group represented by formula -(CH2) a’ -C(=O)-O-(CH2) b’ A base represented by - is preferred. In the formula, a' is an integer from 1 to 10, preferably an integer from 1 to 8, more preferably an integer from 1 to 5, even more preferably 1 or 2, and most preferably 1. b' is an integer from 1 to 10, preferably an integer from 1 to 8, more preferably an integer from 1 to 5, even more preferably 1 or 2, and most preferably 1.

[0205] Ya x1 Preferred members include single bonds, ester bonds [-C(=O)-O-, -OC(=O)-], ether bonds (-O-), linear or branched alkylene groups, or combinations thereof, with single bonds and ester bonds [-C(=O)-O-, -OC(=O)-] being more preferred.

[0206] In the above formula (a10-1), Wa x1 This is an aromatic hydrocarbon group which may have substituents. Wa x1 The aromatic hydrocarbon group in this context may be an aromatic ring that may have substituents (n ax1A group with 1+1 hydrogen atoms removed is an example. The aromatic ring here is not particularly limited as long as it is a cyclic conjugated system with 4n+2 π electrons. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced by heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of aromatic heterocycles include pyridine rings and thiophene rings. Also, Wa x1 The aromatic hydrocarbon group in this context is an aromatic compound containing an aromatic ring which may have two or more substituents (e.g., biphenyl, fluorene, etc.) (n ax1 Another example is a group with (+1) hydrogen atoms removed. Among the above, Wa x1 Examples include benzene, naphthalene, anthracene, or biphenyl (n ax1 A group with (+1) hydrogen atoms removed is preferred, and (n ax1 A group with (+1) hydrogen atoms removed is more preferable, and from benzene (n ax1 A group with (+1) hydrogen atoms removed is even more preferable.

[0207] Wa x1 The aromatic hydrocarbon group in may or may not have substituents. Examples of substituents include alkyl groups, alkoxy groups, halogen atoms, and alkyl halides. Examples of alkyl groups, alkoxy groups, halogen atoms, and alkyl halides as substituents include Ya x1 Examples of substituents for cyclic aliphatic hydrocarbon groups in are similar to those listed above. The substituents are preferably linear or branched alkyl groups having 1 to 5 carbon atoms, more preferably linear or branched alkyl groups having 1 to 3 carbon atoms, even more preferably ethyl or methyl groups, and particularly preferably methyl groups. x1In this context, it is preferable that the aromatic hydrocarbon group does not have substituents.

[0208] In the above formula (a10-1), n ax1 is an integer greater than or equal to 1, preferably an integer between 1 and 10, more preferably an integer between 1 and 5, even more preferably 1, 2, or 3, and particularly preferably 1 or 2.

[0209] The following are specific examples of the constituent unit (a10) represented by the above formula (a10-1). In each of the following equations, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0210] [ka]

[0211] [ka]

[0212] [ka]

[0213] The constituent units (a10) of component (A1) may be one type or two or more types. Component (A1) may or may not have constituent units (a10), but it is preferable that it has constituent units (a10). If component (A1) has constituent units (a10), the proportion of constituent units (a10) in component (A1) is preferably 20 to 80 mol%, more preferably 25 to 70 mol%, even more preferably 30 to 60 mol%, and particularly preferably 30 to 50 mol%, relative to the total amount (100 mol%) of all constituent units that make up component (A1). By setting the proportion of constituent unit (a10) above the lower limit, sensitivity can be more easily increased. On the other hand, by setting it below the upper limit, it becomes easier to balance it with other constituent units.

[0214] Unit of composition (a2): Component (A1) may or may not have a constituent unit (a2) containing a lactone-containing cyclic group (excluding those corresponding to constituent unit (a1)). The lactone-containing cyclic group of component (a2) is effective in improving the adhesion of the resist film to the substrate when component (A1) is used to form a resist film. Furthermore, the presence of component (a2) improves lithography characteristics, for example, by appropriately adjusting the acid diffusion length, improving the adhesion of the resist film to the substrate, and appropriately adjusting the solubility during development.

[0215] A "lactone-containing cyclic group" refers to a cyclic group that contains a ring (lactone ring) containing -OC(=O)- within its cyclic skeleton. The lactone ring is counted as the first ring. If it consists only of a lactone ring, it is called a monocyclic group. If it also has other ring structures, it is called a polycyclic group regardless of those structures. A lactone-containing cyclic group may be a monocyclic group or a polycyclic group. Any lactone-containing cyclic group can be used in the constituent unit (a2) without any particular limitations. Specifically, this includes the groups represented by the general formulas (a2-r-1) to (a2-r-7).

[0216] Among the constituent units (a2), those derived from acrylic acid esters in which the hydrogen atom bonded to the α-carbon atom may be substituted with a substituent are preferred. The constituent unit (a2) is preferably a constituent unit represented by the following general formula (a2-1).

[0217] [ka] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halogen having 1 to 5 carbon atoms. 21 It is a single bond or a divalent linking group. 21The R' is -O-, -COO-, -CON(R')-, -OCO-, -CONHCO-, or -CONHCS-, where R' represents a hydrogen atom or a methyl group. However, La 21 If -O-, Ya 21 It does not become -CO-. 21 It is a lactone-containing cyclic group.

[0218] In formula (a2-1) above, R is the same as above. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and a hydrogen atom or a methyl group is particularly preferred due to their industrial availability.

[0219] In the above formula (a2-1), Ya 21 The divalent linking group in this is not particularly limited, but preferred examples include divalent hydrocarbon groups which may have substituents, and divalent linking groups which contain heteroatoms. 21 The divalent linking group in the above general formula (a10-1) is Ya x1 Examples include divalent linking groups similar to those in [the relevant context].

[0220] Ya 21 Preferably, the group is a single bond, an ester bond [-C(=O)-O-], an ether bond (-O-), a linear or branched alkylene group, or a combination thereof.

[0221] In the above formula (a2-1), Ya 21 It is a single bond, La 21 It is preferable that it be -COO- or -OCO-.

[0222] In the above formula (a2-1), Ra 21 It is a lactone-containing cyclic group. Ra 21 Suitable lactone-containing cyclic groups in this compound include those represented by the general formulas (a2-r-1) to (a2-r-7) mentioned above.

[0223] The constituent units (a2) of component (A1) may be one type or two or more types. Component (A1) may or may not have constituent units (a2). If component (A1) has constituent units (a2), the proportion of constituent units (a2) is preferably 1 to 20 mol%, more preferably 1 to 15 mol%, and even more preferably 1 to 10 mol%, relative to the total amount (100 mol%) of all constituent units that make up component (A1). If the proportion of constituent unit (a2) is set above a preferred lower limit, the effects of including constituent unit (a2) are fully obtained due to the effects described above, and if it is below the upper limit, a balance can be achieved with other constituent units, resulting in good lithography characteristics.

[0224] Unit of composition (a5): Component (A1) may or may not have a constituent unit (a5) that generates acid upon exposure. Known constituent units (a5) can be used. Having constituent unit (a5) makes it easier for the acid generated upon exposure to be uniformly distributed within the resist film. Examples of constituent unit (a5) include a constituent unit containing the structure described in component (B) below. For example, a constituent unit containing a structure represented by any of the general formulas (b-1) to (b-3) below can be used. Suitable constituent units (a5) include, for example, the constituent unit represented by the following general formula (a5-1).

[0225] [ka] [In the formula, R m This is an alkyl group having 1 to 5 carbon atoms, an alkyl halide having 1 to 5 carbon atoms, a halogen atom, or a hydrogen atom. 50 This is a divalent linking group or a single bond. 50 n is a divalent hydrocarbon group which may have substituents. a5 is an integer between 0 and 2. 51 It is a divalent linking group. 5This is a divalent linking group that may have a heteroatom, or a single bond. 51 and Ra 52 Each of these is independently a hydrogen atom, a fluorine atom, or a fluorinated alkyl group. n5 is an integer from 1 to 4. m is an integer of 1 or more, and M' m+ This is an onium cation with a valence of m.

[0226] {Anion Division} In the above formula (a5-1), R m These are alkyl groups having 1 to 5 carbon atoms, alkyl halides having 1 to 5 carbon atoms, halogen atoms, or hydrogen atoms. R m The alkyl group having 1 to 5 carbon atoms is preferably a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc. A halogenated alkyl group having 1 to 5 carbon atoms is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. Fluorine is particularly preferred as the halogen atom in alkyl halides. R m Preferably, the elements are hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, or fluorinated alkyl groups having 1 to 5 carbon atoms, with hydrogen atoms or methyl groups being the most preferred due to their industrial availability.

[0227] In the above formula (a5-1), La 50 This is a divalent linking group or a single bond. La 50 The divalent linking group in is not particularly limited, but preferred examples include a divalent hydrocarbon group which may have substituents, and a divalent linking group which contains a heteroatom, respectively. x1 This is similar to the divalent linking groups exemplified in the above, such as divalent hydrocarbon groups which may have substituents, and divalent linking groups which contain heteroatoms. Among the above, La 50 Preferably, the bonds are ester bonds [-C(=O)-O-, -OC(=O)-], ether bonds (-O-), linear or branched alkylene groups, aromatic hydrocarbon groups or combinations thereof, or single bonds. Among these, La 5 As such, ester bonds [-C(=O)-O-, -OC(=O)-] and single bonds are more preferable, and ester bonds [-C(=O)-O-, -OC(=O)-] are even more preferable.

[0228] In the above formula (a5-1), Ra 50 This is a divalent hydrocarbon group which may have substituents. Ra 50 The divalent hydrocarbon group in this expression may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0229] ··Ra 50 Aliphatic hydrocarbon groups in The aliphatic hydrocarbon group refers to a hydrocarbon group that does not possess aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, but is usually preferred to be saturated. Examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups containing a ring in their structure.

[0230] ...linear or branched aliphatic hydrocarbon groups The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As for the linear aliphatic hydrocarbon group, linear alkylene groups are preferred, specifically the methylene group [-CH2-], ethylene group [-(CH2)2-], trimethylene group [-(CH2)3-], tetramethylene group [-(CH2)4-], pentamethylene group [-(CH2)5-], etc. The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. Preferred branched aliphatic hydrocarbon groups include branched alkylene groups, specifically alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkylalkylene groups such as alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. In the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0231] The linear or branched aliphatic hydrocarbon group described above may or may not have substituents. Examples of substituents include fluorine atoms, fluorinated alkyl groups having 1 to 5 carbon atoms substituted with fluorine atoms, and carbonyl groups.

[0232] ...Aliphatic hydrocarbon groups containing a ring in their structure Examples of aliphatic hydrocarbon groups containing a ring in the structure include cyclic aliphatic hydrocarbon groups that may contain substituents containing heteroatoms in the ring structure (groups from which two hydrogen atoms have been removed from an aliphatic hydrocarbon ring), groups in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which the cyclic aliphatic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group are the same as those described above. The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms. The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. A preferred monocyclic alicyclic hydrocarbon group is a group obtained by removing two hydrogen atoms from a monocycloalkane. The monocycloalkane is preferably one having 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. A preferred polycyclic alicyclic hydrocarbon group is a group obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 Examples include decane and tetracyclododecane.

[0233] The cyclic aliphatic hydrocarbon group may or may not have substituents. Examples of substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, and carbonyl groups. The alkyl group used as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group. As the alkoxy group used as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferred, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group are more preferred, and a methoxy group and an ethoxy group are most preferred. Examples of halogen atoms used as substituents include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, and the like, with fluorine atoms being preferred. Examples of halogenated alkyl groups as substituents include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with halogen atoms. A cyclic aliphatic hydrocarbon group may have some of the carbon atoms constituting its ring structure replaced by substituents containing heteroatoms. Preferred substituents containing heteroatoms are -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0234] ··Ra 50Aromatic hydrocarbon groups in The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. However, this number of carbon atoms does not include the number of carbon atoms in substituents. Specific examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of aromatic heterocycles include pyridine rings and thiophene rings. Specific examples of aromatic hydrocarbon groups include groups obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); groups obtained by removing two hydrogen atoms from aromatic compounds containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and groups in which one hydrogen atom of an aryl group or heteroaryl group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group) is substituted with an alkylene group (e.g., groups obtained by removing one more hydrogen atom from an aryl group in an arylalkyl group such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms in the alkylene group bonded to the aryl group or heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0235] The aromatic hydrocarbon group may have its hydrogen atoms substituted with substituents. For example, the hydrogen atoms bonded to the aromatic ring in the aromatic hydrocarbon group may be substituted with substituents. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, and hydroxyl groups. The alkyl group used as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group. Examples of the substituents include alkoxy groups, halogen atoms, and alkyl halogens that substitute for hydrogen atoms on the cyclic aliphatic hydrocarbon group.

[0236] In the above formula (a5-1), n a5 This is an integer between 0 and 2. Among the above, 50 The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group containing a ring in its structure, more preferably a cyclic aliphatic hydrocarbon group which may contain substituents containing heteroatoms in its ring structure, and even more preferably an alicyclic hydrocarbon group which may have substituents and is a polycyclic or monocyclic group. Alternatively, among the above, Ra 50 Aromatic hydrocarbon groups are preferred.

[0237] n a5 If it is 2, then 2 Ra 50 These may all be alicyclic hydrocarbon groups which may have substituents, or they may all be aromatic hydrocarbon groups which may have substituents, or they may be a combination of alicyclic hydrocarbon groups which may have substituents and aromatic hydrocarbon groups which may have substituents.

[0238] In the above formula (a5-1), La 51 It is a divalent linking group. La 51 Examples of divalent linking groups in this context include non-hydrocarbon oxygen-containing linking groups such as oxygen atoms (ether bond: -O-), ester bonds (-C(=O)-O-), oxycarbonyl groups (-OC(=O)-), amide bonds (-C(=O)-NH-), carbonyl groups (-C(=O)-), and carbonate bonds (-OC(=O)-O-); and combinations of these non-hydrocarbon oxygen-containing linking groups with alkylene groups. A sulfonyl group (-SO2-) may be further linked to this combination. Examples of such divalent linking groups include the linking groups represented by the following general formulas (L-al-1) to (L-al-8). Note that in the following general formulas (L-al-1) to (L-al-8), Ra in formula (a5-1) above 50 The combination with this is V' in the following general formulas (L-al-1)~(L-al-8). 101 That is the case.

[0239] [ka] [In the formula, V' 101 V' is a single bond or an alkylene group with 1 to 5 carbon atoms. 102 It is a divalent saturated hydrocarbon group with 1 to 30 carbon atoms.

[0240] V' 102 The divalent saturated hydrocarbon group in is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 5 carbon atoms.

[0241] V' 101 and V' 102 The alkylene group in this product may be a linear alkylene group or a branched alkylene group, but a linear alkylene group is preferred. V' 101 and V' 102Specifically, the alkylene groups in these include: methylene group [-CH2-]; alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-; ethylene group [-CH2CH2-]; -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2 Examples include alkylethylene groups such as -CH2CH2CH2-; trimethylene groups (n-propylene groups) [-CH2CH2CH2-]; alkyltrimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; tetramethylene groups [-CH2CH2CH2CH2-]; alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-; and pentamethylene groups [-CH2CH2CH2CH2CH2-]. Also, oshiV' 101 or V' 102 Some of the methylene groups in the alkylene group may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms. The aliphatic cyclic group is Ra' in formula (a1-r-1). 3 A divalent group is preferred, which is obtained by removing one more hydrogen atom from a cyclic aliphatic hydrocarbon group (monocyclic aliphatic hydrocarbon group, polycyclic aliphatic hydrocarbon group), and a cyclohexylene group, a 1,5-adamantilene group, or a 2,6-adamantilene group is more preferred.

[0242] La 51 Preferably, the linking group is a divalent linking group containing an ester bond or a divalent linking group containing an ether bond, more preferably the linking groups represented by the above formulas (L-al-1) to (L-al-5) and (L-al-8), and even more preferably the linking group represented by (L-al-3) or (L-al-8).

[0243] In the above formula (a5-1), Ya 5 This is a divalent linking group that may have a heteroatom, or a single bond. Ya 5The divalent linking group in this is not particularly limited, but preferred examples include divalent hydrocarbon groups which may have substituents, and divalent linking groups which contain heteroatoms. Ya 5 In the above, the divalent hydrocarbon group which may have substituents, and the divalent linking group which contains a heteroatom, are as follows: x1 This is similar to the divalent linking groups exemplified in the above, such as divalent hydrocarbon groups which may have substituents, and divalent linking groups which contain heteroatoms. Among the above, Ya 5 The alkylene group is preferably a linear or branched alkylene group, or a single bond, with a single bond being more preferable.

[0244] In the above formula (a5-1), Ra 51 and Ra 52 Each of these is independently a hydrogen atom, a fluorine atom, or a fluorinated alkyl group. Ra 51 and Ra 52 The fluorinated alkyl groups in this compound are preferably linear or branched fluorinated alkyl groups having 1 to 5 carbon atoms, with a trifluoromethyl group being more preferred. In the above formula (a5-1), SO3 - Ra bonds to the adjacent carbon atom. 51 and Ra 52 From the viewpoint of acid strength, it is preferable that at least one of these atoms is a fluorine atom.

[0245] In the above formula (a5-1), n5 is an integer from 1 to 4, and is preferably 1, 2, or 3.

[0246] {cation part} In the above formula (a5-1), M' m+ This represents an m-valent onium cation. Among these, M' m+ The sulfonium cation and iodonium cation are preferred. m is an integer of 1 or more.

[0247] Preferred cation portion ((M' m+ ) 1 / mExamples of these include organic cations represented by the following general formulas (ca-1) to (ca-3).

[0248] [ka] [In the formula, R 201 ~R 207 Each of these independently represents an optionally substituted aryl group, an optionally substituted alkyl group, or an optionally substituted alkenyl group. 201 ~R 203 , R 206 ~R 207 These atoms may bond to each other to form a ring with the sulfur atom in the formula. 208 ~R 209 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 210 This is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted -SO2- containing cyclic group. 201 This represents -C(=O)- or -C(=O)-O-.

[0249] In the above general formulas (ca-1) to (ca-3), R 201 ~R 207 Examples of aryl groups in this context include unsubstituted aryl groups having 6 to 20 carbon atoms, with phenyl and naphthyl groups being preferred. R 201 ~R 207 The alkyl group in this is preferably a linear or cyclic alkyl group having 1 to 30 carbon atoms. R 201 ~R 207 The alkenyl group in this compound preferably has 2 to 10 carbon atoms. R 201 ~R 207 , and R 210Examples of substituents that may be present include alkyl groups, halogen atoms, alkyl halides, carbonyl groups, cyano groups, amino groups, aryl groups, and the groups represented by the general formulas (ca-r-1) to (ca-r-7) mentioned above.

[0250] In the above general formulas (ca-1) to (ca-3), R 201 ~R 203 , R 206 ~R 207 When these atoms bond to each other and form a ring with the sulfur atom in the formula, they may be heteroatoms such as sulfur, oxygen, or nitrogen atoms, or carbonyl groups, -SO-, -SO2-, -SO3-, -COO-, -CONH-, or -N(R N )-(the R N is an alkyl group having 1 to 5 carbon atoms. ) may be bonded via functional groups such as ). The formed ring preferably has 3 to 10 members, and particularly preferably 5 to 7 members, including the sulfur atom in its ring skeleton. Specific examples of the formed ring include, for example, a thiophene ring, a thiazole ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthlene ring, a phenoxatiyne ring, a tetrahydrothiophenium ring, and a tetrahydrothiopyranium ring.

[0251] R 208 ~R 209 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. If an alkyl group is formed, it may bond with other elements to form a ring.

[0252] R 210 This is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted -SO2- containing cyclic group. R 210 Examples of aryl groups in this context include unsubstituted aryl groups having 6 to 20 carbon atoms, with phenyl and naphthyl groups being preferred. R 210The alkyl group in this is preferably a linear or cyclic alkyl group having 1 to 30 carbon atoms. R 210 The alkenyl group in this compound preferably has 2 to 10 carbon atoms. R 210 In this context, the -SO2-containing cyclic group can be any group without particular limitations. Specifically, groups represented by the general formulas (b5-r-1) to (b5-r-4) are used, with "-SO2-containing polycyclic groups" being preferred, and the group represented by the general formula (b5-r-1) being more preferred.

[0253] Specific examples of suitable cations represented by the above formula (ca-1) include the cations represented by the following chemical formulas.

[0254] [ka]

[0255] [ka]

[0256] [ka] [In the formula, g1, g2, and g3 represent the number of repetitions, where g1 is an integer from 1 to 5, g2 is an integer from 0 to 20, and g3 is an integer from 1 to 20.]

[0257] [ka]

[0258] [ka]

[0259] [ka] [In the formula, R” 201 is a hydrogen atom or a substituent, and the substituent is the aforementioned R 201 ~R 207 , and R 210 These are the same as those listed as substituents that may be present.

[0260] [ka]

[0261] Suitable cations represented by the formula (ca-2) include, specifically, diphenyliodonium cation and bis(4-tert-butylphenyl)iodonium cation.

[0262] Specific examples of suitable cations represented by the above formula (ca-3) include the cations represented by the following formulas (ca-3-1) to (ca-3-6).

[0263] [ka]

[0264] The cation portion in the above formula (a5-1) ((M' m+ ) 1 / m As for the cation, a sulfonium cation is preferred, the cations represented by formulas (ca-1) to (ca-3) are more preferred, the cation represented by formula (ca-1) is even more preferred, and the cations represented by formulas (ca-1-1) to (ca-1-84) are particularly preferred. In particular, from the viewpoint of increasing sensitivity, preferred cations represented by the above formula (ca-1) are those having electron-withdrawing groups such as a fluorine atom, a fluorinated alkyl group, or a sulfonyl group as substituents. For example, cations selected from the group consisting of cations represented by the above chemical formulas (ca-1-44), (ca-1-71) to (ca-1-84) are particularly preferred.

[0265] The following are some preferred examples of the constituent unit (a5). In the following equation, R α m and M' represent a hydrogen atom, a methyl group, or a trifluoromethyl group. m+ These are m and M' in the general formula (a5-1) above. m+ It is similar to that.

[0266] [ka]

[0267] [ka]

[0268] [ka]

[0269] (A1) The constituent units (a5) of component (A1) may be one type or two or more types. If component (A1) has constituent units (a5), the proportion of constituent units (a5) in component (A1) is preferably 3 to 25 mol%, more preferably 5 to 25 mol%, and even more preferably 8 to 20 mol%, relative to the total amount (100 mol%) of all constituent units that make up component (A1). If the proportion of the constituent unit (a5) is above the lower limit of the preferred range mentioned above, it becomes easier to achieve further increases in sensitivity and resolution. On the other hand, if it is below the upper limit of the preferred range mentioned above, it becomes easier to balance it with the other constituent units.

[0270] Unit of composition (a6): The constituent unit (a6) is a constituent unit that has acid diffusion control properties. Component (A1) may or may not contain constituent unit (a6). Known constituent units can be used for constituent unit (a6). Examples of constituent unit (a6) include constituent units containing the structures described in components (D1) and (D2) below. For example, a constituent unit containing a structure represented by any of the general formulas (d1-1) to (d1-3) below can be used.

[0271] The constituent units (a6) of component (A1) may be one type or two or more types. If component (A1) has constituent units (a6), the proportion of constituent units (a6) in component (A1) is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and even more preferably 3 to 10 mol%, relative to the total amount (100 mol%) of all constituent units that make up component (A1). If the proportion of the constituent unit (a6) is above the lower limit of the preferred range mentioned above, it becomes easier to achieve even higher sensitivity. On the other hand, if it is below the upper limit of the preferred range mentioned above, it becomes easier to balance it with the other constituent units.

[0272] Unit of composition (a8): The constituent unit (a8) is a constituent unit derived from the compound represented by the following general formula (a8-1). Component (A1) may or may not have the constituent unit (a8).

[0273] [ka] [In the formula, W 2 This is a polymerizable group-containing group. x2 is a single bond or (n ax2 It is a linking group with a +1 valence. x2 and W 2 It may form a fused ring with R. 1 R is a fluorinated alkyl group having 1 to 12 carbon atoms. 2 R is an organic group having 1 to 12 carbon atoms, which may contain a fluorine atom, or a hydrogen atom. 2 and Ya x2 These may be bonded to each other to form a ring structure. ax2 [This is an integer between 1 and 3.]

[0274] W 2 In the context of polymerizable group-containing groups, "polymerizable group" refers to a group that enables a compound containing a polymerizable group to polymerize by radical polymerization or the like, and includes, for example, a group containing multiple bonds between carbon atoms, such as an ethylenic double bond.

[0275] The polymerizable group-containing group may be a group composed solely of a polymerizable group, or a group composed of a polymerizable group and other groups other than the polymerizable group. Examples of other groups other than the polymerizable group include divalent hydrocarbon groups which may have substituents, and divalent linking groups which contain heteroatoms. Examples of polymerizable groups include those with the chemical formula: C(R X11 )(R X12 )=C(R X13 )-Ya x0 The group represented by - is preferably mentioned. In this chemical formula, R X11 , R X12 and R X13 These are, respectively, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, and Ya x0 It is a single bond or a divalent linking group.

[0276] Ya x2 and W 2 The condensed ring formed by these is W 2 Polymerizable groups of the site and Ya x2 The condensed ring formed by and W 2 Other groups besides the polymerizable group of the site and Ya x2 A condensed ring formed by these is one example. Ya x2 and W 2 The fused ring formed by these two components may have substituents.

[0277] The following are specific examples of constituent units (a8). In the following formula, R α This represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0278] [ka]

[0279] Among the examples above, the constituent unit (a8) is preferably at least one selected from the group consisting of constituent units represented by the chemical formulas (a8-1-01) to (a8-1-04), (a8-1-06), (a8-1-08), (a8-1-09), and (a8-1-10), and more preferably at least one selected from the group consisting of constituent units represented by the chemical formulas (a8-1-01) to (a8-1-04) and (a8-1-09).

[0280] The constituent units (a8) of component (A1) may be one type or two or more types. Component (A1) may or may not have constituent units (a8). The proportion of constituent units (a8) in component (A1) is preferably 0 to 50 mol%, and more preferably 0 to 30 mol%, relative to the total amount (100 mol%) of all constituent units that make up component (A1).

[0281] The resin component (A1) may have a constituent unit (a0) derived from a compound represented by the following general formula (a0-m). The constituent unit (a0) is a constituent unit containing the cation (C0).

[0282] [ka] [In the formula, W 0 This represents a polymerizable group-containing group. 0 Rx represents a divalent linking group. - This is an anionic group. + This is a cation represented by the general formula (c0) mentioned above.

[0283] Rx - For example, SO3 - , C(=O)O - , N - , C - These are some examples. The constituent unit (a0) may be, for example, a constituent unit (a0b) that generates acid upon exposure, or a constituent unit (a0d) that has acid diffusion control properties.

[0284] In the above general formula (a0-m), W 0 In the context of polymerizable group-containing groups, "polymerizable group" refers to a group that enables a compound containing a polymerizable group to polymerize by radical polymerization or the like, and includes, for example, a group containing multiple bonds between carbon atoms, such as an ethylenic double bond. Examples of polymerizable groups include vinyl group, allyl group, acryloyl group, methacryloyl group, fluorovinyl group, difluorovinyl group, trifluorovinyl group, difluorotrifluoromethylvinyl group, trifluoroallyl group, perfluoroallyl group, trifluoromethylacryloyl group, nonylfluorobutylacryloyl group, vinyl ether group, fluorinated vinyl ether group, allyl ether group, fluorinated allyl ether group, styryl group, vinylnaphthyl group, fluorinated styryl group, fluorinated vinylnaphthyl group, norbornyl group, fluorinated norbornyl group, and silyl group.

[0285] The polymerizable group-containing group may be a group composed solely of a polymerizable group, or a group composed of a polymerizable group and other groups other than the polymerizable group. Examples of other groups other than the polymerizable group include divalent hydrocarbon groups which may have substituents, and divalent linking groups which contain heteroatoms. Examples of polymerizable groups include those with the chemical formula: C(R X11 )(R X12 )=C(R X13 )-Ya x0 The group represented by - is preferably mentioned. In this chemical formula, R X11 , R X12 and R X13 These are, respectively, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, and Ya x0 It is a single bond or a divalent linking group. Ya x0 Examples of divalent linking groups in this context include divalent hydrocarbon groups which may have substituents, and divalent linking groups which contain heteroatoms. x0Examples of divalent linking groups in this include ester bonds (-C(=O)-O-), oxycarbonyl groups (-OC(=O)-), ether bonds (-O-), linear or branched alkylene groups, or combinations thereof. x0 The preferred components are single bonds, ester bonds (-C(=O)-O-), and oxycarbonyl groups (-OC(=O)-).

[0286] In the above general formula (a0-m), Y 0 The divalent linking group in this context is not particularly limited, but may include a divalent hydrocarbon group having substituents, and a divalent linking group containing a heteroatom.

[0287] • Divalent hydrocarbon groups which may have substituents: The divalent hydrocarbon group, which may have substituents, may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0288] Aliphatic hydrocarbon groups An aliphatic hydrocarbon group refers to a hydrocarbon group that does not possess aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, but is usually preferable to be saturated. Examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups containing a ring in their structure.

[0289] ...linear or branched aliphatic hydrocarbon groups The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As for the linear aliphatic hydrocarbon group, linear alkylene groups are preferred, specifically the methylene group [-CH2-], ethylene group [-(CH2)2-], trimethylene group [-(CH2)3-], tetramethylene group [-(CH2)4-], pentamethylene group [-(CH2)5-], etc. The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. Preferred branched aliphatic hydrocarbon groups include branched alkylene groups, specifically alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkylalkylene groups such as alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. In the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0290] The linear or branched aliphatic hydrocarbon group may or may not have substituents. Examples of substituents include fluorine atoms, fluorinated alkyl groups having 1 to 5 carbon atoms substituted with fluorine atoms, and carbonyl groups.

[0291] ...Aliphatic hydrocarbon groups containing a ring in their structure Examples of aliphatic hydrocarbon groups containing a ring in the structure include cyclic aliphatic hydrocarbon groups that may contain substituents containing heteroatoms in the ring structure (groups obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), groups in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which the cyclic aliphatic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group are the same as those described above. The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. A preferred monocyclic alicyclic hydrocarbon group is a group obtained by removing two hydrogen atoms from a monocycloalkane. The monocycloalkane is preferably one having 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. A preferred polycyclic alicyclic hydrocarbon group is a group obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.

[0292] The cyclic aliphatic hydrocarbon group may or may not have substituents. Examples of substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, and carbonyl groups. The alkyl group used as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group. As the alkoxy group used as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferred, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group are more preferred, and a methoxy group and an ethoxy group are even more preferred. A fluorine atom is preferred as the halogen atom used as the substituent. Examples of halogenated alkyl groups as substituents include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with halogen atoms. A cyclic aliphatic hydrocarbon group may have some of the carbon atoms constituting its ring structure replaced by substituents containing heteroatoms. Preferred substituents containing heteroatoms are -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0293] Aromatic hydrocarbon groups The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. However, this number of carbon atoms does not include the number of carbon atoms in substituents. Examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced by heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of aromatic heterocycles include pyridine rings and thiophene rings. Specific examples of aromatic hydrocarbon groups include groups obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); groups obtained by removing two hydrogen atoms from aromatic compounds containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and groups in which one hydrogen atom of an aryl group or heteroaryl group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group) is substituted with an alkylene group (e.g., groups obtained by removing one more hydrogen atom from an aryl group in an arylalkyl group such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms in the alkylene group bonded to the aryl group or heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0294] The aromatic hydrocarbon group may have its hydrogen atoms substituted with substituents. For example, the hydrogen atoms bonded to the aromatic ring in the aromatic hydrocarbon group may be substituted with substituents. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, and the like. The alkyl group used as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group. Examples of the substituents include alkoxy groups, halogen atoms, and alkyl halides that substitute for hydrogen atoms on the cyclic aliphatic hydrocarbon group.

[0295] • Divalent linking groups containing heteroatoms: Examples of divalent linking groups containing heteroatoms include -O-, -C(=O)-O-, -OC(=O)-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)- (H may be substituted with substituents such as alkyl groups or acyl groups), -S-, -S(=O)2-, -S(=O)2-O-, and the general formula -Y 21 -OY 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 -,-[Y 21 -C(=O)-O] m” -Y 22 -, -Y 21 -OC(=O)-Y 22 - or -Y 21 -S(=O)2-OY 22 - is represented by the base [wherein Y 21 and Y 22 Each of these is a divalent hydrocarbon group which may have substituents independently, O is an oxygen atom, and m'' is an integer from 0 to 3. When the divalent linking group containing the heteroatom is -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, or -NH-C(=NH)-, the H may be substituted with substituents such as alkyl groups or acyl groups. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and particularly preferably 1 to 5. General formula-Y 21 -OY 22 -, -Y 21 -O-, -Y21 -C(=O)-O-, -C(=O)-OY 21 -,-[Y 21 -C(=O)-O] m” -Y 22 -, -Y 21 -OC(=O)-Y 22 - or -Y 21 -S(=O)2-OY 22 - Middle, Y 21 and Y 22 Each of these is independently a divalent hydrocarbon group which may have substituents. Examples of such divalent hydrocarbon groups are the same as those described above. Y 21 Preferably, the group is a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, even more preferably a linear alkylene group having 1 to 5 carbon atoms, and particularly preferably a methylene group or an ethylene group. Y 22 The group is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group, or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group. Formula - [Y 21 -C(=O)-O] m” -Y 22 In the base represented by -, m'' is an integer between 0 and 3, preferably between 0 and 2, more preferably 0 or 1, and particularly preferably 1. That is, in the formula -[Y 21 -C(=O)-O] m” -Y 22 As a base represented by -, formula -Y 21 -C(=O)-OY 22 Groups represented by - are particularly preferred. Among them, the group represented by formula -(CH2) a’ -C(=O)-O-(CH2) b’A base represented by - is preferred. In the formula, a' is an integer from 1 to 10, preferably an integer from 1 to 8, more preferably an integer from 1 to 5, even more preferably 1 or 2, and most preferably 1. b' is an integer from 1 to 10, preferably an integer from 1 to 8, more preferably an integer from 1 to 5, even more preferably 1 or 2, and most preferably 1.

[0296] Constituent units (a0b) that generate acid upon exposure: The constituent unit (a0) may be a constituent unit that generates acid upon exposure (hereinafter also referred to as "constituent unit (a0b)"). The constituent unit (a0b) may have an anion portion in the constituent unit (a5) described above. The constituent unit (a0b) may be a constituent unit represented by the following general formula (a0-1b).

[0297] [ka] [In the formula, R m This is an alkyl group having 1 to 5 carbon atoms, an alkyl halide having 1 to 5 carbon atoms, a halogen atom, or a hydrogen atom. 50 This is a divalent linking group or a single bond. 50 n is a divalent hydrocarbon group which may have substituents. a5 is an integer between 0 and 2. 51 It is a divalent linking group. 5 This is a divalent linking group that may have a heteroatom, or a single bond. 51 and Ra 52 Each of these is independently a hydrogen atom, a fluorine atom, or a fluorinated alkyl group. n5 is an integer from 1 to 4. + This is the aforementioned cation (C0).

[0298] R m , La 50 Ra 50 , n a5 , La 51 Ya 5 Ra 51 Ra 52 , and n5 are the same as those in formula (a5-1) above.

[0299] Specific examples of the constituent unit (a0b) include a constituent unit having an anion portion of the above formulas (a5-1-1) to (a5-1-22) and a cation represented by the above general formula (c0) as a cation portion. That is, in the above formulas (a5-1-1) to (a5-1-22), M' m+ A constituent unit is a cation (C0) represented by the general formula (c0). In this case, m is 1.

[0300] The following are examples of preferred constituent units (a0b). In the following formula, R α This represents a hydrogen atom, a methyl group, or a trifluoromethyl group. + This is the aforementioned cation (C0).

[0301] [ka]

[0302] The following are preferred examples of constituent units (a0b), but are not limited to these.

[0303] [ka]

[0304] Constituent unit (a0d) having acid diffusion control properties: The constituent unit (a0) may also be a constituent unit having acid diffusion control properties (hereinafter also referred to as "constituent unit (a0d)"). The constituent unit (a0d) may also be a constituent unit represented by the following general formula (a0-1d).

[0305] [ka] [In the formula, R m This is an alkyl group having 1 to 5 carbon atoms, an alkyl halide having 1 to 5 carbon atoms, a halogen atom, or a hydrogen atom. d0 This is a divalent linking group or a single bond.d0 n is a divalent hydrocarbon group which may have substituents. d This is an integer between 0 and 2. + This is the aforementioned cation (C0).

[0306] In the above formula (a0-1d), R m This is the same as in equation (a5-1) above. In the above formula (a0-1d), La d0 The divalent linking group in formula (a5-1) is La 50 Examples include divalent linking groups similar to those in [the relevant context]. In the above formula (a0-1d), Ra d0 The divalent hydrocarbon group which may have substituents in formula (a5-1) is Ra 50 Examples include divalent hydrocarbon groups that may have substituents, similar to those in the above. In the above formula (a0-1d), nd is preferably 1 or 2, and more preferably 1.

[0307] The following are preferred examples of constituent units (a0d), but are not limited to these. In the following formula, R α This represents a hydrogen atom, a methyl group, or a trifluoromethyl group. + This is the aforementioned cation (C0).

[0308] [ka]

[0309] [ka]

[0310] The following are preferred examples of constituent units (a0d), but are not limited to these.

[0311] [ka]

[0312] The constituent unit (a0) of component (A1) may be one type or two or more types. Component (A1) may have both constituent unit (a0b) and constituent unit (a0d), or it may have only one of them.

[0313] If component (A1) has constituent units (a0), the proportion of constituent units (a0) in component (A1) is preferably 1 to 40 mol%, more preferably 2 to 35 mol%, and even more preferably 3 to 30 mol%, relative to the total amount (100 mol%) of all constituent units that make up component (A1). When the proportion of constituent unit (a0) is above the lower limit of the preferred range mentioned above, it becomes easier to achieve further increased sensitivity, reduced roughness, suppression of defects, and improved resolution. On the other hand, when it is below the upper limit of the preferred range mentioned above, it becomes easier to balance it with other constituent units.

[0314] If component (A1) has constituent units (a0b), the proportion of constituent units (a0b) in component (A1) is preferably 3 to 25 mol%, more preferably 5 to 25 mol%, and even more preferably 8 to 20 mol%, relative to the total amount (100 mol%) of all constituent units that make up component (A1). When the proportion of the constituent units (a0b) is above the lower limit of the preferred range mentioned above, it becomes easier to achieve further increased sensitivity, reduced roughness, suppression of defects, and improved resolution. On the other hand, when it is below the upper limit of the preferred range mentioned above, it becomes easier to balance it with the other constituent units.

[0315] If component (A1) has constituent units (a0b) and constituent units (a5), the total proportion of constituent units (a0b) and constituent units (a5) in component (A1) is preferably 3 to 25 mol%, more preferably 5 to 25 mol%, and even more preferably 8 to 20 mol%, relative to the total amount of all constituent units (100 mol%) that make up component (A1). If the total ratio of component units (a0b) and (a5) is above the lower limit of the preferred range, it becomes easier to achieve further increased sensitivity, reduced roughness, suppression of defects, and improved resolution. On the other hand, if it is below the upper limit of the preferred range, it becomes easier to balance with other component units.

[0316] If component (A1) has constituent units (a0d), the proportion of constituent units (a0d) in component (A1) is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and even more preferably 3 to 10 mol%, relative to the total amount (100 mol%) of all constituent units that make up component (A1). When the proportion of the constituent unit (a0d) is above the lower limit of the preferred range mentioned above, it becomes easier to achieve further increased sensitivity, reduced roughness, suppression of defects, and improved resolution. On the other hand, when it is below the upper limit of the preferred range mentioned above, it becomes easier to balance it with the other constituent units.

[0317] If component (A1) has constituent units (a0d) and constituent units (a6), the total proportion of constituent units (a0d) and constituent units (a6) in component (A1) is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and even more preferably 3 to 10 mol%, relative to the total amount of all constituent units (100 mol%) that make up component (A1). If the total ratio of component units (a0d) and (a6) is above the lower limit of the preferred range, it becomes easier to achieve further increased sensitivity, reduced roughness, suppression of defects, and improved resolution. On the other hand, if it is below the upper limit of the preferred range, it becomes easier to balance with other component units.

[0318] The (A1) component contained in the resist composition may be used alone or in combination of two or more types.

[0319] (A1) Examples of components include the following polymer compounds. A polymer compound consisting of constituent units (a1) and (a10); A polymer compound consisting of constituent units (a1), (a10), and (a0); A polymer compound consisting of constituent units (a1), (a10), and (a0b); A polymer compound consisting of constituent units (a1), (a10), and (a0d); A polymer compound consisting of constituent units (a1), (a10), (a0b), and (a6); A polymer compound consisting of constituent units (a1), (a10), (a5), and (a0d); A polymer compound consisting of constituent units (a1), (a10), (a0b), and (a0d).

[0320] In a polymer compound consisting of constituent units (a1) and (a10), The proportion of constituent units (a1) is more preferably 10 to 75 mol%, even more preferably 30 to 70 mol%, and still more preferably 40 to 70 mol%, relative to the total amount (100 mol%) of all constituent units that make up the polymer compound. The proportion of constituent units (a10) in the polymer compound is preferably 25 to 90 mol%, more preferably 30 to 70 mol%, and even more preferably 30 to 60 mol%, relative to the total amount (100 mol%) of all constituent units that make up the polymer compound.

[0321] In a polymer compound consisting of constituent units (a1), (a10), and (a0), The proportion of constituent units (a1) is more preferably 10 to 80 mol%, even more preferably 30 to 70 mol%, and even more preferably 40 to 60 mol%, relative to the total amount (100 mol%) of all constituent units that make up the polymer compound. The proportion of constituent units (a10) in the polymer compound is preferably 10 to 70 mol%, more preferably 20 to 60 mol%, and even more preferably 25 to 50 mol%, relative to the total amount (100 mol%) of all constituent units that make up the polymer compound. The proportion of constituent units (a0) in the polymer compound is preferably 1 to 40 mol%, more preferably 2 to 35 mol%, and even more preferably 3 to 30 mol%, relative to the total amount (100 mol%) of all constituent units that make up the polymer compound.

[0322] In a polymer compound consisting of constituent units (a1), (a10), and (a0b), The proportion of constituent units (a1) is more preferably 10 to 80 mol%, even more preferably 30 to 70 mol%, and even more preferably 40 to 60 mol%, relative to the total amount (100 mol%) of all constituent units that make up the polymer compound. The proportion of constituent units (a10) in the polymer compound is preferably 10 to 70 mol%, more preferably 20 to 60 mol%, and even more preferably 25 to 50 mol%, relative to the total amount (100 mol%) of all constituent units that make up the polymer compound. The proportion of constituent units (a0b) in the polymer compound is preferably 3 to 25 mol%, more preferably 5 to 25 mol%, and even more preferably 8 to 20 mol%, relative to the total amount (100 mol%) of all constituent units that make up the polymer compound.

[0323] In a polymer compound consisting of constituent units (a1), (a10), and (a0d), The proportion of constituent units (a1) is more preferably 10 to 80 mol%, even more preferably 30 to 70 mol%, and even more preferably 40 to 60 mol%, relative to the total amount (100 mol%) of all constituent units that make up the polymer compound. The proportion of constituent units (a10) in the polymer compound is preferably 10 to 70 mol%, more preferably 20 to 60 mol%, and even more preferably 25 to 50 mol%, relative to the total amount (100 mol%) of all constituent units that make up the polymer compound. The proportion of constituent units (a0d) in the polymer compound is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and even more preferably 3 to 10 mol%, relative to the total amount (100 mol%) of all constituent units that make up the polymer compound.

[0324] In a polymer compound consisting of constituent units (a1), (a10), (a0b), and (a6), The proportion of constituent units (a1) is more preferably 10 to 80 mol%, even more preferably 30 to 70 mol%, and even more preferably 40 to 60 mol%, relative to the total amount (100 mol%) of all constituent units that make up the polymer compound. The proportion of constituent units (a10) in the polymer compound is preferably 10 to 70 mol%, more preferably 20 to 60 mol%, and even more preferably 25 to 50 mol%, relative to the total amount (100 mol%) of all constituent units that make up the polymer compound. The proportion of constituent units (a0b) in the polymer compound is preferably 3 to 25 mol%, more preferably 5 to 25 mol%, and even more preferably 8 to 20 mol%, relative to the total amount (100 mol%) of all constituent units that make up the polymer compound. The proportion of constituent units (a6) in the polymer compound is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and even more preferably 3 to 10 mol%, relative to the total amount (100 mol%) of all constituent units that make up the polymer compound.

[0325] In a polymer compound consisting of constituent units (a1), (a10), (a5), and (a0d), The proportion of constituent units (a1) is more preferably 10 to 80 mol%, even more preferably 30 to 70 mol%, and even more preferably 40 to 60 mol%, relative to the total amount (100 mol%) of all constituent units that make up the polymer compound. The proportion of constituent units (a10) in the polymer compound is preferably 10 to 70 mol%, more preferably 20 to 60 mol%, and even more preferably 25 to 50 mol%, relative to the total amount (100 mol%) of all constituent units that make up the polymer compound. The proportion of constituent units (a5) in the polymer compound is preferably 3 to 25 mol%, more preferably 5 to 25 mol%, and even more preferably 8 to 20 mol%, relative to the total amount (100 mol%) of all constituent units that make up the polymer compound. The proportion of constituent units (a0d) in the polymer compound is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and even more preferably 3 to 10 mol%, relative to the total amount (100 mol%) of all constituent units that make up the polymer compound.

[0326] In a polymer compound consisting of constituent units (a1), (a10), (a0b), and (a0d), The proportion of constituent units (a1) is more preferably 10 to 80 mol%, even more preferably 30 to 70 mol%, and even more preferably 40 to 60 mol%, relative to the total amount (100 mol%) of all constituent units that make up the polymer compound. The proportion of constituent units (a10) in the polymer compound is preferably 10 to 70 mol%, more preferably 20 to 60 mol%, and even more preferably 25 to 50 mol%, relative to the total amount (100 mol%) of all constituent units that make up the polymer compound. The proportion of constituent units (a0b) in the polymer compound is preferably 3 to 25 mol%, more preferably 5 to 25 mol%, and even more preferably 8 to 20 mol%, relative to the total amount (100 mol%) of all constituent units that make up the polymer compound. The proportion of constituent units (a0d) in the polymer compound is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and even more preferably 3 to 10 mol%, relative to the total amount (100 mol%) of all constituent units that make up the polymer compound.

[0327] Component (A1) can be produced by dissolving monomers that induce each constituent unit in a polymerization solvent and then adding a radical polymerization initiator such as azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyrate (e.g., V-601) to the mixture and polymerizing it. Examples of monomers that induce each constituent unit include monomers that induce constituent unit (a10), monomers that induce constituent unit (a1), and monomers that induce other arbitrary constituent units (e.g., constituent unit (a4), constituent unit (st), etc.). These monomers (e.g., monomers that induce constituent unit (a10)) may have their hydroxyl groups or the like protected as needed. In this case, component (A1) can be produced by carrying out a deprotection reaction after the polymerization reaction as described above. During polymerization, a chain transfer agent such as HS-CH2-CH2-CH2-C(CF3)2-OH may be used in combination to introduce a -C(CF3)2-OH group at the terminal. Copolymers in which a hydroxyalkyl group, in which some of the hydrogen atoms of the alkyl group are replaced with fluorine atoms, are introduced in this way are effective in reducing development defects and LER (line edge roughness: uneven unevenness of the line sidewall).

[0328] The weight-average molecular weight (Mw) of component (A1) (based on polystyrene conversion by gel permeation chromatography (GPC)) is not particularly limited, but is preferably 1,000 to 50,000, more preferably 5,000 to 40,000, and even more preferably 5,000 to 30,000. If the Mw of component (A1) is below the preferred upper limit of this range, it has sufficient solubility in the resist solvent for use as a resist, and if it is above the preferred lower limit of this range, it has good dry etching resistance and a good cross-sectional shape of the resist pattern. (A1) The degree of dispersion of component (Mw / Mn) is not particularly limited, but is preferably 1.0 to 4.0, more preferably 1.0 to 3.0, and particularly preferably 1.0 to 2.0. Mn represents the number-average molecular weight.

[0329] (A2) About the ingredients The resist composition of this embodiment may also include, as component (A), a base component (hereinafter referred to as "component (A2)") that does not correspond to component (A1) and whose solubility in the developer changes due to the action of an acid. (A2) The component is not particularly limited and can be arbitrarily selected from a large number of components that have been conventionally known as base components for chemically amplified resist compositions. (A2) Component may be a single high-molecular-weight compound or a low-molecular-weight compound, or two or more may be used in combination.

[0330] The proportion of component (A1) in component (A) is preferably 25% by mass or more, more preferably 50% by mass or more, even more preferably 75% by mass or more, and may also be 100% by mass, based on the total mass of component (A). When the proportion is 25% by mass or more, sensitivity tends to improve, and a resist pattern with excellent lithography characteristics such as resolution and roughness is more easily formed.

[0331] In the resist composition of this embodiment, the content of component (A) may be adjusted according to the resist film thickness to be formed.

[0332] <Acid generating agent component (B)> The resist composition of this embodiment may contain an acid-generating agent component (B) that generates acid upon exposure. (B) The component is not particularly limited, and any acid generators previously proposed for chemically amplified resist compositions can be used. Examples of such acid generators include onium salt-based acid generators such as iodonium salts and sulfonium salts, oximesulfonate-based acid generators; diazomethane-based acid generators such as bisalkyl or bisarylsulfonyl diazomethanes and poly(bissulfonyl) diazomethanes; nitrobenzyl sulfonate-based acid generators, iminosulfonate-based acid generators, and disulfone-based acid generators, among many others. The form in which component (B) is contained may be in the form of a compound, or it may be incorporated into component (A1) as the above-mentioned constituent unit (a5), or it may be in both of these forms.

[0333] Examples of onium salt-based acid generators include the compound represented by the following general formula (b-1) (hereinafter also referred to as "component (b-1)"), the compound represented by the general formula (b-2) (hereinafter also referred to as "component (b-2)"), or the compound represented by the general formula (b-3) (hereinafter also referred to as "component (b-3)").

[0334] [ka] [In the formula, R 101 and R 104 ~R 108 Each of these is independently a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents. 104 and R 105 These may be bonded to each other to form a ring structure. 102 This is a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom. 101 This is a divalent linking group or single bond containing an oxygen atom. 101 ~V 103 Each of these is independently a single bond, an alkylene group, or a fluorinated alkylene group. However, Y 101 and V 101 L cannot be a single bond at the same time. 101 ~L 102 Each of these is independently either a single bond or an oxygen atom. 103 ~L 105 These are, independently, single bonds, -CO-, or -SO2-. m is an integer greater than or equal to 1, and M' m+ This is an onium cation with a valence of m.

[0335] {Anion Division} • Anion in component (b-1) In formula (b-1), R 101 This is a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents.

[0336] Cyclic groups that may have substituents: The cyclic group is preferably a cyclic hydrocarbon group, which may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity. Furthermore, the aliphatic hydrocarbon group is preferably saturated.

[0337] R 101 The aromatic hydrocarbon group in this formula is a hydrocarbon group having an aromatic ring. The number of carbon atoms in the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, this number of carbon atoms does not include the number of carbon atoms in substituents. R 101 Specific examples of aromatic rings in aromatic hydrocarbon groups include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic heterocycles in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, nitrogen atoms, etc. R 101 Specific examples of aromatic hydrocarbon groups in this context include groups obtained by removing one hydrogen atom from the aromatic ring (aryl groups: for example, phenyl groups, naphthyl groups, etc.), and groups in which one of the hydrogen atoms of the aromatic ring is replaced by an alkylene group (for example, benzyl groups, phenethyl groups, 1-naphthylmethyl groups, etc.). The number of carbon atoms in the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0338] R 101 In this context, cyclic aliphatic hydrocarbon groups include aliphatic hydrocarbon groups that contain a ring in their structure. Examples of aliphatic hydrocarbon groups containing a ring in this structure include alicyclic hydrocarbon groups (groups from which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. A preferred monocyclic alicyclic hydrocarbon group is a group obtained by removing one or more hydrogen atoms from a monocycloalkane. The monocycloalkane is preferably one having 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. A preferred polycyclic alicyclic hydrocarbon group is a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 30 carbon atoms. Among these, adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 Polycycloalkanes having a cross-linked ring polycyclic skeleton such as decane and tetracyclododecane; polycycloalkanes having a fused ring polycyclic skeleton such as a cyclic group having a steroid skeleton are more preferred.

[0339] Among them, R 101 The cyclic aliphatic hydrocarbon group in is preferably a monocycloalkane or polycycloalkane from which one or more hydrogen atoms have been removed, more preferably a polycycloalkane from which one hydrogen atom has been removed, even more preferably an adamantyl group or a norbornyl group, and particularly preferably an adamantyl group.

[0340] The linear aliphatic hydrocarbon group, which may be bonded to the alicyclic hydrocarbon group, preferably has 1 to 10 carbon atoms, more preferably 1 to 6, even more preferably 1 to 4, and most preferably 1 to 3. Examples of linear aliphatic hydrocarbon groups include linear alkylene groups, specifically methylene groups [-CH2-], ethylene groups [-(CH2)2-], trimethylene groups [-(CH2)3-], tetramethylene groups [-(CH2)4-], pentamethylene groups [-(CH2)5-], and the like. The branched aliphatic hydrocarbon group, which may be bonded to the alicyclic hydrocarbon group, preferably has 2 to 10 carbon atoms, more preferably 3 to 6, even more preferably 3 or 4, and most preferably 3. Preferred branched aliphatic hydrocarbon groups include branched alkylene groups, specifically alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkylalkylene groups such as alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. In the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0341] Also, R 101 The cyclic hydrocarbon group in the above may contain heteroatoms, such as heterocycles. Specifically, examples include lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-7), -SO2--containing cyclic groups represented by the general formulas (b5-r-1) to (b5-r-4), and other heterocyclic groups represented by the chemical formulas (r-hr-1) to (r-hr-16).

[0342] R 101 Examples of substituents on the cyclic group include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, and nitro groups. As the alkyl group used as a substituent, an alkyl group having 1 to 5 carbon atoms is preferred. As the substituent, an alkoxy group having 1 to 5 carbon atoms is preferred, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group are more preferred, and a methoxy group and an ethoxy group are most preferred. Preferred halogen atoms as substituents are fluorine, bromine, and iodine atoms. Examples of alkyl halides used as substituents include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, and tert-butyl groups, in which some or all of the hydrogen atoms are substituted with the halogen atoms. A carbonyl group as a substituent is a group that substitutes for a methylene group (-CH2-) that constitutes a cyclic hydrocarbon group.

[0343] R 101 The cyclic hydrocarbon group in may be a fused ring group containing a fused ring formed by the fusion of an aliphatic hydrocarbon ring and an aromatic ring. Examples of the fused ring include a polycycloalkane having a bridging ring system with one or more aromatic rings fused to it. Specific examples of the bridging ring system polycycloalkane include bicycloalkanes such as bicyclo[2.2.1]heptane (norbornane) and bicyclo[2.2.2]octane. The fused ring group is preferably a group containing a fused ring formed by the fusion of two or three aromatic rings to a bicycloalkane, and more preferably a group containing a fused ring formed by the fusion of two or three aromatic rings to bicyclo[2.2.2]octane. 101 Specific examples of fused ring groups in this context include the groups represented by the following formulas (r-br-1) to (r-br-2). In the formulas, * represents Y in formula (b-1). 101 This represents a coupling that connects to something.

[0344] [ka]

[0345] R 101Examples of substituents that the fused ring group in the compound may have include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, nitro groups, aromatic hydrocarbon groups, and alicyclic hydrocarbon groups. The alkyl group, alkoxy group, halogen atom, and halogenated alkyl group as substituents of the fused cyclic group are as described above in R 101 Examples of substituents on cyclic groups in the above are similar to those listed. Examples of aromatic hydrocarbon groups as substituents on the fused ring group include groups obtained by removing one hydrogen atom from an aromatic ring (aryl groups: for example, phenyl groups, naphthyl groups, etc.), groups in which one of the hydrogen atoms of the aromatic ring is replaced by an alkylene group (for example, arylalkyl groups such as benzyl groups, phenethyl groups, 1-naphthylmethyl groups, 2-naphthylmethyl groups, 1-naphthylethyl groups, 2-naphthylethyl groups, etc.), and heterocyclic groups represented by the above formulas (r-hr-1) to (r-hr-6). Examples of alicyclic hydrocarbon groups as substituents on the aforementioned fused ring group include groups obtained by removing one hydrogen atom from monocycloalkanes such as cyclopentane and cyclohexane; adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 Examples include groups obtained by removing one hydrogen atom from polycycloalkanes such as decane and tetracyclododecane; lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-7); -SO2-containing cyclic groups represented by the general formulas (b5-r-1) to (b5-r-4); and heterocyclic groups represented by the formulas (r-hr-7) to (r-hr-16).

[0346] Chain-like alkyl groups that may have substituents: R 101 The chain-like alkyl group may be either linear or branched. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15, and most preferably 1 to 10. The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15, and most preferably 3 to 10. Specifically, examples include 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, and 4-methylpentyl group.

[0347] A chain-like alkenyl group which may have substituents: R 101 The linear alkenyl group may be linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5, even more preferably 2 to 4, and particularly preferably 3. Examples of linear alkenyl groups include vinyl groups, propenyl groups (allyl groups), and butenyl groups. Examples of branched alkenyl groups include 1-methylvinyl groups, 2-methylvinyl groups, 1-methylpropenyl groups, and 2-methylpropenyl groups. Among the above, linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred.

[0348] R 101 Examples of substituents in the chain-like alkyl or alkenyl group include alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, nitro groups, amino groups, and the above R 101 Examples include cyclic groups in this context.

[0349] In formula (b-1), Y 101 It is a single bond or a divalent linking group containing an oxygen atom. Y 101 If Y is a divalent linking group containing an oxygen atom, 101 It may contain atoms other than oxygen atoms. Examples of atoms other than oxygen atoms include carbon atoms, hydrogen atoms, sulfur atoms, nitrogen atoms, etc. Examples of divalent linking groups containing an oxygen atom include the linking groups represented by the general formulas (L-al-1) to (L-al-8) above. Note that in the general formulas (L-al-1) to (L-al-8) below, R in formula (b-1) above 101 The combination with this is V' in the following general formulas (L-al-1)~(L-al-8). 101 That is the case.

[0350] In formula (b-1), V 101 These are single bonds, alkylene groups, or fluorinated alkylene groups. Among them, V 101 It is preferable that the fluorinated alkylene group is a single bond or a linear chain having 1 to 4 carbon atoms.

[0351] In formula (b-1), R 102 R is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. 102 It is preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and more preferably a fluorine atom.

[0352] A specific example of the anion part represented by the above formula (b-1) is, for example, Y 101 When it is a single bond, examples include fluorinated alkyl sulfonate anions such as trifluoromethanesulfonate anions and perfluorobutanesulfonate anions; Y 101 When is a divalent linking group containing an oxygen atom, the anions can be represented by any of the following formulas (an-1) to (an-3).

[0353] [ka] [In the formula, R” 101 R” is an optionally substituted aliphatic cyclic group, a monovalent heterocyclic group represented by the above chemical formulas (r-hr-1) to (r-hr-16), a fused cyclic group represented by the above formula (r-br-1) or (r-br-2), an optionally substituted linear alkyl group, or an optionally substituted aromatic cyclic group. 102R” is an aliphatic cyclic group which may have substituents, a fused cyclic group represented by formula (r-br-1) or (r-br-2), a lactone-containing cyclic group represented by the general formulas (a2-r-1), (a2-r-3) to (a2-r-7), respectively, or a -SO2-containing cyclic group represented by the general formulas (b5-r-1) to (b5-r-4), respectively. 103 V” is an optionally substituted aromatic cyclic group, an optionally substituted aliphatic cyclic group, or an optionally substituted linear alkenyl group. 101 This is a single bond, an alkylene group having 1 to 4 carbon atoms, or a fluorinated alkylene group having 1 to 4 carbon atoms. 102 [wherein 'v' is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms; where 'v' is an independent integer from 0 to 3, where 'q' is an independent integer from 0 to 20, and where 'n' is 0 or 1.]

[0354] R" 101 , R” 102 and R” 103 The aliphatic cyclic group which may have substituents is R in formula (b-1) above. 101 It is preferable that the substituent is the group exemplified as a cyclic aliphatic hydrocarbon group in formula (b-1). 101 Examples include substituents similar to those that may be substituted for the cyclic aliphatic hydrocarbon group in the above.

[0355] R" 101 and R” 103 The aromatic cyclic group which may have substituents in formula (b-1) is R 101 It is preferable that the substituent is the aromatic hydrocarbon group exemplified in the cyclic hydrocarbon group in formula (b-1). 101 Examples include substituents similar to those that may be substituted for the aromatic hydrocarbon group in the above.

[0356] R" 101 The chain-like alkyl group which may have substituents in formula (b-1) is R 101 It is preferable that the group is one of the examples given as a chain-like alkyl group in the compound. R" 103 The chain-like alkenyl group which may have substituents in formula (b-1) is R 101 It is preferable that the group is one of the examples given as a chain-like alkenyl group in the formula.

[0357] • Anion in component (b-2) In formula (b-2), R 104 , R 105 Each of these is independently a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents, and each of them is R in formula (b-1). 101 Similar examples can be given. However, R 104 , R 105 These may be bonded to each other to form a ring. R 104 , R 105 The alkyl group is preferably a linear alkyl group which may have substituents, and more preferably a linear or branched alkyl group, or a linear or branched fluorinated alkyl group. The number of carbon atoms in the chain-like alkyl group is preferably 1 to 10, more preferably 1 to 7, and even more preferably 1 to 3. 104 , R 105 The number of carbon atoms in the chain-like alkyl group is preferably small within the above range of carbon atoms, for reasons such as good solubility in the resist solvent. 104 , R 105 In the chain-like alkyl group, a larger number of hydrogen atoms substituted with fluorine atoms is preferable because it increases the acid strength and improves transparency to high-energy light and electron beams below 250 nm. The proportion of fluorine atoms in the chain-like alkyl group, i.e., the fluorination rate, is preferably 70-100%, more preferably 90-100%, and most preferably a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms. In formula (b-2), V 102 , V 103 These are, independently, a single bond, an alkylene group, or a fluorinated alkylene group, and each is V in formula (b-1).101 Similar examples include the above. In formula (b-2), L 101 , L 102 Each of these is either a single bond or an oxygen atom, independently of the others.

[0358] • Anion in component (b-3) In formula (b-3), R 106 ~R 108 Each of these is independently a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents, and each of them is R in formula (b-1). 101 Similar examples include the above. In formula (b-3), L 103 ~L 105 These are, independently, single bonds, -CO-, or -SO2-.

[0359] Among the above, the anion portion of component (B) is preferably the anion in component (b-1), and more preferably the anion represented by the formula (an-1).

[0360] {cation part} In the above equations (b-1), (b-2), and (b-3), M' m+ This represents an m-valent onium cation. Among these, sulfonium cations and iodonium cations are preferred. m is an integer of 1 or greater.

[0361] As the cation portion of component (B), a sulfonium cation is preferred, the cations represented by formulas (ca-1) to (ca-3) are more preferred, the cation represented by formula (ca-1) is even more preferred, and the cations represented by formulas (ca-1-1) to (ca-1-84) are particularly preferred.

[0362] Compound (B0): Component (B) may include compound (B0) represented by the following general formula (b0).

[0363] [ka] [In the formula, Mc + Xb is a cation represented by the general formula (c0) above. - [b-an-1] is at least one anion selected from the group consisting of anions represented by any of the following general formulas (b-an-1), (b-an-2), and (b-an-3).

[0364] [ka] [In the formula, R 101 and R 104 ~R 108 Each of these is independently a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents. 104 and R 105 These may bond to each other to form a ring structure. 102 This is a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom. 101 This is a divalent linking group or single bond containing an oxygen atom. 101 ~V 103 Each of these is independently an alkylene group, a fluorinated alkylene group, or a single bond. However, Y 101 and V 101 It is impossible for them to be single bonds at the same time. 101 and L 102 Each of these is independently either an oxygen atom or a single bond. 103 ~L 105 These are, independently, -CO-, -SO2-, or single bonds.

[0365] In the above general formulas (b-an-1), (b-an-2), and (b-an-3), R 101 , R 104 ~R 108 , Y 101 , V 101 ~V 103 , L 101 ~L 105 These are the same as those in the general formulas (b-1), (b-2), and (b-3) described above.

[0366] In the above general formula (b-an-1), R 101 The group is preferably an aromatic hydrocarbon group which may have substituents, and more preferably a phenyl group which may have substituents. R 101 However, if the aromatic hydrocarbon group may have substituents, it is preferable that the aromatic hydrocarbon group has iodine atoms as substituents. The number of iodine atoms as substituents can be 1 to 4, preferably 1 to 3, and more preferably 2 or 3.

[0367] The aforementioned Xb - This may be an anion represented by the following general formula (b0-an-001).

[0368] [ka]

[0369] In the above general formula (b0-an-001), R 001 This is a cyclic group which may have substituents. The cyclic group is preferably a cyclic hydrocarbon group, which may be an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or a fused cyclic group which includes a fused ring formed by the fusion of an aliphatic hydrocarbon ring and an aromatic ring. An aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity. Furthermore, the aliphatic hydrocarbon group is preferably saturated.

[0370] R 001 The aromatic hydrocarbon group in this formula is a hydrocarbon group having an aromatic ring. The number of carbon atoms in the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, this number of carbon atoms does not include the number of carbon atoms in substituents. R 001Specific examples of aromatic rings in aromatic hydrocarbon groups include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic heterocycles in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, nitrogen atoms, etc. R 001 Specific examples of aromatic hydrocarbon groups in this context include groups obtained by removing one hydrogen atom from the aromatic ring (aryl groups: for example, phenyl groups, naphthyl groups, etc.), and groups in which one of the hydrogen atoms of the aromatic ring is replaced by an alkylene group (for example, benzyl groups, phenethyl groups, 1-naphthylmethyl groups, etc.). The number of carbon atoms in the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0371] R 001 In this context, cyclic aliphatic hydrocarbon groups include aliphatic hydrocarbon groups that contain a ring in their structure. Examples of aliphatic hydrocarbon groups containing a ring in this structure include alicyclic hydrocarbon groups (groups from which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. A preferred monocyclic alicyclic hydrocarbon group is a group obtained by removing one or more hydrogen atoms from a monocycloalkane. The monocycloalkane is preferably one having 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. A preferred polycyclic alicyclic hydrocarbon group is a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 30 carbon atoms. Among these, adamantane, norbornane, isobornane, tricyclo[5.2.1.02,6 Polycycloalkanes having a cross-linked ring polycyclic skeleton such as decane and tetracyclododecane; polycycloalkanes having a fused ring polycyclic skeleton such as a cyclic group having a steroid skeleton are more preferred.

[0372] Among them, R 001 The cyclic aliphatic hydrocarbon group in is preferably a monocycloalkane or polycycloalkane from which one or more hydrogen atoms have been removed, more preferably a polycycloalkane from which one hydrogen atom has been removed, even more preferably an adamantyl group or a norbornyl group, and particularly preferably an adamantyl group.

[0373] Also, R 001 The cyclic hydrocarbon group in the above may contain heteroatoms, such as heterocycles. Specifically, examples include lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-7), -SO2--containing cyclic groups represented by the general formulas (b5-r-1) to (b5-r-4), and heterocyclic groups represented by the chemical formulas (r-hr-1) to (r-hr-16).

[0374] R 001 Examples of fused ring groups in which an aliphatic hydrocarbon ring and an aromatic ring are fused together include polycycloalkanes having a bridging ring polycyclic skeleton to which one or more aromatic rings are fused. Specific examples of the bridging ring polycycloalkanes include bicycloalkanes such as bicyclo[2.2.1]heptane (norbornane) and bicyclo[2.2.2]octane. The fused ring group preferably includes a fused ring to which two or three aromatic rings are fused to a bicycloalkane, and more preferably includes a fused ring to which two or three aromatic rings are fused to bicyclo[2.2.2]octane. 001 Specific examples of fused ring groups in this context include the groups represented by the following formulas (r-br-1) to (r-br-2). In the formulas, * represents Y in the general formula (b0-an-001). 001 This represents a coupling that connects to something.

[0375] [ka]

[0376] R 001 Substituents in the cyclic group include, for example, alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, nitro groups, acid-degradable groups, or combinations thereof. These are some examples. The alkyl group used as the substituent is preferably an alkyl group having 1 to 5 carbon atoms. The alkoxy group used as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, or tert-butoxy group, and most preferably a methoxy group or ethoxy group. The halogen atom used as a substituent is preferably a fluorine atom, a bromine atom, or an iodine atom, with iodine being more preferred. Examples of alkyl halides used as substituents include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, and tert-butyl groups, in which some or all of the hydrogen atoms are substituted with the halogen atoms. A carbonyl group as a substituent is a group that substitutes for a methylene group (-CH2-) that constitutes a cyclic hydrocarbon group. The acid-degradable group used as a substituent is preferably the group represented by the following formula (Rpg-2).

[0377] [ka] [In the formula, Rpgd' is an acid-dissociable group represented by the general formula (a1-r-1), the general formula (a1-r-2), or the general formula (a1-r-4). * is R in the general formula (b0-an-001). 001 This shows the bonding connections.

[0378] In the formula (Rpg-2), Rpgd' is preferably an acid-dissociable group represented by the general formula (a1-r-2), and more preferably an acid-dissociable group represented by the general formula (a1-r2-1).

[0379] In the above formula (b0-an-001), Y 001 This is a divalent linking group containing a heteroatom. Examples of divalent linking groups containing a heteroatom include non-hydrocarbon oxygen-containing linking groups such as ester bonds [-C(=O)-O-, -OC(=O)-], ether bonds (-O-), amide bonds (-C(=O)-NH-), carbonyl groups (-C(=O)-), and carbonate bonds (-OC(=O)-O-); and combinations of these non-hydrocarbon oxygen-containing linking groups with alkylene groups. Examples of divalent linking groups containing such heteroatoms include the linking groups represented by the following general formulas (L-01) to (L-04). Note that in the following general formulas (L-01) to (L-04), R in the above formula (b0-an-001) 001 The V' in the following general formulas (L-01) to (L-04) is what combines with it. 01 That is the case.

[0380] [ka] [In the formula, V' 01 V' is a single bond or an alkylene group with 1 to 5 carbon atoms. 02 V' is a divalent saturated hydrocarbon group having 1 to 30 carbon atoms. 03 X' is a divalent cyclic group which may have substituents, and X' 01 and X' 02 These are, independently, either -O- or -NH-.

[0381] V' 02 The saturated hydrocarbon group in is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 1 to 5 carbon atoms.

[0382] V' 01 and V' 02 The alkylene group in this product may be a linear alkylene group or a branched alkylene group, but a linear alkylene group is preferred. V' 01 and V'02 Specifically, the alkylene groups in these include: methylene group [-CH2-]; alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-; ethylene group [-CH2CH2-]; -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2 Examples include alkylethylene groups such as -CH2CH2CH2-; trimethylene groups (n-propylene groups) [-CH2CH2CH2-]; alkyltrimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; tetramethylene groups [-CH2CH2CH2CH2-]; alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-; and pentamethylene groups [-CH2CH2CH2CH2CH2-]. V' 01 A single bond is preferred.

[0383] V' 03 The divalent cyclic group in the above formula (b0-an-001) is R 001 One example is the cyclic group in which one more hydrogen atom has been removed. Among them, V' 03 The divalent cyclic group in is preferably a phenylene group, a 1,5-adamantilene group, a 2,6-adamantilene group, or a group represented by the following general formula (r-br-1-1) or (r-br-1-2), with the phenylene group being more preferred. In the formula, * represents a bond.

[0384] [ka]

[0385] V' 03 The substituents that the divalent cyclic group in (b0-an-001) may have include R 001 Examples include substituents similar to those in the cyclic group of . In particular, V' 03The substituents that the cyclic group in this compound may have are preferably halogen atoms, and more preferably iodine atoms.

[0386] In the above formula (b0-an-001), V 001 This is an alkylene group or a fluorinated alkylene group. Among them, V 001 It is preferably a linear fluorinated alkylene group having 1 to 4 carbon atoms. Preferably, it is a fluorinated alkylene group having 1 to 2 carbon atoms, and SO3 - It is preferable that a fluorine atom is bonded to an adjacent carbon atom.

[0387] The anion represented by the above formula (b0-an-001) may be an anion represented by the following general formulas (b0-an-1) to (b0-an-3).

[0388] [ka] [In the formula, R 011 Each of these is independently an optionally substituted aliphatic cyclic group, an optionally substituted aromatic cyclic group, or an optionally substituted fused cyclic group represented by the formula (r-br-1) or (r-br-2). V' 012 These are, independently, a single bond, an alkylene group with 1 to 4 carbon atoms, or a fluorinated alkylene group with 1 to 4 carbon atoms. V' 013 X' is a divalent cyclic group which may have substituents. 011 and X' 012 These are independently -O- or -NH-. 012 [v' is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. Each of v' is an independent integer between 0 and 3.]

[0389] R 011 The aliphatic cyclic group in the above formula (b0-an-001) is R 001 Examples of cyclic aliphatic hydrocarbon groups in are those listed above. Among them, R 011The aliphatic cyclic group in is preferably a monocycloalkane or polycycloalkane from which one or more hydrogen atoms have been removed, more preferably a polycycloalkane from which one hydrogen atom has been removed, even more preferably an adamantyl group or a norbornyl group, and particularly preferably an adamantyl group.

[0390] R 011 The aromatic cyclic group in the above formula (b0-an-001) is R 001 Examples of aromatic hydrocarbon groups in cyclic hydrocarbon groups include those listed above. In particular, R 011 In this compound, a phenyl group or a naphthyl group is preferred as the aromatic cyclic group.

[0391] R 011 The substituent in the above formula (b0-an-001) is R 001 Examples include substituents similar to those that the cyclic group in the above may have. R 011 Among the substituents that the aliphatic cyclic group in this compound may have, a hydroxyl group or a halogen atom is preferred, and an iodine atom is more preferred. R 011 Among the substituents that the aromatic cyclic group in this compound may have, halogen atoms are preferred, and iodine atoms are more preferred. R 011 Among the substituents that the group represented by the general formula (r-br-1-1) or (r-br-1-2) in the above formula may have, an acid-degradable group is preferred, and a group represented by the general formula (Rpg-2) is more preferred. In the above formula (Rpg-2), Rpgd' is preferably an acid-dissociable group represented by the general formula (a1-r-2), and an acid-dissociable group represented by the general formula (a1-r2-1) is more preferred.

[0392] V' 012 The alkylene group in (L-01) to (L-04) is V' 02 Examples of groups similar to the alkylene group in [the text] include [the text]. V' 012The alkylene group in is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and may be a linear alkylene group or a branched alkylene group, with a linear alkylene group being preferred.

[0393] V' 013 The divalent cyclic group in which substituents may be present is V' in formulas (L-01) to (L-04). 03 Examples include groups similar to the divalent cyclic groups in [the relevant context]. V' 013 The preferred divalent cyclic groups in this compound are phenylene groups, 1,5-adamantilene groups, 2,6-adamantilene groups, and groups represented by the general formula (r-br-1-1) or (r-br-1-2).

[0394] R 012 R is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. 012 It is preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and more preferably a fluorine atom.

[0395] Specific examples of compound (B0) are shown below, but are not limited to these. In the formula below, Mc + This is the aforementioned cation (C0).

[0396] [ka]

[0397] [ka]

[0398] Specific examples of compound (B0) are shown below, but are not limited to these.

[0399] [ka]

[0400] [ka]

[0401] If component (B) contains compound (B0), compound (B0) may be used alone or in combination of two or more types. If component (B) contains compound (B0), the proportion of compound (B0) in the total component (B) is, for example, 50% by mass or more, preferably 70% by mass or more, more preferably 95% by mass or more, and may be 100% by mass. (B) If the proportion of compound (B0) in component (B) is above the lower limit of the preferred range mentioned above, it becomes easier to achieve further increased sensitivity, reduced roughness, suppression of defects, and improved resolution.

[0402] In the resist composition of this embodiment, component (B) may be used alone or in combination of two or more types. If the resist composition contains component (B), the content of component (B) in the resist composition is preferably less than 50 parts by mass, more preferably 5 to 45 parts by mass, and even more preferably 10 to 43 parts by mass, per 100 parts by mass of component (A). (B) It is preferable to set the content of component (B) within the above preferred range, as this makes it easier to obtain a uniform solution when each component of the resist composition is dissolved in an organic solvent, resulting in good storage stability of the resist composition.

[0403] <Basic component (D)> The resist composition of this embodiment may contain, in addition to component (A), a basic component (component (D)) that traps the acid generated by exposure (i.e., controls the diffusion of the acid). Component (D) acts as a quencher (acid diffusion control agent) that traps the acid generated by exposure in the resist composition. Examples of component (D) include a photo-disintegrating base (D1) (hereinafter referred to as "component (D1)") that decomposes upon exposure and loses its ability to control acid diffusion, and a nitrogen-containing organic compound (D2) (hereinafter referred to as "component (D2)") that does not fall under component (D1). Among these, a photo-disintegrating base (component (D1)) is preferred because it is easier to improve the characteristics of high sensitivity, roughness reduction, and suppression of coating defects. The components (D1) and (D2) may be in the form of compounds, incorporated into component (A1) as the aforementioned structural unit (a6), or in both forms. The compound exemplified as component (D1) described later may be used as the aforementioned acid-generating component (component (B)) depending on the combination with other compounds.

[0404] • About the (D1) component The (D1) component is not particularly limited as long as it decomposes upon exposure and loses its acid diffusion controllability, and is preferably one or more compounds selected from the group consisting of the compound represented by the following general formula (d1-1) (hereinafter referred to as "(d1-1) component"), the compound represented by the following general formula (d1-2) (hereinafter referred to as "(d1-2) component"), and the compound represented by the following general formula (d1-3) (hereinafter referred to as "(d1-3) component"). Components (d1-1) to (d1-3) decompose in the exposed areas of the resist film and lose their acid diffusion control properties (basicity), so they do not act as quenchers, but they act as quenchers in the unexposed areas of the resist film.

[0405] [ka] [In the formula, Rd 1 ~Rd 4 Rd in formula (d1-2) is a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents. 2 In this example, assume that no fluorine atoms are bonded to the carbon atoms adjacent to the sulfur atoms. 1 is a single bond or a divalent linking group. m is an integer greater than or equal to Mm+ These are each independently m-valent organic cations.

[0406] {(d1-1) component} ··Anion Club In formula (d1-1), Rd 1 R' is a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents, and each of the above R' is... 201 Similar examples include the above. Among these, Rd 1 Preferred substituents are optionally substituted aromatic hydrocarbon groups, optionally substituted aliphatic cyclic groups, or optionally substituted linear alkyl groups. Examples of substituents these groups may have include hydroxyl groups, oxo groups, alkyl groups, aryl groups, fluorine atoms, fluorinated alkyl groups, lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-7), ether bonds, ester bonds, or combinations thereof. When ether bonds or ester bonds are included as substituents, they may be mediated via alkylene groups, and in this case, preferred substituents are the linking groups represented by the general formulas (L-al-1) to (L-al-5). Note that Rd 1 If the aromatic hydrocarbon group, aliphatic cyclic group, or linear alkyl group in has a linking group represented by the general formulas (L-al-1) to (L-al-8) as a substituent, then in the general formulas (L-al-1) to (L-al-8), Rd in formula (d1-1) 1 The carbon atom constituting the aromatic hydrocarbon group, aliphatic cyclic group, or linear alkyl group in the above general formula (L-al-1) to (L-al-8) is V'. 101 That is the case. Suitable examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and a polycyclic structure containing a bicyclooctane skeleton (a polycyclic structure consisting of a bicyclooctane skeleton and other ring structures). Examples of the aliphatic cyclic group include adamantane, norbornane, isobornane, and tricyclo[5.2.1.0 2,6It is more preferable that the group is obtained by removing one or more hydrogen atoms from a polycycloalkane such as decane or tetracyclododecane. The linear alkyl group is preferably one with 1 to 10 carbon atoms, and specifically includes linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups; and branched alkyl groups such as 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, and 4-methylpentyl groups.

[0407] When the chain-like alkyl group is a fluorinated alkyl group having a fluorinated alkyl group as a substituent, the number of carbon atoms in the fluorinated alkyl group is preferably 1 to 11, more preferably 1 to 8, and even more preferably 1 to 4. The fluorinated alkyl group may contain atoms other than fluorine. Examples of atoms other than fluorine include oxygen atoms, sulfur atoms, nitrogen atoms, and the like.

[0408] The following are preferred specific examples of the anionic portion of component (d1-1).

[0409] [ka]

[0410] ··Cation section In formula (d1-1), M m+ This is an m-valent organic cation. M m+ Suitable organic cations include those similar to the cations represented by the general formulas (ca-1) to (ca-3), respectively, with the cation represented by the general formula (ca-1) being more preferred, and the cations represented by the formulas (ca-1-1) to (ca-1-84) being even more preferred. (d1-1) Component may be used alone or in combination of two or more types.

[0411] {(d1-2) component} ··Anion Club In formula (d1-2), Rd 2 R' is a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents. 201 Similar examples include the above. However, Rd 2 In this mixture, we assume that the carbon atom adjacent to the S atom is not bonded to a fluorine atom (i.e., not fluorine-substituted). This results in the anions of components (d1-2) becoming appropriately weak acid anions, improving the quenching ability of component (D). Rd 2 The alkyl group is preferably a chain-like alkyl group which may have substituents, or an aliphatic cyclic group which may have substituents, and more preferably an aliphatic cyclic group which may have substituents.

[0412] The chain-like alkyl group preferably has 1 to 10 carbon atoms, and more preferably 3 to 10 carbon atoms. Examples of the aliphatic cyclic group include adamantane, norbornane, isobornane, and tricyclo[5.2.1.0 2,6 A group obtained by removing one or more hydrogen atoms from decane, tetracyclododecane, etc. (which may have substituents); more preferably a group obtained by removing one or more hydrogen atoms from camphor.

[0413] Rd 2 The hydrocarbon group may have substituents, and such substituents may be Rd of formula (d1-1). 1 Examples include substituents similar to those that may be present on hydrocarbon groups (aromatic hydrocarbon groups, aliphatic cyclic groups, and linear alkyl groups) in the above.

[0414] The following are preferred specific examples of the anionic portion of component (d1-2).

[0415] [ka]

[0416] ··Cation section In formula (d1-2), M m+ is an m-valent organic cation, and M in formula (d1-1) above. m+ It is similar to that. (d1-2) Components may be used individually or in combination of two or more.

[0417] {(d1-3) components} ··Anion Club In formula (d1-3), Rd 3 R' is a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents, and the R' 201 Similar to the above, it is preferable that the group is a cyclic group containing a fluorine atom, a linear alkyl group, or a linear alkenyl group. Among these, a fluorinated alkyl group is preferred, and the above Rd 1 A fluorinated alkyl group similar to the one shown is more preferable.

[0418] In formula (d1-3), Rd 4 R' is a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents. 201 Similar examples include the above. In particular, alkyl groups, alkoxy groups, alkenyl groups, and cyclic groups, which may have substituents, are preferred. Rd 4 The alkyl group in is preferably a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc. 4 Some of the hydrogen atoms in the alkyl group may be substituted with hydroxyl groups, cyano groups, etc. Rd 4The alkoxy group in is preferably an alkoxy group having 1 to 5 carbon atoms. Specifically, examples of alkoxy groups having 1 to 5 carbon atoms include the methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, and tert-butoxy group. Among these, the methoxy group and ethoxy group are preferred.

[0419] Rd 4 The alkenyl group in R' 201 Examples of alkenyl groups similar to those in the above include vinyl groups, propenyl groups (allyl groups), 1-methylpropenyl groups, and 2-methylpropenyl groups, which are preferred. These groups may further have substituents of an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms.

[0420] Rd 4 The cyclic group in is the R' 201 Examples of cyclic groups similar to those in [5.2.1.0] include cyclopentane, cyclohexane, adamantane, norbornane, isobornane, and tricyclo[5.2.1.0]. 2,6 A preferred alicyclic group is obtained by removing one or more hydrogen atoms from a cycloalkane such as decane or tetracyclododecane, or an aromatic group such as a phenyl group or naphthyl group. 4 When Rd is an alicyclic group, the resist composition dissolves well in organic solvents, resulting in good lithography properties. 4 When the group is an aromatic group, the resist composition exhibits excellent light absorption efficiency and good sensitivity and lithographic characteristics in lithography using EUV or the like as the exposure light source.

[0421] In formula (d1-3), Yd 1 It is a single bond or a divalent linking group. Yd 1 The divalent linking group in formula (a2-1) is not particularly limited, but may include divalent hydrocarbon groups (aliphatic hydrocarbon groups, aromatic hydrocarbon groups) which may have substituents, and divalent linking groups containing heteroatoms. 21Examples include divalent hydrocarbon groups that may have substituents, and divalent linking groups containing heteroatoms, as mentioned in the explanation of divalent linking groups in [reference]. Yd 1 The preferred members are carbonyl groups, ester bonds, amide bonds, alkylene groups, or combinations thereof. The alkylene group is more preferably a linear or branched alkylene group, and even more preferably a methylene group or an ethylene group.

[0422] The following are preferred specific examples of the anionic parts of components (d1-3).

[0423] [ka]

[0424] [ka]

[0425] ··Cation section In formula (d1-3), M m+ is an m-valent organic cation, and M in formula (d1-1) above. m+ It is similar to that. (d1-3) Components may be used individually or in combination of two or more.

[0426] Component (D1) may consist of only one of the above components (d1-1) to (d1-3), or it may consist of a combination of two or more components. If the resist composition contains component (D1), the content of component (D1) in the resist composition is preferably 0.5 to 15 parts by mass, more preferably 1 to 15 parts by mass, and even more preferably 2 to 15 parts by mass, per 100 parts by mass of component (A).

[0427] Component (D1) preferably contains the above-mentioned component (d1-1). The content of component (d1-1) in the total amount of component (D1) is preferably 50% by mass or more, preferably 70% by mass or more, and more preferably 90% by mass or more, and component (D1) may consist only of compound (d1-1).

[0428] (D1) Method for producing component: The methods for producing the aforementioned components (d1-1) and (d1-2) are not particularly limited and can be produced by known methods. Furthermore, the method for producing components (d1-3) is not particularly limited and may be, for example, similar to the method described in US2012-0149916. As an example of a basic component (component (D)) that traps the acid generated by exposure, a compound of component (D1) is shown, but the compound of component (D1) may also be used as component (B). For example, in the resist composition of this embodiment, the compound of component (D1) may be used as component (B), and the compound that generates an acid with lower acidity than the acid generated by the compound of component (D1) upon exposure may be used as component (D). Alternatively, in the resist composition of this embodiment, the compound of component (D1) may be used as component (B), and the component (D2), which will be described later, may be used as component (D).

[0429] Compound (D0): Component (D) may include compound (D0) represented by the following general formula (d0).

[0430] [ka] [In the formula, Mc + Xd is a cation represented by the general formula (c0) above. - This is at least one anion selected from the group consisting of anions represented by any of the following general formulas (d1-an-1), (d1-an-2), and (d1-an-3).

[0431] [ka] [In the formula, Rd 1 ~Rd 4 Each of these is independently an optionally substituted cyclic group, an optionally substituted linear alkyl group, or an optionally substituted linear alkenyl group. However, Rd in formula (d1-an-2) 2 In this example, assume that no fluorine atom is bonded to the carbon atom adjacent to the sulfur atom. 1 This is a divalent linking group or a single bond.

[0432] In the above general formulas (d1-an-1), (d1-an-2), and (d1-an-3), Rd 1 ~Rd 4 , Yd 1 This is the same as in the general formulas (d1-1), (d1-2), and (d1-3) described above.

[0433] A concrete example of the general formula (d1-an-1) is the same as the concrete example of the anion part in the above formula (d1-1). A concrete example of the general formula (d1-an-2) is the same as the concrete example of the anion part in the above formula (d1-2). A concrete example of the general formula (d1-an-3) is the same as the concrete example of the anion part in the above formula (d1-3).

[0434] Rd in the above equation (d0-1) 1 The group is preferably an aromatic hydrocarbon group which may have substituents, and more preferably a phenyl group which may have substituents. Rd 1 However, if the aromatic hydrocarbon group may have substituents, it is preferable that the aromatic hydrocarbon group has iodine atoms as substituents. The number of iodine atoms as substituents can be 1 to 4, preferably 1 to 3, and more preferably 2 or 3.

[0435] Specific examples of compound (D0) are shown below, but are not limited to these. In the formula below, Mc + This is the aforementioned cation (C0).

[0436] [ka]

[0437] Specific examples of compound (D0) are shown below, but are not limited to these.

[0438] [ka]

[0439] [ka]

[0440] If component (D1) contains compound (D0), compound (D0) may be used alone or in combination of two or more types. If component (D1) contains compound (D0), the proportion of compound (D0) in the total component (D1) is, for example, 50% by mass or more, preferably 70% by mass or more, more preferably 95% by mass or more, and may be 100% by mass. If the proportion of compound (D0) in component (D) is above the lower limit of the preferred range mentioned above, it becomes easier to achieve further increased sensitivity, reduced roughness, suppression of defects, and improved resolution.

[0441] • About the (D2) component Component (D) may include nitrogen-containing organic compounds that do not fall under component (D1) above (hereinafter referred to as "component (D2)"). Component (D2) is not particularly limited as long as it acts as an acid diffusion control agent and does not fall under component (D1), and any known component may be used. Among these, aliphatic amines are preferred, and among these, secondary aliphatic amines and tertiary aliphatic amines are more preferred. An aliphatic amine is an amine having one or more aliphatic groups, and it is preferable that the aliphatic group has 1 to 12 carbon atoms. Examples of aliphatic amines include amines (alkylamines or alkyl alcoholamines) or cyclic amines in which at least one hydrogen atom of ammonia (NH3) is substituted with an alkyl group or hydroxyalkyl group having 12 or fewer carbon atoms. Specific examples of alkylamines and alkyl alcoholamines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-decylamine; dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine, and dicyclohexylamine; trialkylamines such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, and tri-n-dodecylamine; and alkyl alcoholamines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, and tri-n-octanolamine. Among these, trialkylamines having 6 to 30 carbon atoms are more preferred, and tri-n-pentylamine or tri-n-octylamine are particularly preferred.

[0442] Examples of cyclic amines include heterocyclic compounds containing a nitrogen atom as a heteroatom. These heterocyclic compounds may be monocyclic (aliphatic monocyclic amines) or polycyclic (aliphatic polycyclic amines). Examples of aliphatic monocyclic amines include piperidine and piperazine. As aliphatic polycyclic amines, those having 6 to 10 carbon atoms are preferred, and specifically, examples include 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, hexamethylenetetramine, and 1,4-diazabicyclo[2.2.2]octane.

[0443] Other aliphatic amines include tris(2-methoxymethoxyethyl)amine, tris{2-(2-methoxyethoxy)ethyl}amine, tris{2-(2-methoxyethoxymethoxy)ethyl}amine, tris{2-(1-methoxyethoxy)ethyl}amine, tris{2-(1-ethoxyethoxy)ethyl}amine, tris{2-(1-ethoxypropoxy)ethyl}amine, tris[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]amine, triethanolamine triacetate, etc., with triethanolamine triacetate being preferred.

[0444] Furthermore, an aromatic amine may be used as component (D2). Examples of aromatic amines include 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or their derivatives, trimenzylamine, 2,6-diisopropylaniline, N-tert-butoxycarbonylpyrrolidine, and 2,6-di-tert-butylpyridine.

[0445] (D2) Component may be used alone or in combination of two or more types. When the resist composition contains component (D2), the content of component (D2) in the resist composition is usually in the range of 0.01 to 5 parts by mass per 100 parts by mass of component (A). By using this range, the resist pattern shape, aging stability, etc., are improved.

[0446] <At least one compound (E) selected from the group consisting of organic carboxylic acids, phosphorus oxoacids and their derivatives> The resist composition of this embodiment may contain, as an optional component, at least one compound (E) selected from the group consisting of organic carboxylic acids and phosphorus oxoacids and their derivatives (hereinafter referred to as "component (E)"). Examples of organic carboxylic acids include acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, and salicylic acid, among which salicylic acid is preferred. Examples of phosphorus oxoacids include phosphoric acid, phosphonic acid, and phosphinic acid, with phosphonic acid being particularly preferred among these.

[0447] In the resist composition of this embodiment, component (E) may be used alone or in combination of two or more types. If the resist composition contains component (E), the content of component (E) is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 3 parts by mass, per 100 parts by mass of component (A). By setting the content within the above range, the lithography characteristics are further improved.

[0448] <Fluorine additive component (F)> The resist composition of this embodiment may contain a fluorine additive component (hereinafter referred to as "component (F)") as a hydrophobic resin. Component (F) is used to impart water repellency to the resist film and, when used as a resin separate from component (A), can improve lithography properties. As component (F), for example, fluorine-containing polymer compounds described in Japanese Patent Publication No. 2010-002870, Japanese Patent Publication No. 2010-032994, Japanese Patent Publication No. 2010-277043, Japanese Patent Publication No. 2011-13569, and Japanese Patent Publication No. 2011-128226 can be used. More specifically, component (F) includes polymers having a constituent unit (f1) represented by the following general formula (f1-1). This polymer is preferably a polymer (homopolymer) consisting only of the constituent unit (f1) represented by the following formula (f1-1); a copolymer of the constituent unit (f1) and the constituent unit (a1); and more preferably a copolymer of the constituent unit (f1) and a constituent unit derived from acrylic acid or methacrylic acid and the constituent unit (a1). Here, the constituent unit (a1) copolymerized with the constituent unit (f1) is preferably a constituent unit derived from 1-ethyl-1-cyclooctyl (meth)acrylate, and more preferably a constituent unit derived from 1-methyl-1-adamantyl (meth)acrylate.

[0449] [ka] [In the formula, R is the same as above, and Rf 102 and Rf 103 Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, and Rf 102 and Rf 103 They may be the same or different. 1 Rf is an integer between 0 and 5. 101 It is an organic group containing a fluorine atom.

[0450] In formula (f1-1), R bonded to the α-carbon atom is the same as described above. R is preferably a hydrogen atom or a methyl group. In formula (f1-1), Rf 102 and Rf 103 A fluorine atom is preferred as the halogen atom. Rf 102 and Rf 103 Examples of alkyl groups having 1 to 5 carbon atoms in R include those similar to the alkyl groups having 1 to 5 carbon atoms in R above, with methyl or ethyl groups being preferred. 102 and Rf103 Specifically, examples of halogenated alkyl groups having 1 to 5 carbon atoms include groups in which some or all of the hydrogen atoms of an alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. Fluorine atoms are preferred as the halogen atoms, particularly Rf. 102 and Rf 103 Preferably, the element is a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms; more preferably, a hydrogen atom, a fluorine atom, a methyl group, or an ethyl group; and even more preferably, a hydrogen atom. In formula (f1-1), nf 1 is an integer between 0 and 5, preferably between 0 and 3, and more preferably 1 or 2.

[0451] In formula (f1-1), Rf 101 This is an organic group containing a fluorine atom, and preferably a hydrocarbon group containing a fluorine atom. The hydrocarbon group containing fluorine atoms may be linear, branched, or cyclic, and preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and particularly preferably 1 to 10 carbon atoms. Furthermore, in hydrocarbon groups containing fluorine atoms, it is preferable that 25% or more of the hydrogen atoms in the hydrocarbon group are fluorinated, more preferably 50% or more are fluorinated, and particularly preferable that 60% or more are fluorinated, as this increases the hydrophobicity of the resist film during immersion exposure. Among them, Rf 101 More preferably, fluorinated hydrocarbon groups having 1 to 6 carbon atoms are used, with trifluoromethyl groups, -CH2-CF3, -CH2-CF2-CF3, -CH(CF3)2, -CH2-CH2-CF3, and -CH2-CH2-CF2-CF2-CF2-CF3 being particularly preferred.

[0452] The weight-average molecular weight (Mw) of component (F) (based on polystyrene conversion by gel permeation chromatography) is preferably 1,000 to 50,000, more preferably 5,000 to 40,000, and most preferably 10,000 to 30,000. If it is below the upper limit of this range, it has sufficient solubility in resist solvents for use as a resist, and if it is above the lower limit of this range, the water repellency of the resist film is good. The degree of dispersion of component (F) (Mw / Mn) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.0 to 2.5.

[0453] In the resist composition of this embodiment, component (F) may be used alone or in combination of two or more types. If the resist composition contains component (F), the content of component (F) is preferably 0.5 to 10 parts by mass, and more preferably 1 to 10 parts by mass, per 100 parts by mass of component (A).

[0454] <Organic solvent component (S)> The resist composition of this embodiment can be manufactured by dissolving the resist material in an organic solvent component (hereinafter referred to as "component (S)"). In the resist composition of this embodiment, component (S) may be used alone or as a mixture of two or more solvents. Among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), γ-butyrolactone, ethyl lactate (EL), and cyclohexanone are preferred.

[0455] Furthermore, a mixed solvent obtained by mixing PGMEA and a polar solvent is also preferred as component (S). The mixing ratio (mass ratio) can be appropriately determined considering the compatibility between PGMEA and the polar solvent. As component (S), a mixed solvent of at least one selected from PGMEA and EL and γ-butyrolactone is also preferred. In this case, the mass ratio of the former to the latter is preferably 70:30 to 95:5. The amount of component (S) used is not particularly limited and is set appropriately according to the coating thickness, at a concentration that can be applied to a substrate or the like. Generally, component (S) is used so that the solid content concentration of the resist composition is in the range of 0.1 to 20% by mass, preferably 0.2 to 15% by mass.

[0456] The resist composition of this embodiment may be subjected to removal of impurities after dissolving the resist material in component (S), using a polyimide porous membrane, a polyamide-imide porous membrane, or the like. For example, the resist composition may be filtered using a filter made of a polyimide porous membrane, a filter made of a polyamide-imide porous membrane, or a filter made of a polyimide porous membrane and a polyamide-imide porous membrane. Examples of the polyimide porous membrane and the polyamide-imide porous membrane include those described in Japanese Patent Application Publication No. 2016-155121.

[0457] Each of the above embodiments of the resist composition may contain component (S), and may optionally contain either or both of components (E) and (F).

[0458] The resist composition of this embodiment has an acid-generating ability that generates acid upon exposure. For example, component (A) may generate acid upon exposure, or component (B) may generate acid upon exposure. The resist composition of this embodiment may specifically contain, for example, (1) component (B) as a component that generates acid upon exposure; (2) component (A) as a component that generates acid upon exposure; or (3) component (A) as a component that generates acid upon exposure and also contains component (B). In other words, in the cases of (2) and (3) above, component (A) is a "base component that generates acid upon exposure and whose solubility in the developer changes due to the action of the acid." When component (A) is a base component that generates acid upon exposure and whose solubility in the developer changes due to the action of the acid, it is preferable that component (A1), described later, is a polymer compound that generates acid upon exposure and whose solubility in the developer changes due to the action of the acid.

[0459] When a resist film is formed using the resist composition of this embodiment and selective exposure is performed on the resist film, acid is generated in the exposed areas of the resist film, for example, from component (A) or component (B). The solubility of component (A) in the developer changes due to the action of this acid, while the solubility of component (A) in the developer does not change in the unexposed areas of the resist film. As a result, a difference in solubility in the developer occurs between the exposed and unexposed areas. Therefore, when the resist film is developed, if the resist composition is positive type, the exposed areas of the resist film are dissolved and removed to form a positive type resist pattern, and if the resist composition is negative type, the unexposed areas of the resist film are dissolved and removed to form a negative type resist pattern.

[0460] In this specification, a resist composition in which the exposed portion of the resist film is dissolved and removed to form a positive-type resist pattern is referred to as a positive-type resist composition, and a resist composition in which the unexposed portion of the resist film is dissolved and removed to form a negative-type resist pattern is referred to as a negative-type resist composition. The resist composition of this embodiment may be a positive-type resist composition or a negative-type resist composition. Furthermore, the resist composition of this embodiment may be for an alkaline development process using an alkaline developer in the development process during resist pattern formation, or for a solvent development process using a developer containing an organic solvent (organic developer) in the development process.

[0461] The resist composition of this embodiment may contain compound (B0) as compound (C). The resist composition of this embodiment may contain component (A1), compound (B0), and component (D). Alternatively, the resist composition of this embodiment may contain a component (A1) having a constituent unit (a6) and a compound (B0) component.

[0462] The resist composition of this embodiment may contain compound (D0) as compound (C). The resist composition of this embodiment may contain component (A1), component (B), and compound (D0). Alternatively, the resist composition of this embodiment may contain component (A1) having a constituent unit (a5) and compound (D0).

[0463] The resist composition of this embodiment may contain a resin component having a constituent unit (a0) as compound (C). The resin component may also be component (A1). The resist composition of this embodiment may contain component (A1) and component (D), which have the constituent unit (a0b). The resist composition of this embodiment may contain component (A1) and component (B), which have a constituent unit (a0d). The resist composition of this embodiment may contain a component (A1) having constituent units (a0b) and (a0d). The resist composition of this embodiment may contain a component (A1) having constituent units (a0b) and (a6). The resist composition of this embodiment may contain a component (A1) having constituent units (a5) and (a0d).

[0464] The resist composition of this embodiment may contain compound (B0) and compound (D0) as compound (C). The resist composition of this embodiment may contain component (A1), compound (B0), and compound (D0).

[0465] The resist composition of this embodiment may contain, as compound (C), a resin component having a constituent unit (a0) and compound (B0). The resin component may also be component (A1). The resist composition of this embodiment may contain component (A1) and component (B0) having the constituent unit (a0d).

[0466] The resist composition of this embodiment may contain, as compound (C), a resin component having a constituent unit (a0) and compound (D0). The resin component may also be component (A1). The resist composition of this embodiment may contain a component (A1) having a constituent unit (a0b), and a compound (D0).

[0467] The resist composition of this embodiment may contain, as compound (C), a resin component having a constituent unit (a0), compound (B0), and compound (D0). The resin component may also be component (A1). The resist composition of this embodiment may contain component (A1) having a constituent unit (a0b), compound (B0), and compound (D0). The resist composition of this embodiment may contain a component (A1) having a constituent unit (a0d), a compound (B0), and a compound (D0).

[0468] The resist composition of this embodiment described above contains a compound comprising a sulfonium cation having a succinic anhydride skeleton. Compared to conventional cations, sulfonium cations having a succinic anhydride skeleton are more easily decomposed by EUV (extreme ultraviolet) irradiation, resulting in increased acid generation. Therefore, even with low exposure levels, sufficient acid can be generated to deprotect the protective groups of the resin in the resist composition, which is expected to improve sensitivity. The succinic anhydride skeleton opens its ring during development, increasing its affinity for the developer, which is expected to reduce roughness and suppress the occurrence of defects.

[0469] (Method for forming resist patterns) A resist pattern formation method according to a second aspect of the present invention is a method comprising the steps of forming a resist film on a support using the resist composition according to the first aspect of the present invention described above, exposing the resist film, and developing the exposed resist film to form a resist pattern. One embodiment of such a resist pattern formation method is, for example, a resist pattern formation method carried out as follows.

[0470] First, the resist composition of the above-described embodiment is applied onto a support using a spinner or the like, and a bake (post-application bake (PAB)) treatment is performed for 40 to 120 seconds, preferably 60 to 90 seconds, at a temperature of, for example, 80 to 150°C, to form a resist film. Next, the resist film is subjected to selective exposure using an exposure apparatus such as an electron beam lithography apparatus or an ArF exposure apparatus, either through exposure via a mask (mask pattern) on which a predetermined pattern has been formed, or by direct irradiation with an electron beam without going through a mask pattern. After this, a bake (post-exposure bake (PEB)) treatment is performed for 40 to 120 seconds, preferably 60 to 90 seconds, at a temperature of, for example, 80 to 150°C. Next, the resist film is subjected to a developing process. In the case of an alkaline developing process, an alkaline developer is used, and in the case of a solvent developing process, a developer containing an organic solvent (organic developer) is used.

[0471] After the developing process, a rinsing process is preferably performed. In the case of an alkaline developing process, a water rinse using pure water is preferred, and in the case of a solvent developing process, a rinsing solution containing an organic solvent is preferred. In the case of a solvent development process, after the development or rinsing process, a process may be performed to remove the developer or rinse solution adhering to the pattern using a supercritical fluid. After development or rinsing, the film is dried. In some cases, a bake (post-bake) process may be performed after the development process.

[0472] The support material is not particularly limited and can be any conventionally known material, such as a substrate for electronic components or a substrate on which a predetermined wiring pattern has been formed. More specifically, examples include silicon wafers, metal substrates such as copper, chromium, iron, and aluminum, and glass substrates. As for the wiring pattern material, for example, copper, aluminum, nickel, and gold can be used.

[0473] The wavelength used for exposure is not particularly limited, and can be used with radiation such as ArF excimer lasers, KrF excimer lasers, F2 excimer lasers, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-rays, and soft X-rays. The resist pattern formation method of this embodiment is particularly useful in the step of exposing the resist film to EUV (extreme ultraviolet) or EB (electron beam).

[0474] The method for exposing the resist film may be conventional exposure (dry exposure) performed in an inert gas such as air or nitrogen, or it may be liquid immersion lithography. Immersion lithography is an exposure method in which the space between the resist film and the lens at the lowest position of the exposure apparatus is first filled with a solvent (immersion medium) that has a refractive index greater than that of air, and then exposure (immersion exposure) is performed in that state. The immersion medium is preferably a solvent having a refractive index greater than that of air and less than that of the resist film being exposed. Examples include water, fluorinated inert liquids, silicon-based solvents, and hydrocarbon-based solvents. Water is preferably used as the immersion medium.

[0475] Examples of alkaline developers used in the alkaline development process include 0.1 to 10% by mass of tetramethylammonium hydroxide (TMAH) aqueous solution. The organic solvent contained in the organic developer solution used in the solvent development process can be any solvent capable of dissolving component (A) (component (A) before exposure), and can be appropriately selected from known organic solvents. Specifically, examples include polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, as well as hydrocarbon solvents.

[0476] Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butanoate, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.

[0477] Examples of nitrile solvents include acetonitrile, propionitrile, valeronitrile, and butyronitrile.

[0478] Organic developers may contain known additives as needed. Examples of such additives include surfactants. While not particularly limited, surfactants such as ionic or nonionic fluorine-based and / or silicone-based surfactants can be used.

[0479] The development process can be carried out by known development methods, such as immersing the support in a developer solution for a certain period of time (dip method), piling the developer solution onto the surface of the support using surface tension and leaving it still for a certain period of time (paddle method), spraying the developer solution onto the surface of the support (spray method), or continuously dispensing the developer solution onto a support rotating at a constant speed while scanning the developer dispensing nozzle at a constant speed (dynamic dispensing method).

[0480] In the solvent-based development process, the rinsing solution used for rinsing after development can contain an organic solvent that is less likely to dissolve the resist pattern, selected from among the organic solvents listed above for use in the organic developer. Typically, at least one solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is used. These organic solvents may be used individually or in combination of two or more. They may also be used in mixtures with other organic solvents or water.

[0481] Rinsing (cleaning) using a rinsing solution can be carried out by known rinsing methods. Examples of such rinsing methods include continuously applying the rinsing solution onto a support rotating at a constant speed (rotary coating method), immersing the support in the rinsing solution for a certain period of time (dip method), and spraying the rinsing solution onto the surface of the support (spray method).

[0482] According to the resist pattern formation method of this embodiment described above, since the above-mentioned resist composition is used, when forming a resist pattern, it is possible to form a resist pattern with improved sensitivity, reduced roughness, suppressed defect occurrence, and improved resolution.

[0483] The resist compositions of the embodiments described above, and the various materials used in the pattern forming methods of the embodiments described above (for example, resist solvents, developers, rinse solutions, anti-reflective film forming compositions, topcoat forming compositions, etc.) are preferably free from impurities such as metals, metal salts containing halogens, acids, alkalis, sulfur atoms, or phosphorus atoms. Examples of metal atom-containing impurities include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Cr, Ni, Zn, Ag, Sn, Pb, Li, or salts thereof. The impurity content in these materials is preferably 200 ppb or less, more preferably 1 ppb or less, even more preferably 100 ppt (parts per trillion) or less, particularly preferably 10 ppt or less, and most preferably substantially free (below the detection limit of the measuring device).

[0484] (compound) The compound according to the third aspect of the present invention is a compound (hereinafter also referred to as "compound (M0)") containing a cation represented by the following general formula (c0). The cation in the compound according to the third aspect is the same as the cation (C0) described above in the first aspect.

[0485] [ka] [In the formula, R 01 and R 02 Each of these independently represents an optionally substituted aryl group, an optionally substituted alkyl group, or an optionally substituted alkenyl group. 01 and R 02 These may bond with each other to form a ring together with the sulfur atom in the formula. 03 represents a substituent. k is an integer between 0 and 3.

[0486] The compound according to the third embodiment may have a counter anion. Examples of counter anions include those listed as the anionic portion of the compound represented by the general formula (b0), those listed as the anionic portion of the compound represented by the general formula (d0), and those listed as the anionic portion of the compound represented by the general formula (a0-m).

[0487] Specific examples of compound (M0) include the compounds (B0), (D0), and (a0-m) mentioned above.

[0488] <Method for producing compounds> Compound (M0) can be produced by appropriately combining known methods, as shown in the <Synthesis Example of Compound> in the [Examples] section below.

[0489] (Acid generator) The acid generator according to the fourth aspect of the present invention comprises a compound represented by the following general formula (b0). The compound represented by the following general formula (b0) is the compound (B0) described above in the first aspect.

[0490] [ka] [In the formula, Mc + Xb is a cation represented by the following general formula (c0): - [b-an-1] is at least one anion selected from the group consisting of anions represented by any of the following general formulas (b-an-1), (b-an-2), and (b-an-3).

[0491] [ka] [In the formula, R 01 and R 02 Each of these independently represents an optionally substituted aryl group, an optionally substituted alkyl group, or an optionally substituted alkenyl group. 01 and R 02They may be mutually bonded to form a ring together with the sulfur atom in the formula. R 03 represents a substituent. k is an integer from 0 to 3. R 101 and R 104 ~R 108 are each independently a cyclic group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent. R 104 and R 105 may be mutually bonded to form a ring structure. R 102 is a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom. Y 101 is a divalent linking group containing an oxygen atom or a single bond. V 101 ~V 103 are each independently an alkylene group, a fluorinated alkylene group or a single bond. However, Y 101 and V 101 will not simultaneously become a single bond. L 101 and L 102 are each independently an oxygen atom or a single bond. L 103 ~L 105 are each independently -CO-, -SO2- or a single bond.]

[0492] The acid generator of this embodiment can be used in the production of the resist composition according to the above first aspect.

[0493] (Acid diffusion control agent) The acid diffusion control agent according to the fifth aspect of the present invention contains a compound represented by the following general formula (d0). The compound represented by the following general formula (d0) is the same as the compound (D) described above in the first aspect.

[0494] [Chemical formula] [In the formula, Mc + is a cation represented by the following general formula (c0). Xd -is at least one anion selected from the group consisting of anions represented by any of the following general formulas (d1-an-1), (d1-an-2), and (d1-an-3).

[0495] [Chemical formula] [In the formula, R 01 and R 02 each independently represent an aryl group which may have a substituent, an alkyl group which may have a substituent, or an alkenyl group which may have a substituent. R 01 and R 02 may be bonded to each other to form a ring together with the sulfur atom in the formula. R<​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​Rx represents a divalent linking group. - This is an anionic group. + This is a cation represented by the following general formula (c0). [ka] [In the formula, R 01 and R 02 Each of these independently represents an optionally substituted aryl group, an optionally substituted alkyl group, or an optionally substituted alkenyl group. 01 and R 02 These may bond with each other to form a ring together with the sulfur atom in the formula. 03 represents a substituent. k is an integer between 0 and 3.

[0499] Examples of compounds represented by the general formula (a0-m) include the compound represented by the following general formula (a0-1bm). The compound represented by the following general formula (a0-1bm) is useful for producing polymer compounds having the constituent unit represented by the general formula (a0-1b).

[0500] [ka] [In the formula, R m This is an alkyl group having 1 to 5 carbon atoms, an alkyl halide having 1 to 5 carbon atoms, a halogen atom, or a hydrogen atom. 50 This is a divalent linking group or a single bond. 50 n is a divalent hydrocarbon group which may have substituents. a5 is an integer between 0 and 2. 51 It is a divalent linking group. 5 This is a divalent linking group that may have a heteroatom, or a single bond. 51 and Ra 52 Each of these is independently a hydrogen atom, a fluorine atom, or a fluorinated alkyl group. n5 is an integer from 1 to 4. + This is the aforementioned cation (C0).

[0501] Rm , La 50 Ra 50 , n a5 , La 51 Ya 5 Ra 51 Ra 52 , and n5 are the same as those in formula (a0-1b) above.

[0502] Preferred specific examples of the compound represented by the above general formula (a0-1bm) include the following compounds. In the following formula, R α This represents a hydrogen atom, a methyl group, or a trifluoromethyl group. + This is the aforementioned cation (C0).

[0503] [ka]

[0504] Preferred specific examples of the compound represented by the above general formula (a0-1bm) include the following compounds.

[0505] [ka]

[0506] Examples of compounds represented by the general formula (a0-m) include those represented by the general formula (a0-1dm) below. Compounds represented by the general formula (a0-1dm) below are useful for producing polymer compounds having the constituent units represented by the general formula (a0-1d).

[0507] [ka] [In the formula, R m This is an alkyl group having 1 to 5 carbon atoms, an alkyl halide having 1 to 5 carbon atoms, a halogen atom, or a hydrogen atom. d0 This is a divalent linking group or a single bond. d0 n is a divalent hydrocarbon group which may have substituents.d This is an integer between 0 and 2. + This is the aforementioned cation (C0).

[0508] R m , La d0 Ra d0 , and n d These are the same as those in the above formula (a0-1d).

[0509] Preferred specific examples of compounds represented by the above general formula (a0-1dm) include the following compounds. In the following formula, R α This represents a hydrogen atom, a methyl group, or a trifluoromethyl group. + This is the aforementioned cation (C0).

[0510] [ka]

[0511] [ka]

[0512] Preferred specific examples of the compound represented by the above general formula (a0-1bm) include the following compounds.

[0513] [ka]

[0514] The constituent unit (a0) may also be the constituent unit (a0b) or the constituent unit (a0d). The polymer compound contains either or both of the constituent units (a0b) and (a0d). The polymer compound of this embodiment can be used in the production of the resist composition according to the first embodiment described above. [Examples]

[0515] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0516] <Examples of compound synthesis> As described below, in the synthesis of compounds (B)-1 to (B)-13 and (D)-1 to (D)-11, sulfides were first synthesized, followed by the synthesis of sulfoxides. Then, the sulfoxides were reacted with benzene derivatives, and the aforementioned compounds were obtained by exchanging anions.

[0517] (Synthesis of sulfides) Synthesis of sulfide (SF-01) In a three-necked flask containing thiophenol (TH-01) (8.8g, 80 mmol) and DMF (40 mL), potassium carbonate (11.1g, 80 mmol) was added and the mixture was stirred at 60°C for 1 hour. Next, 4-fluorophthalic anhydride (14.1g, 85 mmol) was added and the mixture was stirred for 5 hours. The reaction mixture was then added to 1 L of 0.1 mol / L hydrochloric acid solution to recover the insoluble material. The insoluble material was added to 1 L of 0.2 mol / L sodium hydroxide solution and stirred at 90°C for 3 hours to dissolve. After acidifying with 35% hydrochloric acid, the mixture was stirred at 90°C for 6 hours. After cooling to room temperature, the precipitated sulfide (SF-01) was recovered (16.6g, yield 81.0%).

[0518] [ka]

[0519] Sulfides (SF-02) to (SF-05) were obtained in the same manner as the synthesis example of sulfide (SF-01), except that thiophenol was replaced with the thio reagents (TH-02) to (TH-05) listed below.

[0520] [ka]

[0521] Synthesis of sulfide (SF-09) Sulfide (SF-09) was obtained in the same manner as the synthesis example of sulfide (SF-01), except that 4-fluorophthalic anhydride was replaced with 3-fluorophthalic anhydride.

[0522] [ka]

[0523] (Synthesis of sulfoxides) Synthesis of sulfoxide (SO-01) In a three-necked flask containing sulfide (SF-01) (10.0 g, 39 mmol) and dichloromethane (70 mL), potassium carbonate (11.1 g, 80 mmol) was added. After cooling to 5°C, a mixture of metachloroperbenzoic acid (mCPBA) (containing approximately 30% water) (6.6 g, 38 mmol) and MeOH (15 g) was added dropwise for 2 hours. Then, while still cooled, 5% NaHCO3 aqueous solution (120 g) was added to stop the reaction. The recovered organic layer was sequentially washed three times with 10% sodium thiosulfate aqueous solution (20 g), three times with 3% NaHCO3 (20 g), and four times with ultrapure water (30 g). Subsequently, the organic layer was concentrated using a rotary evaporator. The concentrate was recrystallized in a mixed solvent of heptane and TBME to obtain sulfoxide (SO-01) (6.1 g, yield = 57.4%).

[0524] [ka]

[0525] Sulfoxides (SO-02) to (SO-05) and (SO-09) were obtained in the same manner as the synthesis example of sulfoxide (SO-01), except that sulfide (SF-01) was replaced with sulfides (SF-02) to (SF-05) and (SF-09), respectively.

[0526] [ka]

[0527] (Synthesis of cations) Sulfoxide (SO-01) (5.0 g, 18.4 mmol), benzene (1.4 g, 18.4 mmol), and trifluoromethanesulfonic anhydride (5.6 g, 20.0 mmol) were stirred in 100 g of dichloromethane at -20°C for 2 hours. 100 g of 5% aqueous sodium bicarbonate solution was added, and the mixture was stirred at room temperature. The organic layer was collected, and the solvent was removed by distillation. The resulting residue was purified by repeated crystallization to obtain compound (B-1-a) (5.3 g, yield 60.0%). A methanol solution (10 wt%) containing compound (B-1-a) was subjected to anion exchange using an ion exchange resin to obtain a solution of chloride (B-1-b).

[0528] [ka]

[0529] Using one of the sulfoxides (SO-01) to (SO-05) or (SO-09) and either benzene or one of the following compounds, the following chlorides (B-2-b) to (B-9-b) and (Bm-1-b) were obtained in the same manner as the synthesis example of chloride (B-1-b). A chloride (B-2-b) was obtained from sulfoxide (SO-02) and benzene. A chloride (B-3-b) was obtained from sulfoxide (SO-03) and anisole. A chloride (B-4-b) was obtained from sulfoxide (SO-04) and anisole. A chloride (B-5-b) was obtained from sulfoxide (SO-05) and anisole. Chloride (B-6-b) was obtained from sulfoxide (SO-01) and 3-iodoanisole. Chloride (B-7-b) was obtained from sulfoxide (SO-02) and iodobenzene. Chloride (B-8-b) was obtained from sulfoxide (SO-02) and 1,2-diiodobenzene. A chloride (B-9-b) was obtained from sulfoxide (SO-09) and benzene. A chloride (Bm-1-b) was obtained from sulfoxide (SO-01) and iodobenzene.

[0530] [ka]

[0531] [ka]

[0532] [ka]

[0533] (Examples of synthesis of compounds (B)-1 to (B)-10) Compound (Bc-1) (10.3 g, 13.0 mmol), 100 g of dichloromethane, and 100 g of ultrapure water were added to a solution of chloride (B-1-b), and the mixture was stirred at room temperature for 15 minutes, followed by salt exchange. After the reaction was complete, the aqueous phase was removed, and the organic phase was washed four times with ultrapure water (100 g). Compound (B)-1 was obtained by concentrating the organic phase to dryness using a rotary evaporator (12.1 g, yield = 95.0%).

[0534] [ka]

[0535] Compounds (B)-2 to (B)-9 were obtained from chlorides (B-2-b) to (B-9-b) by salt exchange using compound (Bc-1), in the same manner as the synthesis example of compound (B)-1. Compound (B)-10 was obtained from chloride (Bm-1-b) by salt exchange using compound (Bc-2).

[0536] [ka]

[0537] [ka]

[0538] [ka]

[0539] Similar to the synthesis example of compound (B)-1, monomer compounds (B)-11 to (B)-13 were obtained from chlorides (B-1-b), (B-6-b), and (Bm-1-b) by salt exchange using compound (Bc-3).

[0540] [ka]

[0541] [ka]

[0542] (Examples of synthesis of compounds (D)-1 to (D)-9) To a chloride (B-1-b) solution, 2,3,5-triiodobenzoic acid (5.5 g, 11.0 mmol), 100 g of dichloromethane, and 100 g of ultrapure water were added. Then, triethylamine (TEA) (1.0 g, 10.0 mmol) was added, and the mixture was stirred at room temperature for 15 minutes. After the reaction was complete, the aqueous phase was removed, and the organic phase was washed four times with ultrapure water (100 g). Compound (D)-1 was obtained by concentrating the organic phase to dryness using a rotary evaporator (7.3 g, yield = 87.0%).

[0543] [ka]

[0544] Compounds (D)-2 to (D)-9 were obtained by salt exchange using 2,3,5-triiodobenzoic acid or 3,5-diiodobenzoic acid from chlorides (B-1-b) to (B-9-b) in the same manner as the synthesis example of compound (D)-1.

[0545] [ka]

[0546] [ka]

[0547] Similar to the synthesis example of compound (B)-1, monomer compounds (D)-10 to (D)-11 were obtained from chlorides (B-6-b) and (Bm-1-b) by salt exchange using compounds (Bc-4) to (Bc-5).

[0548] [ka]

[0549] The compound structure was confirmed by measuring molecular ion peaks using mass spectrometry (Waters ACQUITY UPLC H-Class / SQD system). The measurement results are shown in Tables 1 and 2. In Tables 1 and 2, the molecular ion peak values ​​are shown in "m / z," and ESI stands for electrospray ionization.

[0550] [Table 1]

[0551] [Table 2]

[0552] <Manufacturing of polymer compounds> (Synthesis of polymer compounds (A)-1 to (A)-10) The polymer compounds (A)-1 to (A)-10 were obtained by radical polymerization using the monomers listed below that induce the constituent units of each polymer compound, the monomers (B)-11 to (B)-13 and (D)-10 to (D)-11, in predetermined molar ratios, followed by a deprotection reaction as necessary. Compound (a10-01pre) is a monomer that induces the constituent unit (a10-01) listed below.

[0553] [ka]

[0554] Polymer compounds (A)-1 to (A)-10 are shown below. In the formulas below, l, m, n, and p represent the composition ratio (molar ratio) of each constituent unit.

[0555] [ka]

[0556] [ka]

[0557] [ka]

[0558] [ka]

[0559] Regarding the obtained polymer compounds (A)-1 to (A)-10, 13 Table 3 shows the copolymerization composition ratio of the polymer compound (the proportion (molar ratio) of constituent units derived from each monomer compound) determined by 13C-NMR, as well as the weight-average molecular weight (Mw) and molecular weight dispersion (Mw / Mn) in terms of standard polystyrene, determined by GPC measurement.

[0560] [Table 3]

[0561] <Preparation of the resist composition> (Examples 1-34, Comparative Examples 1-4) Each example of a resist composition was prepared by mixing and dissolving the components shown in Tables 4-5.

[0562] [Table 4]

[0563] [Table 5]

[0564] In Tables 4 and 5, each abbreviation has the following meaning. The numbers in brackets [ ] represent the amount (parts by mass) of the ingredients. (A)-1 to (A)-10: The above polymer compounds (A)-1 to (A)-10.

[0565] (B)-1 to (B)-10: Acid generators consisting of the above compounds (B)-1 to (B)-10. (B)-21~(B)-22: Acid generator consisting of the following compounds (B)-21~(B)-22.

[0566] [ka]

[0567] (D)-1 to (D)-9: Acid diffusion control agents consisting of the above compounds (D)-1 to (D)-9. (D)-21~(D)-22: Acid diffusion control agents consisting of the following compounds (D)-21~(D)-22.

[0568] [ka]

[0569] (S)-1: A mixed solvent of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 60 / 40 (mass ratio).

[0570] <Resist pattern formation> Steps to form a resist film: Each example of the resist composition was applied to an 8-inch silicon substrate treated with hexamethyldisilazane (HMDS) using a spinner, and a 50 nm thick resist film was formed by pre-baking (PAB) on a hot plate at 110°C for 60 seconds and drying.

[0571] The process of exposing the resist film: Next, the resist film was subjected to a JEOL JBX-9300FS electron beam lithography system (manufactured by JEOL Ltd.) at an acceleration voltage of 100kV, and a 1:1 line-and-space pattern (hereinafter referred to as "LS pattern") with a target size of 25nm line width (50nm pitch width) was drawn (exposed). Subsequently, post-exposure heating (PEB) treatment was performed at 110°C for 60 seconds.

[0572] The process of developing the resist film after exposure: Next, alkaline development was performed at 23°C for 60 seconds using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) "NMD-3" (product name, manufactured by Tokyo Ohka Kogyo Co., Ltd.). After that, a water rinse was performed with pure water for 15 seconds. As a result, a 1:1 LS pattern with a line width of 25 nm was formed.

[0573] [Evaluation of optimal exposure (Eop)] The optimal exposure amount Eop(μC / cm²) for forming the target-sized LS pattern through the above <resist pattern formation> method is to form the resist pattern. 2 We calculated this as "Eop(μC / cm²)". 2 )" is shown in Table 6.

[0574] [LWR (Line Wise Roughness) Evaluation] For the LS pattern formed in the above <Formation of Resist Pattern>, 3σ, a measure of LWR, was determined. This is shown in Table 6 as "LWR(nm)". "3σ" represents three times the standard deviation (σ) (unit: nm) obtained from the measurement results of 400 line positions in the longitudinal direction of the line using a scanning electron microscope (acceleration voltage 800V, product name: S-9380, manufactured by Hitachi High-Technologies Corporation). A smaller value of 3σ indicates less roughness on the line sidewalls, resulting in a more uniformly wide LS pattern.

[0575] [Evaluation of limiting resolution] The critical resolution at the optimal exposure dose (Eop) for forming the above LS pattern, specifically the space size (nm) of the pattern that is resolved when gradually decreasing the exposure dose from the optimal exposure dose (Eop) to form the LS pattern, was determined using a scanning electron microscope S-9380 (Hitachi High-Technologies Corporation). The results are shown in Table 6 as "Critical Resolution (nm)".

[0576] [Defect evaluation] For the LS patterns formed in the above <Formation of Resist Patterns>, the total number of foreign matter and defects on the coated film surface of the silicon wafer was measured using a surface defect observation device (product name: KLA2905, manufactured by KLA-Tencor). In the measurement, the number of foreign matter and defects with a size of 1 μm or larger was counted. Ten measurements were taken for each sample, and the average value of the total number of foreign matter and defects was calculated. The average value of the total number of foreign matter and defects in Comparative Example 1 was set to 1.0, and relative values ​​were calculated for the average value of the total number of foreign matter and defects in each example. These relative values ​​are shown as "Defects" in Table 6. A lower relative value indicates a better LS pattern with a smaller total number of foreign objects and defects.

[0577] [Table 6]

[0578] As shown in Table 6, the resist compositions of Examples 1 to 34 were found to have better LWR, limiting resolution, and defect evaluations compared to the resist compositions of Comparative Examples 1 to 4.

Claims

1. A resist composition that generates acid upon exposure and whose solubility in a developer changes due to the action of the acid, A resist composition containing a compound comprising a cation represented by the following general formula (c0). 【Chemistry 1】 [In the formula, R ０１ and R ０２ Each of these independently represents an optionally substituted aryl group, an optionally substituted alkyl group, or an optionally substituted alkenyl group. ０１ and R ０２ These may bond with each other to form a ring together with the sulfur atom in the formula. ０３ represents a substituent. k is an integer between 0 and 3.

2. A base component (A) whose solubility in the developer changes due to the action of acid, An acid-generating agent component (B) that generates acid upon exposure, It contains, The resist composition according to claim 1, wherein the acid generating agent component (B) comprises a compound represented by the following general formula (b0). 【Chemistry 2】 [In the formula, Mc ＋ Xb is a cation represented by the general formula (c0) above. － [b-an-1] is at least one anion selected from the group consisting of anions represented by any of the following general formulas: (b-an-1), (b-an-2), and (b-an-3). 【Transformation 3】 [In the formula, R １０１ and R １０４ to R １０８ are each independently a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent. R １０４ and R １０５ may be bonded to each other to form a ring structure. R １０２ is a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom. Y １０１ is a divalent linking group containing an oxygen atom or a single bond. V １０１ to V １０３ are each independently an alkylene group, a fluorinated alkylene group or a single bond. However, Y １０１ and V １０１ do not simultaneously become a single bond. L １０１ and L １０２ are each independently an oxygen atom or a single bond. L １０３ to L １０５ are each independently -CO-, -SO ２ - or a single bond.]

3. A base component (A) whose solubility in the developer changes due to the action of acid, An acid diffusion control agent component (D) that controls the diffusion of acid generated by exposure, It contains, The resist composition according to claim 1, wherein the acid diffusion control agent component (D) comprises a compound represented by the following general formula (d0). 【Chemistry 4】 [In the formula, Mc ＋ Xd is a cation represented by the general formula (c0) above. － This is at least one anion selected from the group consisting of anions represented by any of the following general formulas: (d1-an-1), (d1-an-2), and (d1-an-3). 【Transformation 5】 [In the formula, Rd １ ~Rd ４ Each of these is independently an optionally substituted cyclic group, an optionally substituted linear alkyl group, or an optionally substituted linear alkenyl group. However, Rd in formula (d1-an-2) ２ In this example, assume that no fluorine atom is bonded to the carbon atom adjacent to the sulfur atom. １ This is a divalent linking group or a single bond.

4. It contains a resin component (A1) whose solubility in the developer changes due to the action of acid, The resist composition according to claim 1, wherein the resin component (A1) has a constituent unit derived from a compound represented by the following general formula (a0-m). 【Transformation 6】 [In the formula, W ０ This represents a polymerizable group-containing group. ０ Rx represents a divalent linking group. － Mc is an anionic group. ＋ This is a cation represented by the general formula (c0) mentioned above.

5. A method for forming a resist pattern, comprising the steps of: forming a resist film on a support using a resist composition according to any one of claims 1 to 4; exposing the resist film; and developing the exposed resist film to form a resist pattern.

6. A compound containing a cation represented by the following general formula (c0). 【Transformation 7】 [In the formula, R ０１ and R ０２ Each of these independently represents an optionally substituted aryl group, an optionally substituted alkyl group, or an optionally substituted alkenyl group. ０１ and R ０２ These may bond with each other to form a ring together with the sulfur atom in the formula. ０３ represents a substituent. k is an integer between 0 and 3.

7. An acid generator containing a compound represented by the following general formula (b0). 【Transformation 8】 [In the formula, Mc ＋ Xb is a cation represented by the following general formula (c0): － [b-an-1] is at least one anion selected from the group consisting of anions represented by any of the following general formulas: (b-an-1), (b-an-2), and (b-an-3). 【Chemistry 9】 [In the formula, R ０１ and R ０２ Each of these independently represents an optionally substituted aryl group, an optionally substituted alkyl group, or an optionally substituted alkenyl group. ０１ and R ０２ These may bond with each other to form a ring together with the sulfur atom in the formula. ０３ represents a substituent. k is an integer between 0 and 3. R １０１ and R １０４ ~R １０８ Each of these is independently a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents. １０４ and R １０５ These may bond to each other to form a ring structure. １０２ This is a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom. １０１ This is a divalent linking group or single bond containing an oxygen atom. １０１ ~V １０３ Each of these is independently an alkylene group, a fluorinated alkylene group, or a single bond. However, Y １０１ and V １０１ It is impossible for them to be single bonds at the same time. １０１ and L １０２ Each of these is independently either an oxygen atom or a single bond. １０３ ~L １０５ These are, independently, -CO- and -SO-. ２ - Or it is a single bond.

8. An acid diffusion control agent comprising a compound represented by the following general formula (d0). 【Chemistry 10】 [In the formula, Mc ＋ Xd is a cation represented by the following general formula (c0): － This is at least one anion selected from the group consisting of anions represented by any of the following general formulas: (d1-an-1), (d1-an-2), and (d1-an-3). 【Chemistry 11】 [In the formula, R ０１ and R ０２ Each of these independently represents an optionally substituted aryl group, an optionally substituted alkyl group, or an optionally substituted alkenyl group. ０１ and R ０２ These may bond with each other to form a ring together with the sulfur atom in the formula. ０３ represents a substituent. k is an integer between 0 and 3. Rd １ ~Rd ４ Each of these is independently an optionally substituted cyclic group, an optionally substituted linear alkyl group, or an optionally substituted linear alkenyl group. However, Rd in formula (d1-an-2) ２ In this example, assume that no fluorine atom is bonded to the carbon atom adjacent to the sulfur atom. １ This is a divalent linking group or a single bond.

9. A polymer compound having a constituent unit derived from a compound represented by the following general formula (a0-m). 【Chemistry 12】 [In the formula, W ０ This represents a polymerizable group-containing group. ０ Rx represents a divalent linking group. － Mc is an anionic group. ＋ This is a cation represented by the following general formula (c0). 【Chemistry 13】 [In the formula, R ０１ and R ０２ Each of these independently represents an optionally substituted aryl group, an optionally substituted alkyl group, or an optionally substituted alkenyl group. ０１ and R ０２ These may bond with each other to form a ring together with the sulfur atom in the formula. ０３ represents a substituent. k is an integer between 0 and 3.

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