Resist composition and method for forming resist pattern

Abstract

The present invention employs a resist composition which contains: a resin component that has a constituent unit derived from a compound represented by general formula (a0-1); and a compound represented by general formula (b0).　In the general formulae, W01 represents a polymerizable group-containing group; W02 represents an aromatic hydrocarbon group; Ya01 represents a linking group or a single bond; Ra01 represents an acid dissociable group; Ra02 represents a chain hydrocarbon group or an alicyclic hydrocarbon group; p represents an integer of 1 or more; and q represents an integer of 1 or more. Rb0 represents a fused ring group containing an aromatic ring and having a functional group that controls solubility in a developer solution. Yb0 represents a linking group or a single bond; Vb0 represents an alkylene group, a fluorinated alkylene group, or a single bond; R0 represents a fluorinated alkyl group or a fluorine atom; Mm+ represents an organic cation; and m represents an integer of 1 or more. According to this resist composition, in the formation of a resist pattern, high sensitivity is achieved, dimensional uniformity is increased, and the occurrence of pattern defects is further suppressed.

Description

Resist composition and method for forming a resist pattern

[0001] The present invention relates to a resist composition and a resist pattern forming method. This application claims priority under Japanese Patent Application No. 2025-009736, filed in Japan on January 23, 2025, the contents of which are incorporated herein by reference.

[0002] In recent years, advances in lithography technology have led to rapid miniaturization of patterns in the manufacturing of semiconductor devices and liquid crystal display elements. Generally, miniaturization is achieved by shortening the wavelength (increasing the energy) of the exposure light source.

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

[0004] In chemically amplified resist compositions, a resin component having multiple structural units is generally used as the substrate component to improve lithography properties, etc. (see, for example, Patent Document 1). A wide variety of acid generating agents have been proposed to date, including onium salt-based acid generating agents such as iodonium salts and sulfonium salts, oxime sulfonate-based acid generating agents, diazomethane-based acid generating agents, nitrobenzyl sulfonate-based acid generating agents, iminosulfonate-based acid generating agents, and disulfone-based acid generating agents.

[0005] International Publication No. 2023 / 140364

[0006] As lithography technology continues to advance and resist patterns become increasingly miniaturized, for example, EUV and EB lithography aim to form fine patterns of several tens of nanometers. As resist pattern dimensions become smaller, there is a need to improve lithographic characteristics such as sensitivity and dimensional uniformity without any trade-offs. Furthermore, with the miniaturization of resist patterns, for example, during development, insufficient solubility of the exposed resist film in the developer solution can lead to insufficient resolution, making it difficult to obtain the desired shape and increasing the likelihood of pattern defects.

[0007] The present invention has been made in view of the above circumstances, and aims to provide a resist composition that enables high sensitivity in resist pattern formation, improves lithography characteristics such as dimensional uniformity, and further improves resolution, thereby suppressing the occurrence of pattern defects, as well as a method for forming a resist pattern using the resist composition.

[0008] To solve the above problems, the present invention employs the following configuration. That is, 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, comprising a resin component (A1) whose solubility in a developer changes due to the action of the acid, and an acid generating agent component (B) that generates acid upon exposure, wherein the resin component (A1) has a constituent unit derived from a compound represented by the following general formula (a0-1), and the acid generating agent component (B) comprises a compound (B0) represented by the following general formula (b0).

[0009] [In the formula, W ０１ This is a polymerizable group-containing group. ０２ This is an aromatic hydrocarbon group which may have substituents. ０１ This is a divalent linking group or a single bond. Ra ０１ Ra is an acid-dissociating group. ０２ [p] is a chain hydrocarbon group which may have substituents, or an alicyclic hydrocarbon group which may have substituents. [p] is an integer of 1 or more. [q] is an integer of 1 or more.

[0010] [In the formula, Rb ０ is a condensed ring group containing a condensed ring having one or more aromatic rings. The condensed ring group has, as a substituent, a functional group (Fab) that controls solubility in a developer. Yb ０ is a divalent linking group or a single bond. Vb ０ is an alkylene group, a fluorinated alkylene group, or a single bond. R ０ is a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom. M ｍ＋ is an m-valent organic cation. m is an integer of 1 or more. ]

[0011] A second aspect of the present invention is a resist pattern forming method including a step of forming a resist film on a support 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.

[0012] According to the present invention, in the formation of a resist pattern, a resist composition capable of achieving high sensitivity, enhancing lithography characteristics such as dimensional uniformity, and further improving resolution and suppressing the occurrence of pattern defects, and a resist pattern forming method using the resist composition can be provided.

[0013] In this specification and the claims, "aliphatic" is a relative concept with respect to aromatic, and is defined to mean a group, compound, etc. that does not have aromaticity. The "alkyl group" includes linear, branched, and cyclic monovalent saturated hydrocarbon groups unless otherwise specified. The same applies to the alkyl group in the alkoxy group. The "alkylene group" includes linear, branched, and cyclic divalent saturated hydrocarbon groups unless otherwise specified. The "halogen atom" includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The "constituent unit" means a monomer unit (monomeric unit) that constitutes a high molecular compound (resin, polymer, copolymer). "Exposure" is a concept that includes all irradiations of radiation.

[0014] When it is described that "it may have a substituent", when a hydrogen atom (-H) is substituted with a monovalent group, and when a methylene group (-CH２ This includes both cases where the methylene group (-H) is substituted with a divalent group. That is, when a monovalent group is listed as the substituent, it means that a hydrogen atom (-H) is substituted. Also, when a divalent group is listed as the substituent, it means that the methylene group (-CH) is substituted. ２ This means substituting a hydrogen atom. Examples of monovalent groups that substitute a hydrogen atom include, but are not limited to, alkyl groups, alkoxy groups, halogen atoms, alkyl halides, and hydroxyl groups. Examples of divalent groups that substitute a methylene group include, but are not limited to, carbonyl groups, ether bonds, ester bonds, and amide bonds.

[0015] "Base material components" are organic compounds that have film-forming ability. Organic compounds used as base material 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 compounds" refer to nonpolymers with a molecular weight of 500 or more and less than 4000. Polymers typically have a molecular weight of 1000 or more. Hereinafter, "resins," "high molecular weight compounds," or "polymers" refer to polymers 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).

[0016] "Induced structural unit" means a structural unit formed by the cleavage of multiple bonds between carbon atoms, such as an ethylenic double bond. "Acrylic acid ester" may have a hydrogen atom bonded to the α-carbon atom substituted with a substituent. A substituent (R) that substitutes 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 αｘThis also includes α-hydroxyacrylic esters in which the α-carbon atom is substituted with a hydroxyalkyl group or a group that modifies its hydroxyl group. Unless otherwise specified, the α-carbon atom of an acrylic acid ester refers to the carbon atom to which the carbonyl group of acrylic acid is bonded. Hereinafter, an acrylic acid ester in which the hydrogen atom bonded to the α-carbon atom is substituted with a substituent may be called an α-substituted acrylic acid ester.

[0017] The term "derivative" is defined as 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, and includes 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. Examples of substituents that substitute the α-position hydrogen atom of hydroxystyrene include R αｘ Similar examples include the above.

[0018] In this specification and within the scope of these claims, some structures represented by chemical formulas may contain a chiral carbon, and may have enantiomers or diastereomers. In such cases, a single chemical formula will represent all of these isomers. These isomers may be used individually or as a mixture.

[0019] (Resist Composition) One embodiment of the resist composition generates acid upon exposure and changes in solubility in a developer solution due to the action of the acid. The resist composition of this embodiment contains a base component (A) (hereinafter also referred to as "component (A)") whose solubility in a developer solution changes due to the action of the acid, and an acid generating agent component (B) (hereinafter also referred to as "component (B)") which generates acid upon exposure.

[0020] The aforementioned component (A) includes a resin component (A1) having a structural unit derived from a compound represented by the following general formula (a0-1). The aforementioned component (B) includes a compound (B0) represented by the following general formula (b0).

[0021] [In the formula, W ０１ This is a polymerizable group-containing group. ０２ This is an aromatic hydrocarbon group which may have substituents. ０１ This is a divalent linking group or a single bond. Ra ０１ Ra is an acid-dissociating group. ０２ [p] is a chain hydrocarbon group which may have substituents, or an alicyclic hydrocarbon group which may have substituents. [p] is an integer of 1 or more. [q] is an integer of 1 or more.

[0022] [In the formula, Rb ０ This is a fused cyclic group containing one or more aromatic rings. The fused cyclic group has a functional group (Fab) as a substituent that controls its solubility in the developer. Yb ０ Vb is a divalent linking group or a single bond. ０ R is an alkylene group, a fluorinated alkylene group, or a single bond. ０ This is a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom. ｍ＋ [where m is an m-valent organic cation, and m is an integer greater than or equal to 1]

[0023] 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, and 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 of the resist film. 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 that uses an alkaline developer for the development process during resist pattern formation, or for a solvent development process that uses an organic developer for the development process. In other words, the resist composition of this embodiment is a "positive-type resist composition for alkaline development processes" that forms a positive-type resist pattern in an alkaline development process, and a "negative-type resist composition for solvent development processes" that forms a negative-type resist pattern in a solvent development process.

[0024] <Component (A): Substrate component> In the resist composition of this embodiment, component (A) includes 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, and component (A1) has a constituent unit derived from a compound represented by the general formula (a0-1) described later. At least component (A1) is used as component (A), and at least one of other polymer compounds and low molecular weight compounds may be used in combination with component (A1). In the resist composition of this embodiment, component (A) may be used alone or two or more may be used in combination.

[0025] • Component (A1): Regarding the resin component, component (A1) has a constituent unit (hereinafter also referred to as "constituent unit (a0)") derived from the compound represented by the general formula (a0-1) described below. In addition to the constituent unit (a0), component (A1) may also have other constituent units other than constituent unit (a0).

[0026] ≪Constituent Unit (a0)≫ Constituent unit (a0) is a constituent unit derived from the compound represented by the following general formula (a0-1). In such constituent unit (a0), Ra in formula (a0-1) ０１ This is an acid-dissociable group, and this acid-dissociable group protects the oxy group (-O-) of the carbonyloxy group [-C(=O)-O-] in formula (a0-1). The "acid-dissociable group" here has the property of being acid-dissociable, meaning that the bond between the acid-dissociable group and the oxygen atom (oxy group (-O-)) adjacent to it can be cleaved by the action of an acid. When the acid-dissociable group dissociates due to the action of an acid, a polar group (carboxyl group) with higher polarity than the acid-dissociable group is generated, increasing the polarity. As a result, the polarity of the entire component (A1) increases. Due to the increased polarity, the solubility of component (A1) in the developer changes relatively; solubility increases when the developer is an alkaline developer, and decreases when the developer is an organic developer.

[0027] [In the formula, W ０１ This is a polymerizable group-containing group. ０２ This is an aromatic hydrocarbon group which may have substituents. ０１ This is a divalent linking group or a single bond. Ra ０１ Ra is an acid-dissociating group. ０２ [p] is a chain hydrocarbon group which may have substituents, or an alicyclic hydrocarbon group which may have substituents. [p] is an integer of 1 or more. [q] is an integer of 1 or more.

[0028] In the above formula (a0-1), W ０１ This is a polymerizable group-containing group. ０１ In this context, a "polymerizable group" refers to a group that enables a compound having a polymerizable group to be polymerized by radical polymerization or the like, and includes, for example, a group containing multiple bonds between carbon atoms, such as an ethylenic double bond. In the constituent unit (a0), the multiple bonds in the polymerizable group are cleaved to form the main chain.

[0029] W ０１Examples of polymerizable groups in this material 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.

[0030] W ０１ The "polymerizable group-containing group" in this context may be a group composed solely of polymerizable groups, 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.

[0031] - Divalent hydrocarbon group which may have substituents: If any group other than the polymerizable group is a divalent hydrocarbon group which may have substituents, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0032] ...Aliphatic hydrocarbon groups in groups other than the polymerizable group. The aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, but is usually preferably saturated. Examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups that contain a ring in their structure.

[0033] ...Linear or branched aliphatic hydrocarbon group 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 the linear aliphatic hydrocarbon group, a linear alkylene group is preferred, specifically a methylene group [-CH ２ -], ethylene group [- (CH ２ ) ２-], trimethylene group [-(CH ２ ) ３ -], tetramethylene group [-(CH ２ ) ４ -], pentamethylene group [-(CH ２ ) ５ Examples include -]. 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. A branched alkylene group is preferred as the branched aliphatic hydrocarbon group, specifically -CH(CH ３ )-,-CH(CH ２ CH ３ )-,-C(CH ３ ) ２ -, -C(CH ３ ) (CH ２ CH ３ )-,-C(CH ３ ) (CH ２ CH ２ CH ３ )-,-C(CH ２ CH ３ ) ２ - Alkyl methylene groups such as -CH(CH ３ )CH ２ -, -CH(CH ３ )CH(CH ３ )-,-C(CH ３ ) ２ CH ２ -, -CH(CH ２ CH ３ )CH ２ -, -C(CH ２ CH ３ ) ２ -CH ２ - Alkyl ethylene groups such as -CH(CH ３ )CH ２ CH ２ -ien-CH ２ CH (CH ３ )CH ２ - Alkyl trimethylene groups such as -CH(CH ３ )CH ２ CH ２ CH ２ -ien-CH ２CH (CH ３ )CH ２ CH ２ Examples include alkylalkylene groups such as alkyltetramethylene groups. In the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0034] 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.

[0035] ...Aliphatic hydrocarbon groups containing a ring in their structure Examples of aliphatic hydrocarbon groups containing a ring in their structure include cyclic aliphatic hydrocarbon groups (groups with two hydrogen atoms removed from an aliphatic hydrocarbon ring) which may contain substituents containing heteroatoms in their ring structure, 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. As a monocyclic alicyclic hydrocarbon group, a group in which two hydrogen atoms have been removed from a monocycloalkane is preferred. As a monocycloalkane, those having 3 to 6 carbon atoms are preferred, and specifically examples include cyclopentane and cyclohexane. As the polycyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a polycycloalkane is preferred, and as the polycycloalkane, those having 7 to 12 carbon atoms are preferred, specifically adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, and the like.

[0036] The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and the like. The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and most preferably a methoxy group or an ethoxy group. Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is preferred. Examples of the halogenated alkyl group as the substituent include a group in which some or all of the hydrogen atoms of the alkyl group are substituted with the halogen atom. Part of the carbon atoms constituting the ring structure of the cyclic aliphatic hydrocarbon group may be substituted with a substituent containing a hetero atom. Examples of the substituent containing a hetero atom include -O-, -C(=O)-O-, -S-, -S(=O) ２ -, -S(=O) ２ -O- is preferred.

[0037] ...Aromatic hydrocarbon groups in groups other than the polymerizable 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 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, the 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: a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); a group obtained by removing two hydrogen atoms from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group) in which one hydrogen atom is replaced by an alkylene group (e.g., a group obtained by removing one more hydrogen atom from the 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.

[0038] The aromatic hydrocarbon group may have a hydrogen atom thereof substituted with a substituent. For example, a hydrogen atom bonded to an aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, etc. The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. Examples of the alkoxy group, the halogen atom, and the halogenated alkyl group as the substituent are those exemplified as the substituent for substituting a hydrogen atom of the cyclic aliphatic hydrocarbon group.

[0039] - A divalent linking group containing a heteroatom: When another group other than the polymerizable group is a divalent linking group containing a heteroatom, preferred examples of the linking group include -O-, -C(=O)-O-, -C(=O)-, -O-C(=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)-(H may be substituted with a substituent such as an alkyl group or an acyl group), -S-, -S(=O) ２ -, -S(=O) ２ -O-, general formula -Y ２１ -O-Y ２２ -, -Y ２１ -O-, -Y ２１ -C(=O)-O-, -C(=O)-O-Y ２１ -, -[Y ２１ -C(=O)-O] ｍ” -Y ２２ -, -Y ２１ -O-C(=O)-Y ２２ - or -Y ２１ -S(=O) ２ -O-Y ２２ - represented by the formula [wherein Y ２１ and Y ２２Each 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. For example, when the divalent linking group containing the heteroatom is -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, -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 -O-Y ２２ -, -Y ２１ -O-, -Y ２１ -C(=O)-O-, -C(=O)-O-Y ２１ -, -[Y ２１ -C (=O) -O] ｍ” -Y ２２ -, -Y ２１ -OC(=O)-Y ２２ - or - Y ２１ -S (=O) ２ -O-Y ２２ - Middle, Y ２１ and Y ２２ These are, independently, divalent hydrocarbon groups which may have substituents. Examples of such divalent hydrocarbon groups are the same as those listed in the description of the divalent linking group (divalent hydrocarbon groups which may have substituents). ２１ Preferably, a linear aliphatic hydrocarbon group is preferred, a linear alkylene group is more preferred, a linear alkylene group having 1 to 5 carbon atoms is even more preferred, and a methylene group or ethylene group is particularly preferred. ２２ Preferably, the group is 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, formula -[Y２１ -C (=O) -O] ｍ” -Y ２２ As a base represented by -, see formula -Y ２１ -C(=O)-O-Y ２２ Groups represented by - are particularly preferred. Among them, the group represented by formula -(CH ２ ) ａ’ -C(=O)-O-(CH ２ ) 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.

[0040] W ０１ For example, the chemical formula: C(R Ｘ１１ ) (Caution Ｘ１２ ) = C(R Ｘ１３ )-Ya ｘ０ A 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.

[0041] R Ｘ１１ , R Ｘ１２ and R Ｘ１３ The alkyl group 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. Among these, R Ｘ１１ and R Ｘ１２Preferably, these are a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and due to their ease of industrial availability, a hydrogen atom and a methyl group are more preferred, and a hydrogen atom is particularly preferred. Also, R Ｘ１３ Preferably, the group is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms. Due to their ease of industrial availability, a hydrogen atom or a methyl group is more preferable, and a hydrogen atom is particularly preferable.

[0042] Ya ｘ０ The divalent linking group in is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have substituents, a divalent linking group which contains a heteroatom, and so on, respectively. ０１ This is similar to the divalent hydrocarbon groups and divalent linking groups containing heteroatoms that were exemplified as other groups besides polymerizable groups in the above.

[0043] Among the above, Ya ｘ０ Preferably, the bonds are ester bonds [-C(=O)-O-, -O-C(=O)-], ether bonds (-O-), linear or branched alkylene groups, aromatic hydrocarbon groups or combinations thereof, or single bonds. Among these, Ya ｘ０ As such, ester bonds [-C(=O)-O-, -O-C(=O)-] and single bonds are more preferable, and single bonds are even more preferable.

[0044] In the above formula (a0-1), W ０２ This is an aromatic hydrocarbon group which may have substituents. ０２Examples of aromatic hydrocarbon groups in this context include groups obtained by removing (p + q + 1) hydrogen atoms from an aromatic ring that may have substituents. The aromatic ring here is not particularly limited as long as it is a cyclic conjugated system having 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 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. ０２ Examples of aromatic hydrocarbon groups in include groups obtained by removing (p + q + 1) hydrogen atoms from aromatic compounds containing an aromatic ring which may have two or more substituents (e.g., biphenyl, fluorene, etc.). Among the above, W ０２ Preferably, the group is obtained by removing (p + q + 1) hydrogen atoms from benzene, naphthalene, anthracene, or biphenyl; more preferably, the group is obtained by removing (p + q + 1) hydrogen atoms from benzene or naphthalene; and even more preferably, the group is obtained by removing (p + q + 1) hydrogen atoms from benzene.

[0045] W ０２The aromatic hydrocarbon group in may or may not have substituents. Examples of substituents include alkyl groups, halogen atoms, and alkyl halides. Preferably, the alkyl group has 1 to 5 carbon atoms, and most preferably it is a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group. Examples of halogen atoms as substituents include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being preferred. Examples of alkyl halides as substituents include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with halogen atoms. Preferably, the substituent is a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably a linear or branched alkyl group having 1 to 3 carbon atoms, even more preferably an ethyl group or a methyl group, and particularly preferably a methyl group. ０２ In this context, it is preferable that the aromatic hydrocarbon group does not have substituents.

[0046] In the above formula (a0-1), Ya ０１ This is a divalent linking group or a single bond. ０１ The divalent linking group in is not particularly limited, but preferred examples include divalent hydrocarbon groups which may have substituents, and divalent linking groups which contain heteroatoms, and the same applies to each as described above. In formula (a0-1), Ya ０１ Among the above, it is preferable that the ester bond [-C(=O)-O-, -O-C(=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-, -O-C(=O)-] and a linear alkylene group is more preferable, and a single bond is even more preferable.

[0047] In the above formula (a0-1), Ra ０１These are acid-dissociable groups. Examples of acid-dissociable groups that have been proposed to date as acid-dissociable groups for base resins used in chemically amplified resist compositions include the following: "acetal-type acid-dissociable groups," "tertiary alkyl ester-type acid-dissociable groups," and "secondary alkyl ester-type acid-dissociable groups."

[0048] Acetal-type acid-dissociating group: Ra ０１ Examples of acid-dissociating groups in this context include the acid-dissociating group represented by the following general formula (a1-r-1) (hereinafter referred to as the "acetal-type acid-dissociating group").

[0049] [In the formula, Ra' １ and Ra' ２ Each of these is either 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.

[0050] 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. １ Or Ra' ２ If the alkyl group is an alkyl group having 1 to 5 carbon atoms, then 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.

[0051] In formula (a1-r-1), Ra' ３Examples 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 groups, ethyl groups, n-propyl groups, n-butyl groups, and n-pentyl groups. Among these, methyl groups, ethyl groups, or n-butyl groups are preferred, and methyl groups or ethyl groups are more preferred.

[0052] 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.

[0053] Ra' ３ When the 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, specifically cyclopentane, cyclohexane, etc. As a polycyclic aliphatic hydrocarbon group, a group obtained by removing one hydrogen atom from a polycycloalkane is preferred, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.

[0054] Ra' ３When a cyclic hydrocarbon group becomes an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. This 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. 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. ３ Specific 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.

[0055] Ra' ３ The cyclic hydrocarbon group in may have substituents. Examples of substituents include -R Ｐ１ , -R Ｐ２ -O-R Ｐ１ , -R Ｐ２ -CO-R Ｐ１ , -R Ｐ２ -CO-OR Ｐ１ , -R Ｐ２ -O-CO-R Ｐ１ , -R Ｐ２ -OH, -R Ｐ２ -CN or -RＰ２ -COOH (These substituents are collectively referred to as "Ra ｘ５ It is also called "." ) are some examples. 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 R is 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 Ｐ２ Some 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 having 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.

[0056] Ra' ３ But, Ra' １ , Ra' ２When 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.

[0057] Tertiary alkyl ester type acid-dissociable group: or Ra ０１ Examples of acid-dissociable groups in this context include the acid-dissociable group represented by the following general formula (a1-r-2). Of the acid-dissociable groups represented by the following formula (a1-r-2), those composed of alkyl groups may hereafter be referred to as "tertiary alkyl ester type acid-dissociable groups" for convenience.

[0058] [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.

[0059] Ra' ４ Examples of hydrocarbon groups include linear or branched alkyl groups, linear or cyclic alkenyl groups, or cyclic hydrocarbon groups. 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 Ra' ４ The linear or cyclic alkenyl group in Ra' is preferably an alkenyl group having 2 to 10 carbon atoms. ５ , Ra' ６ The hydrocarbon group is the Ra' mentioned above. ３ Similar examples include the above.

[0060] Ra' ５ and Ra' ６ When these groups bond to each other to form a ring, the following groups are preferably represented by the general formula (a1-r2-1), the general formula (a1-r2-2), and the general formula (a1-r2-3). On the other hand, Ra' ４ ~Ra' ６When 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.

[0061] [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 together with the bonded carbon atom. In formula (a1-r2-2), Ya is a carbon atom. Xa is a group that forms a cyclic hydrocarbon group together with Ya. Some or all of the hydrogen atoms in this cyclic hydrocarbon group may be substituted. Ra 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. Ra 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 or a hydrogen atom. Some or all of the hydrogen atoms in this chain-like saturated hydrocarbon group may be substituted. Ra' １４ This is a hydrocarbon group that may have substituents. * indicates a bond (the same applies hereafter).

[0062] In the above formula (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.

[0063] 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. １０ In this, the branched alkyl group is the Ra' ３ Similar examples include the above.

[0064] Ra' １０ In this context, 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 here include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of heteroatom-containing groups include (-O-), -C(=O)-O-, -O-C(=O)-, -C(=O)-NH-, -NH-, -S-, and -S(=O). ２ -, -S (=O) ２ Examples include -O-, etc.

[0065] 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.

[0066] 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 a group obtained by further removing one or more hydrogen atoms from a cyclic monovalent hydrocarbon group (aliphatic hydrocarbon group) in the above. The cyclic hydrocarbon group formed by Xa together with Ya may have substituents. An example of such substituent is the above Ra'. ３ Examples include substituents similar to those that the cyclic hydrocarbon group in (a1-r2-2) may have. １０１ ~Ra１０３ 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. 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; 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. 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.

[0067] 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 Ra ｘ５ Similar bases can be cited.

[0068] Ra １０１ ~Ra １０３ Groups containing a carbon-carbon double bond formed by the bonding of two or more carbon atoms 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.

[0069] In formula (a1-r2-3), the aliphatic cyclic group formed by Xaa together with Yaa is Ra' in formula (a1-r-1). ３The groups listed as aliphatic hydrocarbon groups that are monocyclic or polycyclic 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 having 5 to 30 carbon atoms. Among these, Ra １０４ The group is preferably an aromatic hydrocarbon ring having 6 to 15 carbon atoms from which one or more hydrogen atoms have been removed; more preferably a group from which one or more hydrogen atoms have been removed from benzene, naphthalene, anthracene, or phenanthrene; even more preferably a group from which one or more hydrogen atoms have been removed from benzene, naphthalene, or anthracene; particularly preferably a group from which one or more hydrogen atoms have been removed from benzene or naphthalene; and most preferably a group from which one or more hydrogen atoms have been removed from benzene.

[0070] 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.

[0071] 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, or a hydrogen atom. Ra' １２ and Ra' １３ In this, the monovalent chain-like saturated hydrocarbon group having 1 to 10 carbon atoms is the above 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, hydrogen atoms and 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. １２ and Ra' １３ When a chain-like saturated hydrocarbon group represented by is substituted, the substituent may be, for example, the above-mentioned Raｘ５ Similar bases can be cited.

[0072] 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.

[0073] 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.

[0074] Ra' １４ The branched alkyl group in the 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.

[0075] Ra' １４ When the 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, specifically cyclopentane, cyclohexane, etc. As a polycyclic aliphatic hydrocarbon group, a group obtained by removing one hydrogen atom from a polycycloalkane is preferred, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.

[0076] Ra' １４ As for aromatic hydrocarbon groups in this context, Ra １０４Examples 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. １４ The substituents that may be present are Ra １０４ Examples of substituents that may be present include those similar to those that may be present.

[0077] Ra' in equation (a1-r2-4) １４ When is a naphthyl group, the position of bonding to the tertiary carbon atom in formula (a1-r2-4) may be either position 1 or position 2 of the naphthyl group. Ra' in formula (a1-r2-4) １４ If is an anthyl group, the position of bonding to the tertiary carbon atom in formula (a1-r2-4) may be position 1, 2, or 9 of the anthyl group.

[0078] Specific examples of the group represented by the above formula (a1-r2-1) are given below.

[0079]

[0080]

[0081]

[0082] Specific examples of the group represented by the above formula (a1-r2-2) are given below.

[0083]

[0084]

[0085]

[0086] Specific examples of the group represented by the above formula (a1-r2-3) are given below.

[0087]

[0088] Specific examples of the group represented by the above formula (a1-r2-4) are given below.

[0089]

[0090] Secondary alkyl ester type acid-dissociable group: Ra ０１ Examples of acid-dissociable groups in this context include the acid-dissociable group represented by the following general formula (a1-r-4).

[0091] [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. Ra' １２ Ra' is a hydrogen atom or a hydrocarbon group. １０ And, Ra' １１ａ Or Ra' １１ｂ These may be joined together to form a ring. １１ａ Or Ra' １１ｂ And, Ra' １２ These may bond to each other to form a ring. * indicates a bond with the oxygen atom (-O-) of the carbonyloxy group in the general formula (a0-1).

[0092] In the above formula (a1-r-4), Ra' １０ and Ra' １２ The hydrocarbon group in this is the Ra' group. ３ Similar examples can be given. In the above formula (a1-r-4), Ra' １１ａ and Ra' １１ｂ The alkyl group in is the Ra' １ Examples include alkyl groups similar to those in the above formula (a1-r-4), 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 ｘ５ These are some examples.

[0093] Ra' １０ And, Ra'１１ａ Or Ra' １１ｂ These may be joined together to form a ring. １１ａ Or Ra' １１ｂ And, Ra' １２ These elements may combine with each other to form a ring. The ring that these elements may combine to form may be polycyclic or monocyclic, and may be an alicyclic or aromatic ring. The alicyclic and aromatic rings may contain heteroatoms.

[0094] Ra' １０ And, Ra' １１ａ Or Ra' １１ｂ The ring (ring(x)) formed by the bonding of these elements is preferably a monocycloalkene, a ring in which some of the carbon atoms of a monocycloalkene are substituted with heteroatoms (oxygen atoms, sulfur atoms, etc.), or a monocycloalkadiene, preferably a cycloalkene having 3 to 6 carbon atoms, and preferably cyclopentene or cyclohexene.

[0095] Ra' １１ａ Or Ra' １１ｂ And, Ra' １２ Among the above, an aromatic ring is preferred as the ring (ring (y)) formed by the bonding of these elements, and benzene is particularly preferred. The aromatic ring may contain a heteroatom, for example, a thiophene ring.

[0096] Alternatively, the ring (x) and the ring (y) may be bonded to each other to form a fused ring. Specific examples of such fused rings include indane.

[0097] The aforementioned ring (x), ring (y), and the fused ring formed by the bonding of these rings may each have substituents. For example, the above-mentioned Ra ｘ５ These are some examples.

[0098] Specific examples of the group represented by the above formula (a1-r-4) are given below.

[0099]

[0100] Ra in the above general formula (a0-1) ０１The acid-dissociable group in is preferably a cyclic group. Ra in the general formula (a0-1) ０１ Among the above, "tertiary alkyl ester type acid-dissociable group" and "secondary alkyl ester type acid-dissociable group" are preferred, and the acid-dissociable group represented by the general formula (a1-r-2) and the acid-dissociable group represented by the general formula (a1-r-4) are more preferred.

[0101] In the above formula (a0-1), Ra ０２ This is a chain-like hydrocarbon group which may have substituents, or an alicyclic hydrocarbon group which may have substituents. ０２ The chain-like hydrocarbon group in this can be a saturated hydrocarbon group, an unsaturated hydrocarbon group, a linear group, or a branched group.

[0102] Ra ０２ The linear saturated hydrocarbon group (alkyl group) in this compound has, for example, 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, even more preferably 1 to 3 carbon atoms, and particularly 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, n-propyl group, or n-butyl group is preferred, methyl group or ethyl group is more preferred, and methyl group is most preferred.

[0103] Ra ０２ The branched alkyl group in the compound 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 isobutyl group and isopropyl group being preferred.

[0104] Ra ０２ Examples of unsaturated hydrocarbon groups in this context include alkenyl groups. ０２The alkenyl group in this compound preferably has 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 linear alkenyl groups include vinyl groups, propenyl groups (allyl groups), and butynyl groups. Examples of branched alkenyl groups include 1-methylvinyl groups, 2-methylvinyl groups, 1-methylpropenyl groups, and 2-methylpropenyl groups. Among the linear alkenyl groups mentioned above, linear alkenyl groups are preferred, with vinyl groups and propenyl groups being more preferred.

[0105] Ra ０２ The alicyclic hydrocarbon group in this formula may be a polycyclic or monocyclic group. A preferred monocyclic alicyclic hydrocarbon group is a monocycloalkane with one hydrogen atom removed. The monocycloalkane is preferably one having 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. A preferred polycyclic alicyclic hydrocarbon group is a polycycloalkane with one hydrogen atom removed, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.

[0106] Ra ０２ The linear hydrocarbon group or alicyclic hydrocarbon group in each may or may not have substituents. These substituents may include halogen atoms, -CF ３ Substituents selected from the group consisting of -OH, -SH, and -CN are examples. Examples of halogen atoms as substituents include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.

[0107] Ra ０２ Preferably, the group is a chain-like hydrocarbon group which may have substituents, more preferably a chain-like hydrocarbon group which does not have substituents, even more preferably a linear hydrocarbon group which is a linear saturated hydrocarbon group which is particularly preferred, and most preferably an alkyl group having 1 to 4 carbon atoms.

[0108] In the above formula (a0-1), p is an integer greater than or equal to 1, and the upper limit of p is given by W０２ The structure of the aromatic hydrocarbon group in and q(-O-Ra ０２ The number of combinations of the elements is determined accordingly. p is preferably 1 or 2, and more preferably 1. In formula (a0-1), q is an integer of 1 or more, and the upper limit of q is given by W ０２ The structure of the aromatic hydrocarbon group in p(-Ya) ０１ -C(=O)-O-Ra ０１ The number of combinations is determined accordingly. q is, for example, an integer from 1 to 3, preferably 1 or 2, and more preferably 1.

[0109] The constituent unit (a0) is preferably a constituent unit represented by the following general formula (a0-1-u0) among the above.

[0110] [In the formula, R is an alkyl group having 1 to 5 carbon atoms, an alkyl halide having 1 to 5 carbon atoms, or a hydrogen atom. Ya ００１ This is a divalent linking group or a single bond. Yax ０１ This is a divalent linking group or a single bond. Rax ０１ It is an acid-dissociating group. ０２ p0 is an optionally substituted linear hydrocarbon group, or an optionally substituted alicyclic hydrocarbon group. p0 is an integer between 0 and 3. q0 is an integer greater than or equal to 1, where q0 ≤ p0 × 2 + 4.

[0111] In the formula (a0-1-u0), R is an alkyl group having 1 to 5 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a hydrogen atom. The alkyl group having 1 to 5 carbon atoms for R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, specifically including methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc. 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. The halogen atom is particularly preferably a fluorine atom. 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 due to their industrial availability, a hydrogen atom or a methyl group is most preferred.

[0112] In the above formula (a0-1-u0), Ya ００１ This is a divalent linking group or a single bond. ００１ 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. ０１ This is similar to the divalent hydrocarbon groups and divalent linking groups containing heteroatoms that were exemplified as other groups besides polymerizable groups in the above.

[0113] Among the above, Ya ００１ Preferably, the bonds are ester bonds [-C(=O)-O-, -O-C(=O)-], ether bonds (-O-), linear or branched alkylene groups, aromatic hydrocarbon groups or combinations thereof, or single bonds. Among these, Ya ００１ As such, ester bonds [-C(=O)-O-, -O-C(=O)-] and single bonds are more preferable, and single bonds are even more preferable.

[0114] In the above formula (a0-1-u0), Yax ０１ This is a divalent linking group or a single bond. Yax ０１ The divalent linking group in the above formula (a0-1) is Ya ０１This is similar to the explanation of divalent linking groups in Yax. ０１ The combination of an ester bond [-C(=O)-O-, -O-C(=O)-] and a linear alkylene group is more preferable, and a single bond is even more preferable.

[0115] In the above formula (a0-1-u0), Rax ０１ is an acid-dissociable group, and Ra in the above formula (a0-1) ０１ This is similar to the explanation of the acid-dissociating group in Rax. ０１ The above-mentioned "acetal-type acid-dissociating groups," "tertiary alkyl ester-type acid-dissociating groups," and "secondary alkyl ester-type acid-dissociating groups" are preferred, and among these, "tertiary alkyl ester-type acid-dissociating groups" and "secondary alkyl ester-type acid-dissociating groups" are more preferred, and the acid-dissociating group represented by the above general formula (a1-r-2) and the acid-dissociating group represented by the above general formula (a1-r-4) are even more preferred. Among these, Rax ０１ It is preferable that it is a cyclic group.

[0116] In the above formula (a0-1-u0), Rax ０２ is a chain hydrocarbon group which may have substituents, or an alicyclic hydrocarbon group which may have substituents, and Ra in formula (a0-1) ０２ The explanation for optionally substituted linear hydrocarbon groups or optionally substituted alicyclic hydrocarbon groups is the same as in the previous section. ０２ The linear hydrocarbon group or alicyclic hydrocarbon group in each may have substituents. These substituents may include halogen atoms, -CF ３ Substituents selected from the group consisting of -OH, -SH, and -CN are preferred. Examples of halogen atoms as substituents include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc. Rax ０２ Preferably, the group is a chain-like hydrocarbon group which may have substituents, more preferably a chain-like hydrocarbon group which does not have substituents, even more preferably a linear hydrocarbon group which is a linear saturated hydrocarbon group which is particularly preferred, and most preferably an alkyl group having 1 to 4 carbon atoms.

[0117] In the above formula (a0-1-u0), p0 is an integer from 0 to 3. When p0 is 0, it is a benzene structure; when p0 is 1, it is a naphthalene structure; when p0 is 2, it is an anthracene structure; and when p0 is 3, it is a tetracene structure. In the above formula (a0-1-u0), q0 is an integer of 1 or more, preferably an integer from 1 to 5, more preferably an integer from 1 to 3, and even more preferably 1 or 2. However, q0 ≤ p0 × 2 + 4.

[0118] For example, if p0 is 0 and the structure is benzene, then the benzene structure is (-CH ２ -C(R)-)-Ya ００１ - and - Yax ０１ -C(=O)-O-Rax ０１ All hydrogen atoms other than those substituted with the group are -O-Rax ０２ It may be substituted with a group. Also, in the benzene structure, -Yax ０１ -C(=O)-O-Rax ０１ Base, and -O-Rax ０２ The substitution positions of the elements are not particularly limited.

[0119] Below, aromatic hydrocarbon groups (W ０２ The substitution position for ) is fixed, Ra ０１ (Rax ０１ The following shows specific examples of constituent units (a0) with different structures. In each of the following equations, R α This represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0120]

[0121]

[0122]

[0123]

[0124]

[0125] Below, aromatic hydrocarbon groups (W ０２ The substitution position for ) is fixed, Ra ０２ (Rax ０２The following shows specific examples of constituent units (a0) with different structures. In each of the following equations, R α R represents a hydrogen atom, a methyl group, or a trifluoromethyl group. ０１ is any acid-dissociable group.

[0126]

[0127] Below, aromatic hydrocarbon groups (W ０２ The following shows specific examples of constituent units (a0) with different substitution positions for ). In each of the following formulas, R α R represents a hydrogen atom, a methyl group, or a trifluoromethyl group. ０１ R is any acid-dissociable group. ０２ is any chain-like hydrocarbon group or any alicyclic hydrocarbon group.

[0128]

[0129]

[0130] In the resist composition of this embodiment, the constituent unit (a0) is preferably at least one selected from the group consisting of constituent units represented by the above chemical formulas (a0-1-u1) to (a0-1-u39), and among these, it is more preferable that it be at least one selected from the group consisting of constituent units represented by the above chemical formulas (a0-1-u5) to (a0-1-u31) and (a0-1-u33) to (a0-1-u37), from the viewpoint of lithography characteristics such as dimensional uniformity and the ability to suppress the occurrence of pattern defects.

[0131] Alternatively, in the resist composition of this embodiment, the constituent unit (a0) is preferably at least one selected from the group consisting of constituent units represented by the above chemical formulas (a0-1-u51) to (a0-1-u57), and among these, it is more preferable that it be at least one selected from the group consisting of constituent units represented by the above chemical formula (a0-1-u51).

[0132] Alternatively, in the resist composition of this embodiment, it is preferable that the constituent unit (a0) is at least one selected from the group consisting of constituent units represented by the chemical formulas (a0-1-u110) to (a0-1-u190), (a0-1-u210), and (a0-1-u220).

[0133] The constituent units (a0) of component (A1) may be one type or two or more types. The proportion of constituent units (a0) in component (A1) is preferably 20 mol% to 80 mol%, more preferably 30 mol% to 70 mol%, and even more preferably 40 mol% to 60 mol%, based on the total amount (100 mol%) of all constituent units that make up component (A1). If the proportion of constituent units (a0) is above the lower limit of the preferred range described above, lithography characteristics such as sensitivity and dimensional uniformity, as well as the ability to suppress the occurrence of pattern defects, tend to be improved. On the other hand, if it is below the upper limit of the preferred range described above, it becomes easier to balance with the other constituent units.

[0134] <<Other constituent units besides constituent unit (a0)>> Component (A1) may have other constituent units as needed, in addition to the constituent unit (a0) described above. Examples of other constituent units include a constituent unit (a1) containing an acid-degradable group whose polarity increases with the action of an acid; a constituent unit (a10) represented by the general formula (a10-1) described below; a constituent unit (a2) containing a lactone-containing cyclic group; a constituent unit (a8) derived from a compound represented by the general formula (a8-1) described below; a constituent unit (a5) that generates acid upon exposure; and a constituent unit (a6) that has acid diffusion controllability. Note that among the other constituent units, those corresponding to the constituent unit (a0) described above are excluded.

[0135] Regarding constituent unit (a1): Constituent unit (a1) is a constituent unit that contains an acid-degradable group whose polarity increases upon the action of an acid. However, those corresponding to the above-mentioned constituent unit (a0) are excluded. An "acid-degradable group" is a group that has acid-degradability, in which at least some of the bonds in the structure of the acid-degradable group can be cleaved upon 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 these polar groups include carboxyl groups, hydroxyl groups, amino groups, and sulfo groups (-SO4). ３ Examples include H). More specifically, examples of acid-degradable groups include groups in which the 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).

[0136] Examples of acid-dissociable groups include those previously proposed as acid-dissociable groups for base resins used in chemically amplified resist compositions. Specifically, examples of acid-dissociable groups proposed for base resins used in chemically amplified resist compositions include the following: "acetal-type acid-dissociable groups," "tertiary alkyl ester-type acid-dissociable groups," "tertiary alkyloxycarbonyl acid-dissociable groups," and "secondary alkyl ester-type acid-dissociable groups."

[0137] Acetal-type acid-dissociating group: Among the polar groups, an example of an acid-dissociating group that protects a carboxyl group or a hydroxyl group is the acid-dissociating group represented by the general formula (a1-r-1) above (acetal-type acid-dissociating group).

[0138] 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 general formula (a1-r-2). Alternatively, Ra' in formula (a1-r-2) ５ and Ra' ６ When these groups bond to each other to form a ring, the group represented by the general formula (a1-r2-1), the group represented by the general formula (a1-r2-2), or the group represented by the general formula (a1-r2-3) are preferred. Alternatively, Ra' in formula (a1-r-2) ４ ~Ra' ６When these are independent hydrocarbon groups that are not bonded to each other, the group represented by the general formula (a1-r2-4) above is a preferred example.

[0139] Tertiary alkyloxycarbonylic acid dissociable group: Among the polar groups, an example of an acid-dissociable group that protects a hydroxyl group is the acid-dissociable group represented by the following general formula (a1-r-3) (hereinafter referred to as a "tertiary alkyloxycarbonylic acid dissociable group" for convenience).

[0140] [In the formula, Ra' ７ ~Ra' ９ These are each alkyl groups.

[0141] 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.

[0142] 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 general formula (a1-r-4).

[0143] Examples of the constituent unit (a1) include 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, a constituent unit derived from acrylamide, a constituent unit derived from hydroxystyrene or a hydroxystyrene derivative in which at least a portion of the hydrogen atoms in the hydroxyl group of the constituent unit is protected by a substituent containing the acid-degradable group, and a constituent unit derived from vinylbenzoic acid or a vinylbenzoic acid derivative in which at least a portion of the hydrogen atoms in the -C(=O)-OH group is protected by a substituent containing the acid-degradable group.

[0144] The following are specific examples of constituent units (a1). In each of the following formulas, R α This represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153] The constituent unit (a1) of component (A1) may be one type or two or more types. When component (A1) has constituent unit (a1), the proportion of constituent unit (a1) in component (A1) is preferably 20 mol% or less, and more preferably greater than 0 mol% and less than 20 mol%, relative to the total amount (100 mol%) of all constituent units that make up component (A1).

[0154] Regarding the constituent unit (a10): The constituent unit (a10) is a constituent unit represented by the following general formula (a10-1).

[0155] [In the formula, R is an alkyl group having 1 to 5 carbon atoms, an alkyl halide having 1 to 5 carbon atoms, or a hydrogen atom. Ya ｘ１ This is a divalent linking group or a single bond. Wa ｘ１ n is an aromatic hydrocarbon group which may have substituents. ａｘ１ [ is an integer greater than or equal to 1.]

[0156] In the above formula (a10-1), R is preferably an alkyl group having 1 to 5 carbon atoms, a fluorinated alkyl group having 1 to 5 carbon atoms, or a hydrogen atom. From the standpoint of industrial availability, a hydrogen atom, a methyl group, or a trifluoromethyl group is more preferred, a hydrogen atom or a methyl group is even more preferred, and a hydrogen atom is particularly preferred.

[0157] In the above formula (a10-1), Ya ｘ１is a divalent linking group or a single bond. In the above chemical formula, Ya ｘ１ The divalent linking group in is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have substituents, a divalent linking group which contains a heteroatom, and so on, respectively, as described above in W ０１ This is similar to the divalent hydrocarbon groups and divalent linking groups containing heteroatoms that were exemplified as other groups besides polymerizable groups in the above.

[0158] Ya ｘ１ Preferably, the group is a single bond, an ester bond [-C(=O)-O-, -O-C(=O)-], an ether bond (-O-), a linear or branched alkylene group, or a combination thereof, with single bonds and ester bonds [-C(=O)-O-, -O-C(=O)-] being more preferred.

[0159] In the above formula (a10-1), Wa ｘ１ Wa is an aromatic hydrocarbon group which may have substituents. ｘ１ The aromatic hydrocarbon group in this case is an aromatic ring which may have substituents (n ａｘ１ A 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 having 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 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. 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 A group with 1) hydrogen atoms removed can also be cited. Among the above, Wa ｘ１Examples 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 atom removed is even more preferable.

[0160] 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 the above W ０１ Examples of substituents for cyclic aliphatic hydrocarbon groups 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. Wa ｘ１ In this context, it is preferable that the aromatic hydrocarbon group does not have substituents.

[0161] In the above formula (a10-1), n ａｘ１ is an integer of 1 or more, preferably an integer from 1 to 10, more preferably an integer from 1 to 5, even more preferably 1, 2, or 3, and particularly preferably 1 or 2.

[0162] The following are specific examples of the constituent unit (a10) represented by the above formula (a10-1). In each of the following formulas, R α This represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0163]

[0164]

[0165]

[0166] The constituent unit (a10) of component (A1) may be one type or two or more types. When component (A1) has constituent unit (a10), the proportion of constituent unit (a10) in component (A1) is preferably 20 mol% to 80 mol%, more preferably 30 mol% to 70 mol%, and even more preferably 40 mol% to 60 mol%, based on the total amount (100 mol%) of all constituent units that make up component (A1). By having a proportion of constituent unit (a10) above the lower limit of the above preferred range, sensitivity can be more easily increased. On the other hand, by having a proportion below the upper limit of the above preferred range, it becomes easier to balance with other constituent units.

[0167] Regarding the constituent unit (a2): In addition to the constituent unit (a0), component (A1) may also have a constituent unit (a2) containing a lactone-containing cyclic group (excluding those corresponding to constituent units (a0) and (a1)). The lactone-containing cyclic group of constituent unit (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 constituent unit (a2) improves lithography characteristics, etc., through effects such as appropriately adjusting the acid diffusion length, improving the adhesion of the resist film to the substrate, and appropriately adjusting the solubility during development.

[0168] A "lactone-containing cyclic group" refers to a cyclic group that contains a ring (lactone ring) containing -O-C(=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, examples include the groups represented by the general formulas (a2-r-1) to (a2-r-8) described below.

[0169] 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. Such constituent units (a2) are preferably those represented by the following general formula (a2-1).

[0170] [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. Ya ２１ It is a single bond or a divalent linking group. La ２１ The group 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-. Ra ２１ This is a lactone-containing cyclic group.

[0171] 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.

[0172] In the above formula (a2-1), Ya ２１ The divalent linking group in is not particularly limited, but preferably includes a divalent hydrocarbon group which may have substituents, a divalent linking group which contains a heteroatom, and so on, respectively, as described above in W ０１ This is similar to the divalent hydrocarbon groups and divalent linking groups containing heteroatoms that were exemplified as other groups besides polymerizable groups in the above. ２１ The preferred elements are single bonds, ester bonds [-C(=O)-O-], ether bonds (-O-), linear or branched alkylene groups, or combinations thereof, with single bonds being particularly preferred.

[0173] In the above formula (a2-1), Ya ２１ It is a single bond, La ２１ It is preferable that it be -COO- or -OCO-.

[0174] In the formula (a2-1), Ra ２１ Ra is a lactone-containing cyclic group. ２１ Suitable lactone-containing cyclic groups in this compound include those represented by the general formulas (a2-r-1) to (a2-r-8), as described below.

[0175] The constituent unit (a2) of component (A1) may be one type or two or more types. When component (A1) has constituent unit (a2), the proportion of constituent unit (a2) is preferably more than 0 mol% and 20 mol% or less with respect to the total amount (100 mol%) of all constituent units that make up component (A1). If the proportion of constituent unit (a2) is above the lower limit of the preferred range mentioned above, the effect of including constituent unit (a2) is fully obtained, while if it is below the upper limit of the preferred range mentioned above, a balance with other constituent units can be maintained, resulting in good lithography characteristics in various fields.

[0176] Regarding the constituent unit (a8): The constituent unit (a8) is derived from the compound represented by the following general formula (a8-1).

[0177] [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. 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.]

[0178] In the above formula (a8-1), W ２ The explanation of the polymerizable group-containing group in the above-mentioned general formula (a0-1) is W ０１ This is similar to the explanation regarding polymerizable group-containing groups in W. ２ Examples of polymerizable groups include those with the chemical formula: C(R Ｘ１１) (Caution 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 an alkyl halogenated group having 1 to 5 carbon atoms, and Ya ｘ０ is a single bond or a divalent linking group, and W in the general formula (a0-1) described above. ０１ The chemical formula: C(R) Ｘ１１ ) (Caution Ｘ１２ ) = C(R Ｘ１３ )-Ya ｘ０ This is similar to the base represented by -.

[0179] The following shows specific examples of constituent units (a8). In the following formula, R α This represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0180]

[0181] The constituent units (a8) of component (A1) may be one type or two or more types. If component (A1) has constituent units (a8), the proportion of constituent units (a8) is preferably more than 0 mol% and 20 mol% or less, relative to the total amount (100 mol%) of all constituent units that make up component (A1).

[0182] Regarding the constituent unit (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 a constituent unit (a5) makes it easier for the acid generated upon exposure to be uniformly distributed within the resist film. Having a constituent unit (a5) makes it easier for the acid generated upon exposure to be uniformly distributed within the resist film. Examples of constituent units (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.

[0183] Regarding the constituent unit (a6) having acid diffusion controllability: Constituent unit (a6) is a constituent unit having acid diffusion controllability. Component (A1) may or may not have constituent unit (a6). Constituent unit (a6) can be one of known types. 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.

[0184] The resist composition may contain one type of component (A1) alone, or two or more types may be used in combination. In the resist composition of this embodiment, component (A1) includes a polymer compound having a repeating structure of constituent unit (a0). Among the above, a polymer compound having a repeating structure of constituent unit (a0) and constituent unit (a10) is preferred as component (A1).

[0185] More specifically, suitable polymer compounds for component (A1) include polymer compounds consisting only of a repeating structure of constituent unit (a0) (homopolymers), and polymer compounds having a repeating structure of constituent unit (a0) and constituent unit (a10).

[0186] In a polymer compound having a repeating structure of constituent units (a0) and constituent units (a10), the proportion of constituent units (a0) is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, even more preferably 30 to 70 mol%, and particularly preferably 40 to 60 mol%, based on the total amount (100 mol%) of all constituent units constituting the polymer compound. Furthermore, the proportion of constituent units (a10) in the polymer compound is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, even more preferably 30 to 70 mol%, and particularly preferably 40 to 60 mol%, based on the total amount (100 mol%) of all constituent units constituting the polymer compound.

[0187] Such 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) and polymerizing the mixture. Alternatively, such component (A1) can be produced by dissolving a monomer that induces constituent unit (a0) and, if necessary, a monomer that induces a constituent unit other than constituent unit (a0) (e.g., constituent unit (a10), etc.) in a polymerization solvent, adding a radical polymerization initiator as described above and polymerizing the mixture, and then carrying out a deprotection reaction. Note that during polymerization, for example, HS-CH ２ -CH ２ -CH ２ -C(CF ３ ) ２ By using a chain transfer agent such as -OH in combination, -C (CF) can be attached to the terminal. ３ ) ２ -OH groups may also be introduced. Copolymers into which hydroxyalkyl groups, in which some of the hydrogen atoms of the alkyl group are replaced with fluorine atoms, are introduced are effective in reducing development defects and LER (line edge roughness: uneven unevenness of the line sidewall).

[0188] The weight-average molecular weight (Mw) of component (A1) (based on polystyrene equivalent by gel permeation chromatography (GPC)) is not particularly limited, but is preferably 1,000 to 50,000, more preferably 2,000 to 30,000, and even more preferably 3,000 to 20,000. If the Mw of component (A1) is below the preferred upper limit of this range, it has sufficient solubility in resist solvents 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. The dispersion degree (Mw / Mn) of component (A1) is not particularly limited, but is preferably 1.0 to 3.0, more preferably 1.0 to 2.5, and particularly preferably 1.0 to 2.0. Mn represents the number-average molecular weight.

[0189] • Component (A2): Regarding the base material component, the resist composition of this embodiment may also use a base material component (hereinafter referred to as "component (A2)") as component (A), which does not fall under component (A1) and whose solubility in the developer solution changes due to the action of an acid. Component (A2) is not particularly limited and may be arbitrarily selected from a large number of base material components conventionally known for chemically amplified resist compositions. Component (A2) may be a single polymer compound or a low molecular weight compound, or two or more may be used in combination.

[0190] 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 be 100% by mass, based on the total mass of component (A). When the proportion is 25% by mass or more, it becomes easier to form a resist pattern that is excellent in various lithography characteristics such as high sensitivity, dimensional uniformity, suppression of pattern defect occurrence, and roughness improvement.

[0191] In the resist composition of this embodiment, the content of component (A) may be adjusted according to the resist film thickness to be formed.

[0192] <Component (B): Acid Generating Agent Component> In the resist composition of this embodiment, component (B) includes a compound (B0) represented by the following general formula (b0) (hereinafter also referred to as "component (B0)"). At least component (B0) is used as component (B), and other acid generating agents may be used in combination with component (B0). In the resist composition of this embodiment, component (B) may be used alone or two or more may be used in combination.

[0193] ≪Component (B0): Regarding the compound represented by general formula (b0)≫ Component (B0) is the compound represented by the following general formula (b0).

[0194] [In the formula, Rb ０ This is a fused cyclic group containing one or more aromatic rings. The fused cyclic group has a functional group (Fab) as a substituent that controls its solubility in the developer. Yb ０ Vb is a divalent linking group or a single bond. ０R is an alkylene group, a fluorinated alkylene group, or a single bond. ０ This is a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom. ｍ＋ [where m is an m-valent organic cation, and m is an integer greater than or equal to 1]

[0195] {Anion part of component (B0)} In the above formula (b0), Rb ０ This is a fused ring group containing one or more aromatic rings. The fused ring group has a functional group (Fab) as a substituent that controls its solubility in the developer.

[0196] Rb in the above formula (b0) ０ Specifically, the aromatic rings in this context 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.

[0197] Rb ０ The fused ring group in this product may be a polycyclic aromatic ring group formed by the condensation of multiple aromatic rings, or an aromatic ring-aliphatic hydrocarbon ring fused ring group formed by the condensation of an aromatic ring and an aliphatic hydrocarbon ring.

[0198] Examples of the polycyclic aromatic ring include 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. Rb ０Specific examples of polycyclic aromatic rings in this context include groups obtained by removing one hydrogen atom from the aromatic ring (aryl groups: for example, naphthyl groups), and groups in which one of the hydrogen atoms of the aromatic ring is replaced by an alkylene group (for example, arylalkyl groups such as phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, and 2-naphthylethyl groups). 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.

[0199] Rb ０ Examples of aromatic ring-aliphatic hydrocarbon ring-fused cyclic groups in this context include fluorene; and polycycloalkanes having a crosslinked ring system with one or more aromatic rings fused to it. Specific examples of the crosslinked ring system polycycloalkanes include bicycloalkanes such as bicyclo[2.2.1]heptane (norbornane) and bicyclo[2.2.2]octane. The aromatic ring-aliphatic hydrocarbon ring-fused cyclic 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. Rb ０ 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 Yb in formula (b0). ０ This represents a coupling that connects to something.

[0200]

[0201] In the above formula (b0), Rb ０ The fused ring group in is preferably an aromatic ring-aliphatic hydrocarbon ring fused ring group among the above, more preferably a group containing a fused ring in which two or three aromatic rings are fused to a bicycloalkane, even more preferably a group containing a fused ring in which two or three aromatic rings are fused to bicyclo[2.2.2]octane, and even more preferably the groups represented by the above formulas (r-br-1) to (r-br-2).

[0202] In the above formula (b0), Rb ０The fused ring group in this material has a substituent, a functional group (Fab), that controls solubility in the developer. Here, "functional group (Fab) that controls solubility in the developer" refers to an atomic group that, in the formation of a resist pattern, allows for adjustment of the solubility of the resist film in the developer when the resist film is developed, either increasing or decreasing its solubility in the developer. Examples of such functional groups (Fab) include acid-degradable groups (Fa) that decompose upon the action of an acid to produce a polar group, and base-degradable groups (Fb) that have the decomposition property of cleaving at least some of the bonds in the structure upon the action of a base.

[0203] Regarding acid-degradable groups (Fa): The acid-degradable group (Fa) referred to here 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. An example of this is an acid-degradable group that decomposes to produce a polar group by the action of an acid. In the above formula (b0), Rb ０ The fused cyclic group in this compound has an acid-degradable group (Fa) as a substituent that decomposes upon the action of an acid to produce a polar group. Specifically, examples of acid-dissociable groups constituting this acid-degradable group include "acetal-type acid-dissociable groups," "tertiary alkyl ester-type acid-dissociable groups," and "tertiary alkyloxycarbonyl acid-dissociable groups." Examples of the polar group include a carboxyl group, a hydroxyl group, an amino group, and a sulfo group (-SO ３ Examples include H).

[0204] Acetal-type acid-dissociating groups: Examples of acid-dissociating groups that protect hydroxyl groups include the acid-dissociating group represented by the following general formula (a1-r-1).

[0205] [In the formula, Ra' １ , Ra' ２ Ra' is a hydrogen atom or an alkyl group. ３ is a hydrocarbon group, Ra' ３ Ra' １ , Ra' ２ It may combine with any of the following to form a ring.

[0206] Tertiary alkyl ester type acid-dissociating group: 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).

[0207] [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.

[0208] Tertiary alkyloxycarbonylic acid dissociable group: An example of an acid-dissociable group that protects a hydroxyl group is the acid-dissociable group represented by the following general formula (a1-r-3).

[0209] [In the formula, Ra' ７ ~Ra' ９ These are each alkyl groups.

[0210] The "acetal-type acid-dissociable group," "tertiary alkyl ester-type acid-dissociable group," and "tertiary alkyloxycarbonylic acid-dissociable group" are the same as those described above for the constituent unit (a0) or constituent unit (a1) of component (A).

[0211] Rb ０ The acid-dissociable group constituting the acid-degradable group (Fa) of the fused cyclic group in is not particularly limited and may be any acid-dissociable group other than the "acetal-type acid-dissociable group," "tertiary alkyl ester-type acid-dissociable group," and "tertiary alkyloxycarbonyl acid-dissociable group" described above.

[0212] Rb ０ Among the above, the acid-degradable group (Fa) of the fused ring group in is preferably the acid-degradable group represented by the following general formula (pg-1).

[0213] [In formula (pg-1), Rpg is an acid-dissociable group represented by the following general formula (pg-r-1), an acid-dissociable group represented by the following general formula (pg-r-2), an acid-dissociable group represented by the following general formula (pg-r-3), or an acid-dissociable group represented by the following general formula (pg-r-4). * indicates a bond.]

[0214] [In formula (pg-r-1), Rb １ ~Rb ３ Each of these is independently a hydrocarbon group, and Rb １ and Rb ２ These may be bonded to each other to form a ring. In formula (pg-r-2), Rb ００１ It is a linear or branched aliphatic hydrocarbon group. ００２ Rb is a single bond or a divalent linking group. ００２ This Ar is a hydrogen atom or substituent. This Ar is a benzene ring or a naphthalene ring. Rm ０１ is a substituent. n01 is an integer from 1 to 4. In formula (pg-r-3), Xb is a secondary carbon atom. X is an alicyclic hydrocarbon ring which may have substituents. This Ar is a benzene ring or a naphthalene ring. Rm ０２ is a substituent. n02 is an integer from 1 to 4. In formula (pg-r-4), Rb' １ and Rb' ２ Each of these is independently either a hydrogen atom or an alkyl group. Rb' ３ Rb' is a hydrocarbon group. ３ is Rb' １ , Rb' ２ It may bond with any of the following to form a ring. * indicates a bond with the oxygen atom (-O-) in the general formula (pg-1).

[0215] The acid-dissociable group represented by the above general formula (pg-r-1) is the same as the acid-dissociable group represented by the above general formula (a1-r-2) in the constituent unit (a1) of component (A) described above. That is, Rb in the above general formula (pg-r-1) １ and Ra' in the above general formula (a1-r-2) ４ , Rb in the above general formula (pg-r-1) ２and Ra' in the above general formula (a1-r-2) ５ , Rb in the above general formula (pg-r-1) ３ and Ra' in the above general formula (a1-r-2) ６ These are all similar examples.

[0216] In the acid-dissociable group represented by the above general formula (pg-r-1), Rb １ and Rb ２ When these groups bond to each other to form a ring, the groups represented by the following general formula (a1-r2-1), the group represented by the following general formula (a1-r2-2), and the group represented by the following general formula (a1-r2-3) are preferred. On the other hand, Rb １ ~Rb ３ 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.

[0217] [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 together with the bonded carbon atom. In formula (a1-r2-2), Ya is a carbon atom. Xa is a group that forms a cyclic hydrocarbon group together with Ya. Some or all of the hydrogen atoms in this cyclic hydrocarbon group may be substituted. Ra 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. Ra 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 or a hydrogen atom. Some or all of the hydrogen atoms in this chain-like saturated hydrocarbon group may be substituted. Ra' １４ This is a hydrocarbon group that may have substituents. * indicates a bond.

[0218] The groups represented by the general formulas (a1-r2-1) to (a1-r2-4) are the same as the groups represented by the general formulas (a1-r2-1) to (a1-r2-4) in the constituent unit (a0) of component (A) described above.

[0219] In the above general formula (pg-r-2), Rb ００１ Rb is a linear or branched aliphatic hydrocarbon group. ００１ The linear or branched aliphatic hydrocarbon group in is preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms, more preferably a methyl group, ethyl group, propyl group, 1-methylethyl group, 1-methylpropyl group, or 2-methylpropyl group, and even more preferably a methyl group.

[0220] In the above general formula (pg-r-2), Ya ００２ It is a single bond or a divalent linking group. ００２ As for the divalent linking group in, Ya in the constituent unit (a10) of component (A) described above ｘ１ Similar examples include divalent hydrocarbon groups which may have substituents, and divalent linking groups which contain heteroatoms.

[0221] Ya ００２ Among the above, single-bonded, linear, or branched aliphatic hydrocarbon groups are preferred, single-bonded or linear aliphatic hydrocarbon groups are more preferred, and single-bonded or methylene groups [-CH ２ -] or ethylene group [- (CH ２ ) ２ -] is even more preferable, with a single bond or methylene group [-CH ２ - is particularly preferred, and a single bond is most preferred.

[0222] In the above general formula (pg-r-2), Rb ００２Rb is a hydrogen atom or a substituent. ００２ Examples of substituents in Rb include carboxyl groups, hydroxyl groups, amino groups, sulfol groups, halogen atoms, alkyl halides, alkoxy groups, alkyloxycarbonyl groups, and nitro groups, among which hydroxyl groups are preferred. ００２ Among the above, it is preferably a hydrogen atom or a hydroxyl group, and more preferably a hydrogen atom.

[0223] In the above general formula (pg-r-2), Ar is a benzene ring or a naphthalene ring, and is preferably a benzene ring.

[0224] In the above general formula (pg-r-2), Rm ０１ Specifically, examples of substituents in include carboxyl groups, hydroxyl groups, amino groups, sulfol groups, halogen atoms, alkyl halides, alkoxy groups, alkyloxycarbonyl groups, nitro groups, etc., among which hydroxyl groups are preferred. In the above general formula (pg-r-2), Rm ０１ It is preferable that it be a hydrogen atom.

[0225] In the above general formula (pg-r-2), n01 is an integer from 1 to 4, preferably 1 or 2.

[0226] In the above general formula (pg-r-3), X is an alicyclic hydrocarbon ring which may have substituents. The alicyclic hydrocarbon ring is preferably one having 4 to 20 carbon atoms, more preferably one having 5 to 15 carbon atoms, and even more preferably one having 5 to 10 carbon atoms. Specifically, examples include aliphatic rings such as cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, and cyclododecane, and spiroalkanes such as spiro[4.5]decane and spiro[5.5]undecane.

[0227] In the above general formula (pg-r-3), Ar is a benzene ring or a naphthalene ring, and is preferably a benzene ring.

[0228] In the above general formula (pg-r-3), Rm ０２Examples of substituents in this compound include carboxyl groups, hydroxyl groups, amino groups, sulfol groups, halogen atoms, alkyl halides, alkoxy groups, alkyloxycarbonyl groups, and nitro groups, with hydroxyl groups being preferred among them.

[0229] In the above general formula (pg-r-3), n02 is an integer from 1 to 4, preferably 1 or 2.

[0230] The acid-dissociable group represented by the above general formula (pg-r-4) is the same as the acid-dissociable group represented by formula (a1-r-1) in the constituent unit (a0) of component (A) described above. That is, Rb' in the above general formula (pg-r-4) １ and Ra' in the above general formula (a1-r-1) １ , Rb' in the above general formula (pg-r-4) ２ and Ra' in the above general formula (a1-r-1) ２ , Rb' in the above general formula (pg-r-4) ３ and Ra' in the above general formula (a1-r-1) ３ These are all similar examples.

[0231] In the acid-degradable group represented by the general formula (pg-1) above, Rpg is preferably a cyclic acid-dissociable group from the viewpoint of further improving acid dissociation ability, more preferably an acid-dissociable group represented by any of the general formulas (pg-r-1) to (pg-r-3), and even more preferably the acid-dissociable group represented by the general formula (pg-r-1). More specifically, Rpg is preferably an acid-dissociable group represented by the general formula (a1-r2-1).

[0232] If Rpg in the acid-degradable group represented by the above general formula (pg-1) is an acid-dissociable group represented by the above general formula (a1-r2-1), then Ra' in the above general formula (a1-r2-1) １０ The Ra' in the above general formula (a1-r2-1) is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and more preferably a linear alkyl group having 1 to 5 carbon atoms. １１ (Ra' １０The aliphatic cyclic group formed with the bonded carbon atom is preferably a monocyclic alicyclic hydrocarbon group, more preferably a cyclopentyl group or a cyclohexyl group, and even more preferably a cyclopentyl group.

[0233] In the above formula (b0), Rb ０ The fused ring group in may have substituents other than the functional group (Fab) described above. Examples of substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, nitro groups, and carbonyl groups. Preferably, alkyl groups have 1 to 5 carbon atoms, with methyl, ethyl, propyl, n-butyl, and tert-butyl groups being the most preferred. Preferably, alkoxy groups have 1 to 5 carbon atoms, with methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, and tert-butoxy groups being the most preferred, with methoxy and ethoxy groups being the most preferred. Preferably, fluorine atoms are used as halogen atoms. Examples of alkyl halides are 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. The carbonyl group as a substituent is a methylene group (-CH) that constitutes a cyclic hydrocarbon group. ２ It is a substituting group for -).

[0234] Regarding base-degradable groups (Fb): The base-degradable group (Fb) referred to here is a group that has base-degradability, meaning that at least some of the bonds in its structure can be cleaved by the action of a base. An example of such a group is a base-degradable group that decomposes upon the action of an alkaline developer to produce a polar group. Examples of such polar groups include carboxyl groups and hydroxyl groups. "Base-degradability, meaning that the bonds can be cleaved upon the action of a base" means, for example, that the group decomposes upon the action of a 0.1 to 30% by mass alkaline developer (preferably, decomposition upon the action of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 23°C), and its solubility in the alkaline developer increases. This is because, for example, the ester bond decomposes (hydrolyzes) upon the action of the alkaline developer (base), producing a polar group.

[0235] The base-degradable group (Fb) is not particularly limited as long as it is a group that decomposes with a base and changes the (B0) component to be soluble in an alkaline developer. Any base-degradable group previously proposed in chemically amplified resist compositions can be used, for example, a structure containing an ester bond. Among these, Rb in formula (b0) is particularly important. ０ The (condensed cyclic group) is preferably a group that includes a lactone-containing cyclic group as a substituent.

[0236] A "lactone-containing cyclic group" refers to a cyclic group that contains a ring (lactone ring) containing -O-C(=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, and if it 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. Such a lactone-containing cyclic group is not particularly limited and any group can be used. Specifically, examples include the groups represented by the following general formulas (a²-r-1) to (a²-r-8).

[0237] [In the formula, Ra' ２１Each 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.

[0238] In the formulas (a2-r-1) to (a2-r-8), 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-). ２１ In this, 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.

[0239] Ra' ２１In -COOR'' and -OC(=O)R'', R'' is a hydrogen atom, an alkyl group, or a lactone-containing cyclic group. The alkyl group in R'' may be linear, branched, or cyclic, and preferably has 1 to 15 carbon atoms. If R'' is a linear or branched alkyl group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and is particularly preferably a methyl group or an ethyl group. If 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, examples include 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; and a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as bicycloalkanes, tricycloalkanes, or tetracycloalkanes. More specifically, examples include groups obtained by removing one or more hydrogen atoms from monocycloalkanes such as cyclopentane and cyclohexane; and groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Examples of lactone-containing cyclic groups in R'' include those similar to those represented by the general formulas (a²-r-1) to (a²-r-8) above. Ra' ２１ The hydroxyalkyl group in is preferably one having 1 to 6 carbon atoms, specifically the Ra' ２１ Examples include groups in which at least one hydrogen atom of the alkyl group is substituted with a hydroxyl group.

[0240] Ra' ２１ Among the above, it is preferable that each is independently a hydrogen atom or a cyano group.

[0241] In the general formulas (a2-r-2), (a2-r-3), and (a2-r-5), 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. When the alkylene group contains an oxygen atom or a sulfur atom, a specific example is a group in which -O- or -S- is interposed at the end or between carbon atoms of the alkylene group, for example, -O-CH ２ -ien-CH ２ -O-CH ２ -, -S-CH ２ -ien-CH ２ -S-CH ２ Examples include the following. A'' 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 most preferably a methylene group.

[0242] The following are specific examples of the groups represented by the general formulas (a²-r-1) to (a²-r-8).

[0243]

[0244]

[0245] In the above formula (b0), Rb ０ The functional group (Fab) that controls the solubility in the developer, which is a substituent of the fused cyclic group in the compound, is preferably a functional group selected from the group consisting of an acid-degradable group (Fa) that decomposes upon the action of an acid to produce a polar group, and a base-degradable group (Fb) that has the decomposition ability to cleave at least some of the bonds in the structure upon the action of a base, and more preferably the acid-degradable group (Fa). Among the base-degradable groups (Fb), it is preferably a group containing a lactone-containing cyclic group, more preferably the groups represented by the general formulas (a2-r-1) to (a2-r-8), and even more preferably the groups represented by the general formulas (a2-r-1) to (a2-r-2).

[0246] In the above formula (b0), Yb ０ Yb is a divalent linking group or a single bond. ０In this context, a divalent linking group containing an oxygen atom is preferred. ０ If Yb is a divalent linking group containing an oxygen atom, ０ This may include 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 oxygen atoms include non-hydrocarbon oxygen-containing linking groups such as oxygen atoms (ether bond: -O-), ester bonds (-C(=O)-O-), oxycarbonyl groups (-O-C(=O)-), amide bonds (-C(=O)-NH-), carbonyl groups (-C(=O)-), and carbonate bonds (-O-C(=O)-O-); and combinations of these non-hydrocarbon oxygen-containing linking groups with alkylene groups. This combination may further include sulfonyl groups (-SO ２ A -) may be linked. Examples of such divalent linking groups containing an oxygen atom include the linking groups represented by the following general formulas (y-al-1) to (y-al-9). Note that in the following general formulas (y-al-1) to (y-al-9), Rb in formula (b0) above is... ０ The combination with this is V' in the following general formulas (y-al-1) to (y-al-9). １０１ That is the case.

[0247] [In the formula, V' １０１ V' is an alkylene group or single bond having 1 to 5 carbon atoms. １０２ This is a divalent hydrocarbon group having 1 to 30 carbon atoms.

[0248] V' １０１ V' is an alkylene group having 1 to 5 carbon atoms or a single bond, preferably a single bond. １０２ The divalent hydrocarbon group in this expression may be a saturated hydrocarbon group or an aromatic hydrocarbon group. These saturated hydrocarbon groups and aromatic hydrocarbon groups may each have substituents.

[0249] V' １０２In this, the divalent saturated hydrocarbon group 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.

[0250] V' １０１ and V' １０２ The alkylene group in V' may be a linear alkylene group or a branched alkylene group, but a linear alkylene group is preferred. １０１ and V' １０２ Specifically, the alkylene group in this case is the methylene group [-CH ２ -come; -CH(CH ３ )-,-CH(CH ２ CH ３ )-,-C(CH ３ ) ２ -, -C(CH ３ ) (CH ２ CH ３ )-,-C(CH ３ ) (CH ２ CH ２ CH ３ )-,-C(CH ２ CH ３ ) ２ - Alkylmethylene groups such as; ethylene groups [-CH ２ CH ２ -come; -CH(CH ３ )CH ２ -, -CH(CH ３ )CH(CH ３ )-,-C(CH ３ ) ２ CH ２ -, -CH(CH ２ CH ３ )CH ２ - Alkylethylene groups such as; trimethylene group (n-propylene group) [-CH ２ CH ２ CH ２ -come; -CH(CH ３ )CH ２ CH ２ -ien-CH ２ CH (CH ３ )CH ２- Alkyl trimethylene groups such as; tetramethylene groups [-CH ２ CH ２ CH ２ CH ２ -come; -CH(CH ３ )CH ２ CH ２ CH ２ -ien-CH ２ CH (CH ３ )CH ２ CH ２ - Alkyltetramethylene groups such as; pentamethylene groups [-CH ２ CH ２ CH ２ CH ２ CH ２ -] are some examples. Also, V' 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 preferably a cyclohexylene group, a 1,5-adamantilene group, or a 2,6-adamantilene group.

[0251] V' １０２ The aromatic hydrocarbon group in this context refers to a group obtained by removing two or more hydrogen atoms from an aromatic ring, which may have substituents. The aromatic ring here is not particularly limited as long as it is a cyclic conjugated system having 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 substituted with heteroatoms. Examples of heteroatoms in the aromatic heterocycle include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of aromatic heterocycles include pyridine rings and thiophene rings. V' １０２ Examples of aromatic hydrocarbon groups in this context include groups obtained by removing two or more hydrogen atoms from aromatic compounds containing aromatic rings that may have substituents (e.g., biphenyl, fluorene, etc.). Among the above, V' １０２The aromatic hydrocarbon group in is preferably a group obtained by removing two or more hydrogen atoms from benzene, naphthalene, anthracene, or biphenyl, more preferably a group obtained by removing two or more hydrogen atoms from benzene or naphthalene, and even more preferably a group obtained by removing two or more hydrogen atoms from benzene.

[0252] V' １０２ Examples of substituents that may be present on a divalent hydrocarbon group (saturated hydrocarbon group, aromatic hydrocarbon group) include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, nitro groups, and carbonyl groups. Preferred alkyl groups as substituents are alkyl groups having 1 to 5 carbon atoms, with methyl, ethyl, propyl, n-butyl, and tert-butyl groups being the most preferred. Preferred alkoxy groups as substituents are alkoxy groups having 1 to 5 carbon atoms, with methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, and tert-butoxy groups being more preferred, with methoxy and ethoxy groups being the most preferred. Examples of halogen atoms as substituents include fluorine, chlorine, bromine, and iodine atoms, with iodine being the preferred atom. Examples of alkyl halides 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. The carbonyl group as a substituent is a methylene group (-CH) that constitutes a cyclic hydrocarbon group. ２ It is a substituting group for -).

[0253] V' １０２ In this context, the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group which may have substituents. If substituents are present, halogen atoms are preferred, and iodine atoms are more preferred.

[0254] Yb ０Preferably, the linking group is a divalent linking group containing an ester bond or a divalent linking group containing an ether bond, more preferably a divalent linking group containing an ester bond, even more preferably the linking groups represented by the general formulas (y-al-1) to (y-al-5), respectively, particularly preferably the linking groups represented by the general formulas (y-al-1), (y-al-2), or (y-al-4), and most preferably the linking groups represented by the general formulas (y-al-2) or (y-al-4).

[0255] In the formula (b0), Vb ０ This is an alkylene group, a fluorinated alkylene group, or a single bond. Vb ０ In this compound, the alkylene group and the fluorinated alkylene group each preferably have 1 to 4 carbon atoms, and more preferably 1 to 3 carbon atoms. Vb ０ Examples of fluorinated alkylene groups include groups in which some or all of the hydrogen atoms of the alkylene group are replaced with fluorine atoms. Among these, Vb ０ It is preferably an alkylene group having 1 to 4 carbon atoms, a fluorinated alkylene group having 1 to 4 carbon atoms, or a single bond, and more preferably an alkylene group having 1 to 3 carbon atoms in which some of the hydrogen atoms are replaced by fluorine atoms, or a single bond.

[0256] In the above formula (b0), R ０ R is a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom. ０ It is preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and more preferably a fluorine atom.

[0257] In this embodiment, the anion portion of component (B0) is preferably an anion represented by the following general formula (b0-an0) from the viewpoint of in-plane uniformity of pattern dimensions (CDU) and resolution performance.

[0258] [In the formula, Rx １ ~Rx ４ Each of these independently represents a hydrocarbon group or hydrogen atom which may have substituents, or two or more may be bonded to each other to form a ring structure. １ ~Ry ２Each of these elements independently represents a hydrocarbon group or hydrogen atom which may have substituents, or they may be bonded to each other to form a ring structure. It is either a double bond or a single bond. Rz １ ~Rz ４ Each of these independently represents a hydrocarbon group or hydrogen atom that may have substituents if the valence allows, or two or more may be bonded to each other to form a ring structure. However, Rx １ ~Rx ４ Two or more of the following, １ ~Ry ２ , or Rz １ ~Rz ４ At least one of the two or more of these is bonded to each other to form an aromatic ring. Also, Rx １ ~Rx ４ , Ry １ ~Ry ２ and Rz １ ~Rz ４ At least one of them has an anionic group represented by the following general formula (b0-r-an1), and the entire anionic part forms an n-valent anion. Also, Rx １ ~Rx ４ , Ry １ ~Ry ２ and Rz １ ~Rz ４ At least one of them has the functional group (Fab). n is an integer of 1 or more.

[0259] [In the formula, Yb ０ Vb is a divalent linking group or a single bond. ０ R is an alkylene group, a fluorinated alkylene group, or a single bond. ０ This is a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom. * indicates a bond.

[0260] In the formula (b0-an0), Rx １ ~Rx ４ Each of these independently represents a hydrocarbon group or hydrogen atom which may have substituents, or two or more may be bonded to each other to form a ring structure. １ ~Ry ２Each of these independently represents a hydrocarbon group or hydrogen atom which may have substituents, or they may be bonded to each other to form a ring structure. １ ~Rz ４ Each of these independently represents a hydrocarbon group or hydrogen atom that may have substituents, provided the valence is permissible, or two or more may be bonded to each other to form a ring structure.

[0261] Rx １ ~Rx ４ , Ry １ ~Ry ２ , Rz １ ~Rz ４ The hydrocarbon groups in each of these may be aliphatic hydrocarbon groups, aromatic hydrocarbon groups, cyclic hydrocarbon groups, or chain-like hydrocarbon groups. For example, Rx １ ~Rx ４ , Ry １ ~Ry ２ , Rz １ ~Rz ４ Examples of optionally substituted hydrocarbon groups include optionally substituted cyclic groups, optionally substituted linear alkyl groups, or optionally substituted linear alkenyl groups.

[0262] A cyclic group which 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. Also, Rx １ ~Rx ４ , Ry １ ~Ry ２ , Rz １ ~Rz ４ The cyclic hydrocarbon group in this example may contain heteroatoms, such as heterocycles.

[0263] Rx １ ~Rx ４ , Ry １ ~Ry ２ , Rz １ ~Rz ４The aromatic hydrocarbon group in this expression 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 12. However, this number of carbon atoms does not include the number of carbon atoms in substituents. Rx １ ~Rx ４ , Ry １ ~Ry ２ , Rz １ ~Rz ４ 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. １ ~Rx ４ , Ry １ ~Ry ２ , Rz １ ~Rz ４ The aromatic ring of the aromatic hydrocarbon group in (A) is preferably free of heteroatoms from the viewpoint of compatibility with component (A), and aromatic rings such as benzene, fluorene, naphthalene, anthracene, phenanthrene, and biphenyl are more preferred. １ ~Rx ４ , Ry １ ~Ry ２ , Rz １ ~Rz ４ 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, arylalkyl groups such as benzyl groups, phenethyl groups, 1-naphthylmethyl groups, 2-naphthylmethyl groups, 1-naphthylethyl groups, 2-naphthylethyl 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.

[0264] Rx １ ~Rx ４ , Ry １ ~Ry ２ , Rz １ ~Rz ４ The cyclic aliphatic hydrocarbon group in this context refers to an aliphatic hydrocarbon group that contains a ring in its structure. Examples of aliphatic hydrocarbon groups containing a ring in their 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 has 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. As a monocyclic alicyclic hydrocarbon group, a group from which one or more hydrogen atoms have been removed from a monocycloalkane is preferred. The monocycloalkane preferably has 3 to 6 carbon atoms, and specifically examples include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably 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.

[0265] 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 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. A linear alkylene group is preferred as the linear aliphatic hydrocarbon group, specifically a methylene group [-CH] ２ -], ethylene group [- (CH ２ ) ２ -], trimethylene group [-(CH ２ ) ３ -], tetramethylene group [-(CH ２ ) ４ -], pentamethylene group [-(CH ２ ) ５Examples include -]. 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 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. A branched alkylene group is preferred as the branched aliphatic hydrocarbon group, specifically -CH(CH ３ )-,-CH(CH ２ CH ３ )-,-C(CH ３ ) ２ -, -C(CH ３ ) (CH ２ CH ３ )-,-C(CH ３ ) (CH ２ CH ２ CH ３ )-,-C(CH ２ CH ３ ) ２ - Alkyl methylene groups such as -CH(CH ３ )CH ２ -, -CH(CH ３ )CH(CH ３ )-,-C(CH ３ ) ２ CH ２ -, -CH(CH ２ CH ３ )CH ２ -, -C(CH ２ CH ３ ) ２ -CH ２ - Alkyl ethylene groups such as -CH(CH ３ )CH ２ CH ２ -ien-CH ２ CH (CH ３ )CH ２ - Alkyl trimethylene groups such as -CH(CH ３ )CH ２ CH ２ CH ２ -ien-CH ２ CH (CH ３ )CH ２ CH ２Examples include alkylalkylene groups such as alkyltetramethylene groups. In the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0266] Also, Rx １ ~Rx ４ , Ry １ ~Ry ２ , Rz １ ~Rz ４ The cyclic group is -COOR ＸＹＺ -OC(=O)R ＸＹＺ Regarding R ＸＹＺ is a lactone-containing cyclic group, a carbonate-containing cyclic group, or -SO ２ - This also includes those containing cyclic groups.

[0267] Rx １ ~Rx ４ , Ry １ ~Ry ２ , Rz １ ~Rz ４ As for substituents in the cyclic group, the above-mentioned Rb ０ Examples of substituents similar to those that may be present on the polycyclic aromatic cyclic group in Rx. １ ~Rx ４ , Ry １ ~Ry ２ , Rz １ ~Rz ４ Among the substituents on the cyclic group, alkyl groups, halogen atoms, and alkyl halides are preferred from the viewpoint of compatibility with component (A).

[0268] A chain-like alkyl group which may have substituents: Rx １ ~Rx ４ , Ry １ ~Ry ２ , Rz １ ~Rz ４The linear alkyl group may be linear or branched. Linear alkyl groups preferably have 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. Specifically, examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decanyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, isohexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, henicosyl, and docosyl groups. Branched alkyl groups preferably have 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, 1,1-dimethylethyl 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.

[0269] A chain-like alkenyl group which may have substituents: Rx １ ~Rx ４ , Ry １ ~Ry ２ , Rz １ ~Rz ４ The linear alkenyl group may be 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 linear alkenyl groups include vinyl groups, propenyl groups (allyl groups), and butynyl groups. Examples of branched alkenyl groups include 1-propenyl groups, 2-propenyl groups (allyl groups), 1-methylpropenyl groups, and 2-methylpropenyl groups.

[0270] Rx １ ~Rx ４ , Ry １ ~Ry ２ , Rz １~Rz ４ Substituents in the chain-like alkyl or alkenyl group include, for example, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, nitro groups, amino groups, and the above Rx １ ~Rx ４ , Ry １ ~Ry ２ , Rz １ ~Rz ４ Examples include cyclic groups in [the following]. Among them, Rx １ ~Rx ４ , Ry １ ~Ry ２ , Rz １ ~Rz ４ As substituents in the chain-like alkyl or alkenyl group, from the viewpoint of compatibility with component (A), halogen atoms, alkyl halides, and the above Rx １ ~Rx ４ , Ry １ ~Ry ２ , Rz １ ~Rz ４ The cyclic groups listed in this context are preferred.

[0271] In the above formula (b0 - an0), Ry １ ~Ry ２ These may be bonded to each other to form a ring structure. １ ~Ry ２ The ring structure formed is one side (Ry) of the six-membered ring in formula (b0-an0). １ and Ry ２ Each ring structure shares a bond between carbon atoms, and this ring structure may be an alicyclic hydrocarbon or an aromatic hydrocarbon. Furthermore, this ring structure may be a polycyclic structure consisting of other ring structures.

[0272] Ry １ ~Ry ２The alicyclic hydrocarbons formed may be polycyclic or monocyclic. Monocyclic alicyclic hydrocarbons are preferred, and monocycloalkanes are preferred. Monocycloalkanes with 3 to 6 carbon atoms are preferred, and specific examples include cyclopentane and cyclohexane. Polycyclic alicyclic hydrocarbons are preferred, and polycycloalkanes with 7 to 30 carbon atoms are preferred.

[0273] Ry １ ~Ry ２ The aromatic hydrocarbon rings formed by these 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. １ ~Ry ２ The aromatic hydrocarbon ring formed is preferably free of heteroatoms from the viewpoint of compatibility with component (A), and aromatic rings such as benzene, fluorene, naphthalene, anthracene, phenanthrene, and biphenyl are more preferable.

[0274] Ry １ ~Ry ２ The ring structure formed by (alicyclic hydrocarbon, aromatic hydrocarbon) may have substituents. Examples of substituents here include the Rx mentioned above. １ ~Rx ４ , Ry １ ~Ry ２ , Rz １ ~Rz ４ Examples include substituents on the cyclic group (for example, alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, nitro groups, carbonyl groups, etc.). Among them, Ry １ ~Ry ２ From the viewpoint of compatibility with component (A), alkyl groups, halogen atoms, and alkyl halides are preferred as substituents in the ring structure formed by (A).

[0275] Ry １ ~Ry ２ Of the ring structures formed, aromatic hydrocarbons, which may have substituents, are more preferred from the viewpoint of shortening the diffusion of acid generated by exposure and controlling the diffusion of acid.

[0276] In the above formula (b0 - an0), Rz １ ~Rz ４ Two or more of these may be bonded to each other to form a ring structure. For example, Rz １ Rz ２ ~Rz ４ Either of them may form a ring structure. Specifically, one side (Rz) of the six-membered ring in formula (b0-an0) １ and Rz ２ The carbon atom to which it is bonded, and Rz ３ and Rz ４ A ring structure that shares a bond with the carbon atom to which it is bonded, Rz １ and Rz ２ A ring structure formed by the bonding of Rz ３ and Rz ４ Examples include ring structures formed by the bonding of Rz. １ ~Rz ４ The ring structure formed by two or more of these elements may be an alicyclic hydrocarbon or an aromatic hydrocarbon, and is preferably an aromatic hydrocarbon. Furthermore, this ring structure may be a polycyclic structure consisting of other ring structures.

[0277] Rz １ ~Rz ４ The alicyclic hydrocarbon formed by two or more of these atoms may be polycyclic or monocyclic. Monocyclic alicyclic hydrocarbons are preferred, and monocycloalkanes are preferred. Monocycloalkanes are preferred, and those having 3 to 6 carbon atoms are preferred, specifically cyclopentane and cyclohexane. Polycyclic alicyclic hydrocarbons are preferred, and polycycloalkanes are preferred, and those having 7 to 30 carbon atoms are preferred, specifically polycycloalkanes having a bridging ring system polycyclic skeleton such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; polycycloalkanes having a fused ring system polycyclic skeleton such as a cyclic group having a steroid skeleton are more preferred. Heterocyclic structures in which some carbon atoms are substituted with heteroatoms are also possible, and nitrogen-containing heterocycles are particularly preferred, specifically cyclic imides.

[0278] Rz １ ~Rz４ Two or more of them form an aromatic hydrocarbon ring, such as benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or an aromatic heterocyclic ring in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms. Rz １ ~Rz ４ Two or more of them form an aromatic hydrocarbon ring, which preferably does not contain heteroatoms from the viewpoint of compatibility with the (A) component, and aromatic rings such as benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl are more preferable.

[0279] Rz １ ~Rz ４ The ring structure (alicyclic hydrocarbon, aromatic hydrocarbon) formed by Rz １ ~Rx ４ 、Ry １ ~Ry ２ 、Rz １ ~Rz ４ may have substituents. Examples of the substituents here are the same as those in the cyclic groups of Rx １ ~Rx ４ 、Ry １ ~Ry ２ 、Rz １ ~Rz ４ (for example, alkyl group, alkoxy group, halogen atom, halogenated alkyl group, hydroxyl group, nitro group, carbonyl group, etc.). Among them, from the viewpoint of compatibility with the (A) component, the substituents in the ring structure formed by Rz １ ~Rz ４ are preferably an alkyl group, a halogen atom, and a halogenated alkyl group.

[0280] Rz １ ~Rz ４ Among two or more of them, the ring structure formed is preferably a ring structure that shares one side of the six-membered ring in the formula (b0 - an0) (the bond between the carbon atom to which Rz １ and Rz ２ are attached and the carbon atom to which Rz ３ and Rz ４ are attached), and an aromatic ring structure is more preferable, from the viewpoint of the diffusion control property of the acid generated by exposure.

[0281] Incidentally, in the above formula (b0 - an0), "when the valence allows" is as follows. That is, Rz １ and Rz ２The carbon atom to which it is bonded, and Rz ３ and Rz ４ When the bond between the carbon atom to which Rz is bonded and the carbon atom to which Rz is bonded is a single bond, Rz １ Rz ２ Rz ３ and Rz ４ All of them are present. Rz １ and Rz ２ When the bond between the carbon atom to which Rz is bonded and the carbon atom to which Rz is bonded is a double bond, Rz ３ and Rz ４ When the bond between the carbon atom to which Rz is bonded and the carbon atom to which Rz is bonded is a double bond, only one of Rz １ or Rz ２ is present, and only one of Rz ３ and Rz ４ is present. Also, for example, when Rz １ and Rz ３ are bonded to form an aromatic ring structure, Rz ２ and Rz ４ do not exist.

[0282] In the formula (b0 - an0), Rx １ to Rx ４ Two or more of them may be bonded to each other to form a ring structure. For example, Rx １ may form a ring structure with any of Rx ２ to Rx ４ Such a ring structure formed by two or more of Rx １ to Rx ４ may be an alicyclic hydrocarbon or an aromatic hydrocarbon. Also, this ring structure may be a polycyclic structure composed of other ring structures.

[0283] Rx １ to Rx ４The alicyclic hydrocarbon formed by two or more of these groups may be polycyclic or monocyclic. Monocyclic alicyclic hydrocarbons are preferred, and monocycloalkanes are preferred. Monocycloalkanes are preferred, and those having 3 to 6 carbon atoms are preferred, specifically cyclopentane, cyclohexane, etc. Polycyclic alicyclic hydrocarbons are preferred, and polycycloalkanes are preferred, and those having 7 to 30 carbon atoms are preferred, specifically polycycloalkanes having a cross-linked ring system polycyclic skeleton such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc., and polycycloalkanes having a fused ring system polycyclic skeleton such as a cyclic group having a steroid skeleton are more preferred.

[0284] Rx １ ~Rx ４ The aromatic hydrocarbon ring formed by two of these atoms includes benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic heterocycles in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms. １ ~Rx ４ From the viewpoint of compatibility with component (A), the aromatic hydrocarbon ring formed by two of these atoms is preferably free of heteroatoms, and aromatic rings such as benzene, fluorene, naphthalene, anthracene, phenanthrene, and biphenyl are more preferable.

[0285] Rx １ ~Rx ４ The ring structure formed by (alicyclic hydrocarbon, aromatic hydrocarbon) may have substituents. Examples of substituents here include the Rx mentioned above. １ ~Rx ４ , Ry １ ~Ry ２ , Rz １ ~Rz ４ Examples include substituents on the cyclic group (for example, alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, nitro groups, carbonyl groups, etc.). Among them, Rx １ ~Rx ４ From the viewpoint of compatibility with component (A), alkyl groups, halogen atoms, and alkyl halides are preferred as substituents in the ring structure formed by (A).

[0286] Rx １ ~Rx ４ Among two or more of them, the ring structure formed is preferably an alicyclic hydrocarbon, particularly from the viewpoint of acid diffusion control. Also, Rx １ ~Rx ４ Among two or more of them, the ring structure formed is preferably an alicyclic hydrocarbon, particularly from the viewpoint of acid diffusion control, of the above Rx １ ~Rx ２ at least one of them and the above Rx ３ ~Rx ４ at least one of them are preferably bonded to each other to form a crosslinked ring structure, and more preferably this ring structure is an alicyclic hydrocarbon.

[0287] The above Rx １ ~Rx ２ 中at least one of them and the above Rx ３ ~Rx ４ When at least one of them are bonded to each other to form a ring structure, the number of carbon atoms constituting the bicyclic structure (the ring structure including the carbon atoms to which Ry １ 、Ry ２ 、Rz １ and Rz ２ 、Rz ３ and Rz ４ are respectively bonded) is preferably 7 to 16.

[0288] In the above formula (b0 - an0), at least one of two or more of Rx １ ~Rx ４ 、Ry １ ~Ry ２ 、or Rz １ ~Rz ４ are bonded to each other to form an aromatic ring. The aromatic ring is the same as the aromatic ring described in the above formula (b0).

[0289] In the above formula (b0 - an0), Rx １ ~Rx ４ 、Ry １ ~Ry ２ and Rz １ ~Rz ４At least one of them has an anionic group represented by the general formula (b0-r-an1), and the entire anionic portion forms an n-valent anion. n is an integer of 1 or more. Rx １ ~Rx ４ , Ry １ ~Ry ２ , Rz １ ~Rz ４ Each of these may be the aforementioned anionic group. Also, Rx １ ~Rx ４ If two or more of these atoms are bonded to each other to form a ring structure, the carbon atoms forming the ring structure or the hydrogen atoms bonded to these carbon atoms may be substituted with the anionic group. １ ~Ry ２ If two or more of these atoms are bonded to each other to form a ring structure, the carbon atoms forming the ring structure or the hydrogen atoms bonded to these carbon atoms may be substituted with the anionic group. Rz １ ~Rz ４ If two or more of these atoms are bonded to each other to form a ring structure, the carbon atoms forming the ring structure or the hydrogen atoms bonded to these carbon atoms may be substituted with the anionic group.

[0290] In the above formula (b0 - r - an1), Yb ０ The divalent linking group in formula (b0) is Yb ０ It is the same as the divalent linking group in the above formula (b0-r-an1), Vb ０ The alkylene group or fluorinated alkylene group in formula (b0) is Vb ０ It is identical to the alkylene group or fluorinated alkylene group in [the specified product].

[0291] A specific example of the anionic group represented by the formula (b0-r-an1) is, for example, Yb ０ When it is a single bond, examples include fluorinated alkyl sulfonate anions such as trifluoromethanesulfonate anions and perfluorobutanesulfonate anions. Yb ０ When is a divalent linking group containing an oxygen atom, anions represented by any of the following formulas (b0-r-an11) to (b0-r-an13) are included.

[0292] [In the formula, Vb” 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. Rb １０２ [vb'' is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. vb'' is an independent integer from 0 to 3. qb'' is an independent integer from 1 to 20. nb'' is 0 or 1.]

[0293] In the above formulas (b0 - r - an11) to (b0 - r - an13), Vb'' 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. Vb” １０１ The preferred elements are a single bond, an alkylene group (methylene group) with 1 carbon atom, or a fluorinated alkylene group with 1 to 3 carbon atoms.

[0294] In the above formulas (b0-r-an11) to (b0-r-an13), Rb １０２ Rb is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. １０２ It is preferably a perfluoroalkyl group having 1 to 5 carbon atoms or a fluorine atom, and more preferably a fluorine atom.

[0295] In the above formulas (b0 - r - an11) to (b0 - r - an13), vb'' is an integer from 0 to 3, preferably 0 or 1. qb'' is an integer from 1 to 20, preferably 1 to 10, more preferably 1 to 5, even more preferably 1, 2 or 3, and particularly preferably 1 or 2. nb'' is 0 or 1, preferably 0.

[0296] The number of anionic groups in component (B0) may be one or two or more. Component (B0) is an n-valent anion in its entirety. n is an integer of 1 or more, preferably 1 or 2, and more preferably 1.

[0297] In the above formula (b0 - an0), Rx １ ~Rx ４ , Ry １ ~Ry ２ and Rz １ ~Rz ４At least one of these groups has the acid-degradable group described above. A preferred embodiment of the acid-degradable group is the same as the acid-degradable group described in formula (b0) above.

[0298] As the anion portion of component (B0), an anion represented by the following general formula (b0-an1) is more preferred from the viewpoint of suppressing acid diffusion.

[0299] [In the formula, Rx ５ ~Rx ６ Each of these independently represents a hydrocarbon group or hydrogen atom that may have substituents. ７ ~Rx ８ Each of these independently represents a hydrocarbon group or hydrogen atom which may have substituents, or they may be bonded to each other to form a ring structure. p is 1 or 2, and when p = 2, multiple Rx ７ ~Rx ８ They may be different from each other. １ ~Ry ２ Each of these elements independently represents a hydrocarbon group or hydrogen atom which may have substituents, or they may be bonded to each other to form a ring structure. It is either a double bond or a single bond. Rz １ ~Rz ４ Each of these independently represents a hydrocarbon group or hydrogen atom that may have substituents if the valence allows, or two or more may be bonded to each other to form a ring structure. However, Rx ５ ~Rx ６ Rx ７ ~Rx ８ , Ry １ ~Ry ２ , or Rz １ ~Rz ４ At least one of the two or more of these is bonded to each other to form an aromatic ring. Also, Rx ５ ~Rx ８ , Ry １ ~Ry ２ and Rz １ ~Rz ４ At least one of them has an anionic group represented by the following general formula (b0-r-an1), and the entire anionic part forms an n-valent anion. Also, Rx ５ ~Rx８ , Ry １ ~Ry ２ and Rz １ ~Rz ４ At least one of them has an acid-degradable group. n is an integer of 1 or more.

[0300] [In the formula, Yb ０ Vb is a divalent linking group or a single bond. ０ R is an alkylene group, a fluorinated alkylene group, or a single bond. ０ This is a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom. * indicates a bond.

[0301] In the above formula (b0 - an1), Rx ５ ~Rx ６ Each of these independently represents a hydrocarbon group or hydrogen atom that may have substituents. ５ ~Rx ６ In this, the hydrocarbon group which may have substituents is Rx in the above formula (b0-an0). １ ~Rx ４ This is similar to the explanation for hydrocarbon groups that may have substituents.

[0302] In the above formula (b0 - an1), Rx ７ ~Rx ８ Each of these independently represents a hydrocarbon group or hydrogen atom which may have substituents, or they may be bonded to each other to form a ring structure. ７ ~Rx ８ Rx in the above-mentioned formula (b0 - an0) １ ~Rx ４ This is similar to the explanation regarding [the other topic].

[0303] In the above formula (b0 - an1), p is 1 or 2, and when p = 2, multiple Rx ７ ~Rx ８ These may be different from each other. In the anion represented by the general formula (b0-an1), when p=1, it has a bicycloheptane ring structure, and when p=2, it has a bicyclooctane ring structure.

[0304] In the above formula (b0 - an1), Ry １ ~Ry２ Each of these independently represents a hydrocarbon group or hydrogen atom which may have substituents, or they may be bonded to each other to form a ring structure. １ ~Ry ２ Ry in the above-mentioned formula (b0 - an0) １ ~Ry ２ It is similar to Rz １ ~Rz ４ Each of these independently represents a hydrocarbon group or hydrogen atom that may have substituents, provided the valence is permissible, or two or more may be bonded to each other to form a ring structure. １ ~Rz ４ This is Rz in the above-mentioned formula (b0 - an0). １ ~Rz ４ It is similar to that.

[0305] In the above formula (b0 - an1), Rx ５ ~Rx ６ Rx ７ ~Rx ８ , Ry １ ~Ry ２ , or Rz １ ~Rz ４ At least one of the two or more of these atoms is bonded to each other to form an aromatic ring. The aromatic ring is the same as that described in formula (b0) above.

[0306] In the above formula (b0 - an1), Rx ５ ~Rx ８ , Ry １ ~Ry ２ and Rz １ ~Rz ４ At least one of these groups has an anionic group represented by the above formula (b0-r-an1), and the entire anionic portion forms an n-valent anion. n is an integer of 1 or more, preferably 1 or 2, and more preferably 1.

[0307] In the above formula (b0 - an1), Rx ５ ~Rx ８ , Ry １ ~Ry ２ and Rz １ ~Rz ４At least one of these groups has an acid-degradable group. A preferred embodiment of the acid-degradable group is the same as the acid-degradable group described in formula (b0) above.

[0308] Among the above, the anion portion of component (B0) is more preferably the anion represented by p=2 in formula (b0-an1), that is, the anion represented by the following general formula (b0-an2), from the viewpoint of controlling the diffusion of the acid.

[0309] [In the formula, Rx ５ ~Rx ６ Each of these independently represents a hydrocarbon group or hydrogen atom which may have substituents. Multiple Rx ７ ~Rx ８ Each of these independently represents a hydrocarbon group or hydrogen atom which may have substituents, or two or more may be bonded to each other to form a ring structure. １ ~Ry ２ Each of these elements independently represents a hydrocarbon group or hydrogen atom which may have substituents, or they may be bonded to each other to form a ring structure. It is either a double bond or a single bond. Rz １ ~Rz ４ Each of these independently represents a hydrocarbon group or hydrogen atom that may have substituents if the valence allows, or two or more may be bonded to each other to form a ring structure. However, Rx ５ ~Rx ６ Rx ７ ~Rx ８ Two or more of the following, １ ~Ry ２ , or Rz １ ~Rz ４ At least one of the two or more of these is bonded to each other to form an aromatic ring. Also, Rx ５ ~Rx ８ , Ry １ ~Ry ２ and Rz １ ~Rz ４ At least one of them has an anionic group represented by the following general formula (b0-r-an1), and the entire anionic part forms an n-valent anion. Also, Rx ５ ~Rx ８ , Ry１ ~Ry ２ and Rz １ ~Rz ４ At least one of them has an acid-degradable group. n is an integer of 1 or more.

[0310] [In the formula, Yb ０ Vb is a divalent linking group or a single bond. ０ R is an alkylene group, a fluorinated alkylene group, or a single bond. ０ This is a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom. * indicates a bond.

[0311] In the above formula (b0 - an2), Rx ５ ~Rx ６ Rx ７ ~Rx ８ , Ry １ ~Ry ２ , Rz １ ~Rz ４ Rx in the above-mentioned formula (b0-an1) is ５ ~Rx ６ Rx ７ ~Rx ８ , Ry １ ~Ry ２ , Rz １ ~Rz ４ These are similar in each case.

[0312] In the above formula (b0 - an2), Rx ５ ~Rx ６ Rx ７ ~Rx ８ Two or more of the following, １ ~Ry ２ , or Rz １ ~Rz ４ At least one of the two or more of these atoms is bonded to each other to form an aromatic ring. The aromatic ring is the same as that described in formula (b0) above.

[0313] In the above formula (b0 - an2), Rx ５ ~Rx ８ , Ry １ ~Ry ２ and Rz １ ~Rz ４At least one of these groups has an anionic group represented by the above formula (b0-r-an1), and the entire anionic portion forms an n-valent anion. n is an integer of 1 or more, preferably 1 or 2, and more preferably 1.

[0314] In the above formula (b0 - an2), Rx ５ ~Rx ８ , Ry １ ~Ry ２ and Rz １ ~Rz ４ At least one of these groups has the acid-degradable group described above. A preferred embodiment of the acid-degradable group is the same as the acid-degradable group described in formula (b0) above.

[0315] In the above equations (b0-an0), (b0-an1), and (b0-an2), Ry １ ~Ry ２ From the viewpoint of shortening the diffusion of acid generated by exposure and controlling the diffusion of acid, it is preferable that the elements are bonded to each other to form a ring structure, and the ring structure formed is more preferably an aromatic hydrocarbon (aromatic ring, aromatic heterocycle) which may have substituents.

[0316] In the above equations (b0-an0), (b0-an1), and (b0-an2), Rz １ ~Rz ４ From the viewpoint of controlling the diffusion of acid generated by exposure, it is preferable that the elements are bonded to each other to form a ring structure, and the ring structure formed is one side (Rz) of the six-membered ring in the formula. １ and Rz ２ The carbon atom to which it is bonded, and Rz ３ and Rz ４ A ring structure that shares a bond with a carbon atom to which it is bonded is preferred, and aromatic hydrocarbons (aromatic rings, aromatic heterocycles) which may have substituents are more preferred.

[0317] In the above equations (b0-an1) and (b0-an2), Rx ７ ~Rx ８ From the viewpoint of shortening the diffusion of the acid generated by exposure and controlling the diffusion of the acid, it is preferable that the elements are bonded to each other to form a ring structure, and the ring structure formed is more preferably an aromatic hydrocarbon (aromatic ring, aromatic heterocycle) which may have substituents. In the above formula (b0-an2), Rx７ ~Rx ８ The ring structure formed in this case is one side (Rx) of the six-membered ring in the formula. ７ and Rx ８ A ring structure sharing bonds between identical carbon atoms is preferred, and aromatic hydrocarbons (aromatic rings, aromatic heterocycles) which may have substituents are more preferred.

[0318] For the entire anion represented by the above formula (b0 - an2), such Rx ７ ~Rx ８ , Ry １ ~Ry ２ , Rz １ ~Rz ４ In each of these, the number of ring structures formed by mutual bonding may be one or two or more, with two or three being preferred.

[0319] In this embodiment, the anion portion of component (B0) is particularly preferably an anion represented by the following general formula (b0-an3) from the viewpoint of CDU and resolution improvement.

[0320] [In the formula, Rx ５ ~Rx ６ Each of these independently represents a hydrocarbon group or hydrogen atom that may have substituents. It is either a double bond or a single bond. Rz １ ~Rz ４ Each of these independently represents a hydrocarbon group or hydrogen atom that may have substituents if the valence allows, or two or more may be bonded to each other to form a ring structure. However, Rx ５ ~Rx ６ and Rz １ ~Rz ４ At least one of them has an anionic group represented by the following general formula (b0-r-an1), and the entire anionic part forms an n-valent anion. n is an integer of 1 or more. Also, Rx ５ ~Rx ６ and Rz １ ~Rz ４ At least one of them has an acid-degradable group. ０２１R is an alkyl group, alkoxy group, halogen atom, alkyl halide, hydroxyl group, carbonyl group, or nitro group. n1 is an integer from 1 to 3. n11 is an integer from 0 to 8. ０２２ n2 is an alkyl group, alkoxy group, halogen atom, alkyl halide, hydroxyl group, carbonyl group, or nitro group. n2 is an integer from 1 to 3. n21 is an integer from 0 to 8.

[0321] [In the formula, Yb ０ Vb is a divalent linking group or a single bond. ０ R is an alkylene group, a fluorinated alkylene group, or a single bond. ０ This is a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom. * indicates a bond.

[0322] In the above formula (b0 - an3), Rx ５ ~Rx ６ , Rz １ ~Rz ４ Rx in the above formula (b0 - an1) ５ ~Rx ６ , Rz １ ~Rz ４ These are similar in each case.

[0323] In the above formula (b0 - an3), R ０２１ R is an alkyl group, alkoxy group, halogen atom, alkyl halide, hydroxyl group, carbonyl group, or nitro group. ０２１ The alkyl group in 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. ０２１ The alkoxy group in 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 even more preferably a methoxy group or an ethoxy group. ０２１ In this case, a fluorine atom is preferred as the halogen atom. ０２１Examples of halogenated alkyl groups in R 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. ０２１ From the viewpoint of compatibility with component (A), alkyl groups, halogen atoms, and alkyl halides are preferred.

[0324] In the above formula (b0 - an3), n1 is an integer from 1 to 3, preferably 1 or 2, and more preferably 1. In the above formula (b0 - an3), n11 is an integer from 0 to 8, preferably 0 to 4, more preferably 0, 1 or 2, and even more preferably 0 or 1.

[0325] In the above formula (b0 - an3), R ０２２ R is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide, a hydroxyl group, a carbonyl group, or a nitro group, and each of the above R ０２１ Similar examples include R ０２２ As for component (A), alkyl groups, halogen atoms, and alkyl halides are preferred from the viewpoint of compatibility with component (A). In formula (b0-an3), n2 is an integer from 1 to 3, preferably 1 or 2, and particularly preferably 1. In formula (b0-an3), n21 is an integer from 0 to 8, preferably an integer from 0 to 4, more preferably 0, 1 or 2, and particularly preferably 0 or 1.

[0326] However, in the above formula (b0-an3), Rx ５ ~Rx ６ and Rz １ ~Rz ４ At least one of these groups has an anionic group represented by the above formula (b0-r-an1), and the entire anionic portion forms an n-valent anion. n is an integer of 1 or more, preferably 1 or 2, and more preferably 1.

[0327] In the above formula (b0 - an3), Rx ５ ~Rx ６ and Rz １ ~Rz ４At least one of these groups has the acid-degradable group described above. A preferred embodiment of the acid-degradable group is the same as the acid-degradable group described in formula (b0) above.

[0328] In the above formulas (b0-an0), (b0-an1), (b0-an2), and (b0-an3), the Rz is superior in terms of the effects of the present invention. １ ~Rz ４ Preferably, at least one of them has an anionic group. １ ~Rz ４ If two or more of these atoms are bonded to each other to form a ring structure, the carbon atoms forming the ring structure or the hydrogen atoms bonded to these carbon atoms may be substituted with the anionic group.

[0329] In the above formulas (b0-an0), (b0-an1), (b0-an2), and (b0-an3), the Rz is superior in terms of the effects of the present invention. １ ~Rz ４ Preferably, at least one of them has an acid-degradable group. １ ~Rz ４ If two or more of these groups are bonded to each other to form a ring structure, the hydrogen atoms bonded to the carbon atoms forming the ring structure may be substituted with the acid-degradable group.

[0330] The following shows a specific example of the anion portion of component (B0).

[0331]

[0332]

[0333]

[0334]

[0335] {(B0) component cation} In the above general formula (b0), M ｍ＋ m is an m-valent organic cation, where m is an integer greater than or equal to 1. Among these, sulfonium cations and iodonium cations are preferred.

[0336] Preferred cation portion ((M ｍ＋ ) １／ｍExamples of these include organic cations represented by the following general formulas (ca-1) to (ca-5).

[0337] [In the formula, R ２０１ ~R ２０７ , and R ２１１ ~R ２１２ Each of these independently represents an aryl group, alkyl group, or alkenyl group, which may have substituents. ２０１ ~R ２０３ , R ２０６ ~R ２０７ , R ２１１ ~R ２１２ 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 may be an aryl group having a substituent, an alkyl group having a substituent, an alkenyl group having a substituent, or an SO group having a substituent. ２ - Contains a cyclic group. L ２０１ This represents -C(=O)- or -C(=O)-O-. ２０１ Each of these independently represents an arylene group, an alkylene group, or an alkenylene group. x is either 1 or 2. W ２０１ [This represents a (x+1) valence linking group.]

[0338] In the above general formulas (ca-1) to (ca-5), R ２０１ ~R ２０７ , and R ２１１ ~R ２１２ Examples of aryl groups in this compound include unsubstituted aryl groups having 6 to 20 carbon atoms, with phenyl and naphthyl groups being preferred. ２０１ ~R ２０７ , and R ２１１ ~R ２１２ The alkyl group in is preferably a linear or cyclic alkyl group having 1 to 30 carbon atoms. ２０１ ~R ２０７ , and R ２１１ ~R ２１２ The alkenyl group in is preferably one with 2 to 10 carbon atoms.２０１ ~R ２０７ , and R ２１０ ~R ２１２ Examples of substituents that may be present include alkyl groups, halogen atoms, alkyl halides, carbonyl groups, cyano groups, amino groups, aryl groups, and groups represented by the following general formulas (ca-r-1) to (ca-r-7).

[0339] [In the formula, R' ２０１ Each 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.

[0340] A cyclic group which 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.

[0341] R' ２０１ The aromatic hydrocarbon group in R' 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 10. However, this carbon number does not include the carbon atoms in substituents. 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. ２０１Specific 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.

[0342] R' ２０１ The cyclic aliphatic hydrocarbon group in this context refers to an aliphatic hydrocarbon group that contains a ring in its structure. Examples of aliphatic hydrocarbon groups containing a ring in their 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 from which one or more hydrogen atoms have been removed from a monocycloalkane. The preferred monocycloalkane has 3 to 6 carbon atoms, and specifically includes cyclopentane and cyclohexane. A preferred polycyclic alicyclic hydrocarbon group is a group from which one or more hydrogen atoms have been removed from a polycycloalkane, and the preferred polycycloalkane has 7 to 30 carbon atoms. Among these, polycycloalkanes having a cross-linked ring polycyclic skeleton such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane are more preferred; polycycloalkanes having a fused ring polycyclic skeleton such as a cyclic group having a steroid skeleton are more preferred.

[0343] Among them, R' ２０１The 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.

[0344] 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. A linear alkylene group is preferred as the linear aliphatic hydrocarbon group, specifically a methylene group [-CH₂]. ２ -], ethylene group [- (CH ２ ) ２ -], trimethylene group [-(CH ２ ) ３ -], tetramethylene group [-(CH ２ ) ４ -], pentamethylene group [-(CH ２ ) ５ Examples include -CH(CH ３ )-,-CH(CH ２ CH ３ )-,-C(CH ３ ) ２ -, -C(CH ３ ) (CH ２ CH ３ )-,-C(CH ３ ) (CH ２ CH ２ CH ３ )-,-C(CH ２ CH ３ ) ２ - Alkyl methylene groups such as -CH(CH ３ )CH ２ -, -CH(CH ３ )CH(CH ３ )-,-C(CH ３ ) ２ CH ２ -, -CH(CH ２ CH ３ )CH ２-, -C(CH ２ CH ３ ) ２ -CH ２ - Alkyl ethylene groups such as -CH(CH ３ )CH ２ CH ２ -ien-CH ２ CH (CH ３ )CH ２ - Alkyl trimethylene groups such as -CH(CH ３ )CH ２ CH ２ CH ２ -ien-CH ２ CH (CH ３ )CH ２ CH ２ Examples include alkylalkylene groups such as alkyltetramethylene groups. In the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0345] Also, R' ２０１ The cyclic hydrocarbon group in may contain heteroatoms, such as heterocycles. Specifically, lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-8), and -SO groups represented by the general formulas (a5-r-1) to (a5-r-4) below. ２ - Examples include cyclic groups and heterocyclic groups represented by the following chemical formulas (r-hr-1) to (r-hr-16).

[0346] [In the formula, 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; R'' is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, or -SO ２ - It is a cyclic group containing; 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.

[0347] In the general formulas (b5-r-1) to (b5-r-2) above, 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. B'' is preferably an alkylene group having 1 to 5 carbon atoms or -O-, more preferably an alkylene group having 1 to 5 carbon atoms, and even more preferably a methylene group.

[0348] 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.

[0349] 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.

[0350]

[0351]

[0352]

[0353]

[0354] R' ２０１Examples of substituents on the cyclic group include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, and nitro groups. Preferred alkyl groups as substituents are alkyl groups having 1 to 5 carbon atoms, with methyl, ethyl, propyl, n-butyl, and tert-butyl groups being the most preferred. Preferred alkoxy groups as substituents are alkoxy groups having 1 to 5 carbon atoms, with methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, and tert-butoxy groups being more preferred, with methoxy and ethoxy groups being the most preferred. Preferred halogen atoms as substituents are fluorine atoms. Examples of alkyl halides 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. Carbonyl groups as substituents are methylene groups (-CH) that constitute the cyclic hydrocarbon group. ２ It is a substituting group for -).

[0355] A chain-like alkyl group which may have substituents: R' ２０１ The linear alkyl group may be linear or branched. Linear alkyl groups preferably have 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. Branched alkyl groups preferably have 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.

[0356] A chain-like alkenyl group which may have substituents: R' ２０１The linear alkenyl group may be 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 linear alkenyl groups include vinyl groups, propenyl groups (allyl groups), and butynyl groups. Examples of branched alkenyl groups include 1-methylvinyl groups, 2-methylvinyl groups, 1-methylpropenyl groups, and 2-methylpropenyl groups. Among the linear alkenyl groups listed above, linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred.

[0357] R' ２０１ 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'. ２０１ Examples include cyclic groups in this context.

[0358] R' ２０１ In addition to those mentioned above, the optionally substituted cyclic groups, optionally substituted linear alkyl groups, or optionally substituted linear alkenyl groups may also include those similar to the acid-dissociable group represented by formula (a1-r-2) above, as optionally substituted cyclic groups or optionally substituted linear alkyl groups.

[0359] Among them, R' ２０１ The cyclic group is preferably a cyclic group which may have substituents, and more preferably a cyclic hydrocarbon group which may have substituents. 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-8); and a -SO group represented by the general formulas (a5-r-1) to (a5-r-4). ２ - A cyclic group is preferred.

[0360] In the above general formulas (ca-1) to (ca-5), R ２０１ ~R ２０３ , R ２０６ ~R ２０７ , R２１１ ~R ２１２ When these atoms bond to each other and form a ring with the sulfur atom in the formula, they can be heteroatoms such as sulfur, oxygen, and nitrogen atoms, or carbonyl groups, -SO-, -SO ２ -, -SO ３ -, -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, a tetrahydrothiopyranium ring, and the like.

[0361] 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 present, it may bond to each other to form a ring.

[0362] R ２１０ This may be an aryl group having a substituent, an alkyl group having a substituent, an alkenyl group having a substituent, or an SO group having a substituent. ２ - Contains a cyclic group. R ２１０ Examples of aryl groups in this compound include unsubstituted aryl groups having 6 to 20 carbon atoms, with phenyl and naphthyl groups being preferred. ２１０ The alkyl group in is preferably a linear or cyclic alkyl group having 1 to 30 carbon atoms. ２１０ The alkenyl group in is preferably one with 2 to 10 carbon atoms. ２１０ SO, which may have substituents ２ - As for the contained cyclic group, "-SO ２ - A polycyclic group containing the above formula is preferred, and a group represented by the general formula (a5-r-1) is more preferred.

[0363] Y ２０１ Each of these independently represents an arylene group, an alkylene group, or an alkenylene group. ２０１ The arylene group in the above formula (b-1) is R １０１ An example of an aromatic hydrocarbon group in this context is the aryl group exemplified above, with one hydrogen atom removed. ２０１ The alkylene group and alkenylene group in the above formula (b-1) are R １０１ Examples of the chain-like alkyl groups and chain-like alkenyl groups mentioned above include groups obtained by removing one hydrogen atom from the examples provided.

[0364] In the above formula (ca-4), x is either 1 or 2. ２０１ This is a (x+1) valence, i.e., a divalent or trivalent linking group. ２０１ In this, the divalent linking group is preferably a divalent hydrocarbon group which may have substituents, and Ya in the above general formula (a2-1) ２１ Examples of divalent hydrocarbon groups that may have substituents, similar to the above, can be given. ２０１ The divalent linking group in this compound may be linear, branched, or cyclic, with cyclic being preferred. Among these, a group in which two carbonyl groups are combined at both ends of an arylene group is preferred. Examples of arylene groups include phenylene groups and naphthylene groups, with phenylene groups being particularly preferred. ２０１ The trivalent linking group in is the aforementioned W ２０１ Examples include a group obtained by removing one hydrogen atom from a divalent linking group, and a group in which another divalent linking group is bonded to the aforementioned divalent linking group. ２０１ In this compound, a trivalent linking group is preferably a group in which two carbonyl groups are bonded to an arylene group.

[0365] Specific examples of suitable cations represented by the above formula (ca-1) include the cations represented by the following chemical formulas (ca-1-1) to (ca-1-84).

[0366]

[0367]

[0368] [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.]

[0369]

[0370]

[0371] [In the formula, R” ２０１ [wherein is a hydrogen atom or a substituent, and examples of substituents include alkyl groups, halogen atoms, alkyl halides, cyano groups, amino groups, aryl groups, and groups represented by the general formulas (ca-r-1) to (ca-r-7), respectively.]

[0372]

[0373] Specific examples of suitable cations represented by the formula (ca-2) include diphenyliodonium cation and bis(4-tert-butylphenyl)iodonium cation.

[0374] 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).

[0375]

[0376] Specific examples of suitable cations represented by the above formula (ca-4) include the cations represented by the following formulas (ca-4-1) to (ca-4-2).

[0377]

[0378] Specific examples of preferred cations represented by the above formula (ca-5) include the cations represented by the following general formulas (ca-5-1) to (ca-5-3).

[0379]

[0380] Among the above, the cation part ((M ｍ＋ ) １／ｍThe cation represented by the general formula (ca-1) is preferred, and the cations represented by formulas (ca-1-1) to (ca-1-84) are particularly preferred. Particularly from the viewpoint of increasing sensitivity, the preferred cation represented by formula (ca-1) is a cation having electron-withdrawing groups such as a fluorine atom, a fluorinated alkyl group, or a sulfonyl group as a substituent. For example, a cation selected from the group consisting of the cations represented by the above chemical formulas (ca-1-44), (ca-1-71) to (ca-1-84) is particularly preferred.

[0381] In the resist composition of this embodiment, component (B0) is preferably a compound represented by the following general formula (b0-1) among the above.

[0382] [In the formula, Rx １ ~Rx ４ Each of these independently represents a hydrocarbon group or hydrogen atom which may have substituents, or two or more may be bonded to each other to form a ring structure. １ ~Ry ２ Each of these elements independently represents a hydrocarbon group or hydrogen atom which may have substituents, or they may be bonded to each other to form a ring structure.

[0383] It is either a double bond or a single bond. Rz １ ~Rz ４ Each of these independently represents a hydrocarbon group or hydrogen atom that may have substituents if the valence allows, or two or more may be bonded to each other to form a ring structure. However, Rx １ ~Rx ４ Two or more of the following, １ ~Ry ２ , or Rz １ ~Rz ４ At least one of the two or more of these is bonded to each other to form an aromatic ring. Also, Rx １ ~Rx ４ , Ry １ ~Ry ２ and Rz １ ~Rz ４At least one of them has an anionic group represented by the following general formula (b0-r-an1), and the entire anionic part forms an n-valent anion. Also, Rx １ ~Rx ４ , Ry １ ~Ry ２ and Rz １ ~Rz ４ At least one of them has the functional group (Fab). n is an integer of 1 or more. ｍ＋ [where m is an m-valent organic cation, and m is an integer greater than or equal to 1]

[0384] [In the formula, Yb ０ Vb is a divalent linking group or a single bond. ０ R is an alkylene group, a fluorinated alkylene group, or a single bond. ０ This is a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom. * indicates a bond.

[0385] The anionic portion of the compound represented by the above general formula (b0-1) is the same as the anion represented by the above general formula (b0-an0). The anionic portion of the compound represented by the above general formula (b0-1) is the same as the anionic portion of the compound represented by the above general formula (b0).

[0386] Specific examples of component (B0) are listed below, but are not limited to these.

[0387]

[0388]

[0389] In the resist composition of this embodiment, component (B0) may be used alone or in combination of two or more types. In the resist composition of this embodiment, the content of component (B0) is preferably 5 to 65 parts by mass, more preferably 5 to 55 parts by mass, even more preferably 10 to 45 parts by mass, and particularly preferably 10 to 30 parts by mass, per 100 parts by mass of component (A1). If the content of component (B0) is above the lower limit of the above preferred range, lithography characteristics such as sensitivity, resolution performance, CDU, LWR (linewise roughness) reduction, and shape are further improved in resist pattern formation. On the other hand, if it is below the upper limit of the preferred range, a uniform solution is more easily obtained when each component of the resist composition is dissolved in an organic solvent, and the storage stability of the resist composition is further improved.

[0390] In the resist composition of this embodiment, the proportion of component (B0) to the total amount of component (B) is, for example, 50% by mass or more, preferably 70% by mass or more, and more preferably 95% by mass or more. It may also be 100% by mass.

[0391] ≪Component (B1)≫ The (B) component in the resist composition of this embodiment may contain an acid generating agent component (B1) other than the (B0) component described above (hereinafter also referred to as "component (B1)").

[0392] (B1) components include a wide variety of substances such as onium salt-based acid generators like iodonium salts and sulfonium salts; oxime sulfonate-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. The form in which component (B1) 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.

[0393] 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)").

[0394] [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 These are, independently, a single bond, an alkylene group, or a fluorinated alkylene group. 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 -SO-. ２ - is true. m is an integer greater than or equal to 1, and M' ｍ＋ This is an onium cation with a positive (m) charge.

[0395] {Anion part} • In the anion formula (b-1) of component (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.

[0396] A cyclic group which 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.

[0397] R １０１ The aromatic hydrocarbon group in 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. 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. 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, arylalkyl groups such as benzyl groups, phenethyl groups, 1-naphthylmethyl groups, 2-naphthylmethyl groups, 1-naphthylethyl groups, and 2-naphthylethyl groups). 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.

[0398] R １０１The cyclic aliphatic hydrocarbon group in this context refers to an aliphatic hydrocarbon group that contains a ring in its structure. Examples of aliphatic hydrocarbon groups containing a ring in their 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 from which one or more hydrogen atoms have been removed from a monocycloalkane. The preferred monocycloalkane has 3 to 6 carbon atoms, and specifically includes cyclopentane and cyclohexane. A preferred polycyclic alicyclic hydrocarbon group is a group from which one or more hydrogen atoms have been removed from a polycycloalkane, and the preferred polycycloalkane has 7 to 30 carbon atoms. Among these, polycycloalkanes having a cross-linked ring polycyclic skeleton such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane are more preferred; polycycloalkanes having a fused ring polycyclic skeleton such as a cyclic group having a steroid skeleton are more preferred.

[0399] 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.

[0400] 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. A linear alkylene group is preferred as the linear aliphatic hydrocarbon group, specifically a methylene group [-CH₂]. ２ -], ethylene group [- (CH ２ ) ２ -], trimethylene group [-(CH２ ) ３ -], tetramethylene group [-(CH ２ ) ４ -], pentamethylene group [-(CH ２ ) ５ Examples include -]. 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. A branched alkylene group is preferred as the branched aliphatic hydrocarbon group, specifically -CH(CH ３ )-,-CH(CH ２ CH ３ )-,-C(CH ３ ) ２ -, -C(CH ３ ) (CH ２ CH ３ )-,-C(CH ３ ) (CH ２ CH ２ CH ３ )-,-C(CH ２ CH ３ ) ２ - Alkyl methylene groups such as -CH(CH ３ )CH ２ -, -CH(CH ３ )CH(CH ３ )-,-C(CH ３ ) ２ CH ２ -, -CH(CH ２ CH ３ )CH ２ -, -C(CH ２ CH ３ ) ２ -CH ２ - Alkyl ethylene groups such as -CH(CH ３ )CH ２ CH ２ -ien-CH ２ CH (CH ３ )CH ２ - Alkyl trimethylene groups such as -CH(CH ３ )CH ２ CH ２ CH ２ -ien-CH ２ CH (CH ３ )CH２ CH ２ Examples include alkylalkylene groups such as alkyltetramethylene groups. In the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0401] Also, R １０１ The cyclic hydrocarbon group in may contain heteroatoms, such as heterocycles. Specifically, lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-8), and -SO groups represented by the general formulas (a5-r-1) to (a5-r-4), respectively. ２ - Examples include cyclic groups and heterocyclic groups represented by the above chemical formulas (r-hr-1) to (r-hr-16). * in the formula represents Y in formula (b-1). １０１ This represents a coupling that connects to something.

[0402] 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. Preferred alkyl groups as substituents are those having 1 to 5 carbon atoms, with methyl, ethyl, propyl, n-butyl, and tert-butyl groups being the most preferred. Preferred alkoxy groups as substituents are those having 1 to 5 carbon atoms, with methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, and tert-butoxy groups being more preferred, with methoxy and ethoxy groups being the most preferred. Examples of halogen atoms as substituents include fluorine, chlorine, bromine, and iodine atoms, with fluorine atoms being preferred. Examples of alkyl halides 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. The carbonyl group as a substituent is a methylene group (-CH) that constitutes a cyclic hydrocarbon group. ２ It is a substituting group for -).

[0403] R １０１The 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 those represented by the above-mentioned formulas (r-br-1) to (r-br-2). In this case, * in the formulas represents Y in formula (b-1). １０１ This represents a coupling that connects to something.

[0404] R １０１ Examples of substituents that the fused ring group in R may have include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, nitro groups, aromatic hydrocarbon groups, alicyclic hydrocarbon groups, etc. The alkyl groups, alkoxy groups, halogen atoms, and alkyl halides as substituents of the fused ring group are as described above. １０１Examples of substituents for cyclic groups in the above are similar to those listed above. Aromatic hydrocarbon groups as substituents for the fused cyclic group include groups obtained by removing one hydrogen atom from an aromatic ring (aryl groups: for example, phenyl group, naphthyl group, 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 group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.), and heterocyclic groups represented by the above formulas (r-hr-1) to (r-hr-6), respectively. The alicyclic hydrocarbon groups used as substituents on the fused cyclic group include: monocycloalkanes such as cyclopentane and cyclohexane with one hydrogen atom removed; polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane with one hydrogen atom removed; lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-8); and -SO groups represented by the general formulas (a5-r-1) to (a5-r-4). ２ - Containing cyclic groups; examples include heterocyclic groups represented by formulas (r-hr-7) to (r-hr-16), respectively.

[0405] A chain-like alkyl group which may have substituents: R １０１ The linear alkyl group may be linear or branched. Linear alkyl groups preferably have 1 to 20 carbon atoms, more preferably 1 to 15, and most preferably 1 to 10. Branched alkyl groups preferably have 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.

[0406] A chain-like alkenyl group which may have substituents: R １０１The 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 butynyl groups. Examples of branched alkenyl groups include 1-methylvinyl groups, 2-methylvinyl groups, 1-methylpropenyl groups, and 2-methylpropenyl groups. Among the linear alkenyl groups listed above, linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred.

[0407] 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.

[0408] Among the above, R １０１ The cyclic group is preferably a cyclic group which may have substituents, and more preferably a cyclic hydrocarbon group which may have substituents. More specifically as cyclic hydrocarbon groups, the cyclic hydrocarbon group is 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-8); and a -SO group represented by the general formulas (a5-r-1) to (a5-r-4). ２ -A cyclic group is preferred, which is a group obtained by removing one or more hydrogen atoms from a polycycloalkane or a group represented by the general formulas (a5-r-1) to (a5-r-4), respectively -SO ２ -A cyclic group is more preferably contained, an adamantyl group or -SO represented by the general formula (a5-r-1) above. ２ - A cyclic group is even more preferable.

[0409] If the cyclic hydrocarbon group has substituents, the substituents are preferably hydroxyl groups.

[0410] In formula (b-1), Y １０１ Y is a single bond or a divalent linking group containing an oxygen atom. １０１If 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 oxygen atoms include non-hydrocarbon oxygen atom-containing linking groups such as oxygen atoms (ether bond: -O-), ester bonds (-C(=O)-O-), oxycarbonyl groups (-O-C(=O)-), amide bonds (-C(=O)-NH-), carbonyl groups (-C(=O)-), and carbonate bonds (-O-C(=O)-O-); and combinations of the non-hydrocarbon oxygen atom-containing linking group and alkylene groups. This combination may further include sulfonyl groups (-SO ２ A -) may be linked. Examples of such divalent linking groups containing an oxygen atom include the linking groups represented by the general formulas (y-al-1) to (y-al-9) described above. In this case, in the general formulas (y-al-1) to (y-al-9) described above, the R in formula (b-1) above may be linked. １０１ The V' in the general formulas (y-al-1) to (y-al-9) mentioned above is what combines with it. １０１ That is the case.

[0411] Y １０１ Preferably, the linking group is a divalent linking group containing an ester bond or a divalent linking group containing an ether bond, and more preferably the linking groups represented by the above formulas (y-al-1) to (y-al-5).

[0412] In formula (b-1), V １０１ This is a single bond, an alkylene group, or a fluorinated alkylene group. V １０１ The alkylene group and fluorinated alkylene group in this compound preferably have 1 to 4 carbon atoms. １０１ As for the fluorinated alkylene group in V １０１ Examples include groups in which some or all of the hydrogen atoms of the alkylene group are replaced with fluorine atoms. Among these, V １０１ It is preferable that it is a single bond or a fluorinated alkylene group having 1 to 4 carbon atoms.

[0413] In formula (b-1), R １０２R 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.

[0414] A specific example of the anion part represented by 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, anions represented by any of the above formulas (an-1) to (an-3) can be cited.

[0415] • In the anionic formula (b-2) of component (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 They may be bonded to each other to form a ring. １０４ , R １０５ The linear alkyl group is preferably a substituted linear alkyl group, more preferably a linear or branched alkyl group, or a linear or branched fluorinated alkyl group. The number of carbon atoms in the linear 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 １０５In the chain-like alkyl group, the greater the number of hydrogen atoms substituted with fluorine atoms, the stronger the acidity and the better the transparency to high-energy light and electron beams below 250 nm, which is preferable. The proportion of fluorine atoms in the chain-like alkyl group, i.e., the fluorination rate, is preferably 70 to 100%, more preferably 90 to 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 can be given. In equation (b-2), L １０１ , L １０２ Each of these is either a single bond or an oxygen atom, independently of the others.

[0416] • In the anionic formula (b-3) of component (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 can be given. In equation (b-3), L １０３ ~L １０５ These are, independently, single bonds, -CO-, or -SO-. ２ - is the case.

[0417] Among the above, the anion in component (b-1) is preferred as the anion portion of component (B1). Among these, an anion represented by any of the above general formulas (an-1) to (an-3) is more preferred, an anion represented by either general formula (an-1) or (an-2) is even more preferred, and an anion represented by general formula (an-2) is particularly preferred.

[0418] {Cation part} In the above formulas (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 more.

[0419] Preferred cation portion ((M' ｍ＋ ) １／ｍ Examples of these include the organic cations represented by the general formulas (ca-1) to (ca-5) mentioned above.

[0420] In the resist composition of this embodiment, component (B1) may be used alone or in combination of two or more types. When the resist composition contains component (B1), the content of component (B1) in the resist composition is preferably less than 40 parts by mass, more preferably 1 to 30 parts by mass, and even more preferably 1 to 20 parts by mass, per 100 parts by mass of component (A1). By setting the content of component (B1) within the above preferred range, sufficient pattern formation is achieved. Furthermore, when each component of the resist composition is dissolved in an organic solvent, a uniform solution is easily obtained, which is preferable as it results in good storage stability as a resist composition.

[0421] <Other Components> In addition to the above-described components (A) and (B), the resist composition of this embodiment may further contain other components. Examples of other components include components (D), (E), (F), and (S) shown below.

[0422] <<Basic Component (D)>> In the resist composition of this embodiment, it is preferable to further contain a basic component (hereinafter also referred to as "component (D)") that traps the acid generated by exposure (i.e., controls the diffusion of the acid). Such component (D) acts as a quencher (acid diffusion control agent) that traps the acid generated by exposure in the resist composition.

[0423] Examples of component (D) include a photodegradable base (D1) that decomposes upon exposure and loses its ability to control acid diffusion (hereinafter referred to as "component (D1)"), and a nitrogen-containing organic compound (D2) that does not fall under component (D1) (hereinafter referred to as "component (D2)"). Among these, a photodegradable base (component (D1)) is preferred because it is easy to improve sensitivity, reduce surface roughness of the pattern, improve in-plane uniformity of pattern dimensions (CDU), and enhance fine resolution. Compounds exemplified as component (D1) described later may be used as the acid-generating agent component (component (B)) described above, depending on the combination with other compounds.

[0424] Regarding component (D1): Component (D1) is not particularly limited as long as it decomposes upon exposure and loses its acid diffusion controllability. Preferably, it is one or more compounds selected from the group consisting of the compound represented by the following general formula (d1-1) (hereinafter referred to as "component (d1-1)"), the compound represented by the following general formula (d1-2) (hereinafter referred to as "component (d1-2)"), and the compound represented by the following general formula (d1-3) (hereinafter referred to as "component (d1-3)"). Components (d1-1) to (d1-3) do not act as quenchers in the exposed areas of the resist film because they decompose and lose their acid diffusion controllability (basicity), but they act as quenchers in the unexposed areas of the resist film.

[0425] [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 atom. １ is a single bond or a divalent linking group. m is an integer of 1 or more, and M ｍ＋ These are each independently m-valent cations.

[0426] {(d1-1) component} ... in the anionic component of formula (d1-1), Rd １R' 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 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-8), 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 preferred substituents in this case are the linking groups represented by the general formulas (y-al-1) to (y-al-5) and (y-al-9), respectively. 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 (y-al-1) to (y-al-9) as a substituent, then in the general formulas (y-al-1) to (y-al-9), Rd in formula (d1-1) １ The carbon atom constituting the aromatic hydrocarbon group, aliphatic cyclic group, or chain-like alkyl group in the above general formula (y-al-1) to (y-al-9) is bonded to the carbon atom. １０１ The aromatic hydrocarbon group can be preferably a phenyl group, a naphthyl group, or a polycyclic structure containing a bicyclooctane skeleton (a polycyclic structure consisting of a bicyclooctane skeleton and other ring structures). The aliphatic cyclic group can be adamantane, norbornane, isobornane, or 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 chain-like alkyl group is preferably one to ten carbon atoms in number, and specifically, examples include linear alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group; and branched alkyl groups such as 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.

[0427] 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.

[0428] The following are preferred specific examples of the anion portion of component (d1-1).

[0429]

[0430] ...In the cation component (d1-1), M ｍ＋ This is a cation with an m-valence. ｍ＋ Suitable cations include those similar to those represented by the general formulas (ca-1) to (ca-5), 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. The (d1-1) component may be used alone or in combination of two or more types.

[0431] {(d1-2) component} ... in the anionic component of 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 following. However, Rd ２ In this case, the carbon atom adjacent to the S atom is assumed to be unbonded to a fluorine atom (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 Preferably, the group is 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.

[0432] The linear alkyl group is preferably having 1 to 10 carbon atoms, and more preferably 3 to 10 carbon atoms. The aliphatic cyclic group is adamantane, norbornane, isobornane, 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.

[0433] 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 a hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, chain-like alkyl group) in the above may have.

[0434] The following are preferred specific examples of the anion portion of component (d1-2).

[0435]

[0436] ...In the cation component formula (d1-2), M ｍ＋ is an m-valent cation, and M in formula (d1-1) ｍ＋ The same applies. (d1-2) Components may be used individually or in combination of two or more.

[0437] {(d1-3) component} ... in the anionic component of formula (d1-3), Rd ３R' 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 groups are mentioned, and it is preferable that they are cyclic groups containing a fluorine atom, linear alkyl groups, or linear alkenyl groups. Among these, fluorinated alkyl groups are preferred, and the aforementioned Rd １ A fluorinated alkyl group similar to the one shown is more preferable.

[0438] 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 alkyl groups, alkoxy groups, alkenyl groups, and cyclic groups, which may have substituents. 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 ４ The 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 methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, and tert-butoxy groups. Among these, methoxy and ethoxy groups are preferred.

[0439] Rd ４ The alkenyl group in R' is ２０１ Examples of groups similar to the alkenyl group 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.

[0440] Rd ４ The cyclic group in is R' ２０１Examples 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 resist group is an aromatic group, in lithography using EUV or the like as the exposure light source, the resist composition exhibits excellent light absorption efficiency, resulting in good sensitivity and lithographic characteristics.

[0441] In formula (d1-3), Yd １ Yd is a single bond or a divalent linking group. 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. ２１ Examples of divalent linking groups include divalent hydrocarbon groups that may have substituents, and divalent linking groups containing heteroatoms, as mentioned in the explanation of divalent linking groups in 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.

[0442] The following are preferred specific examples of the anionic portion of components (d1-3).

[0443]

[0444]

[0445] ...In the cation component formula (d1-3), M ｍ＋ is an m-valent cation, and M in formula (d1-1) ｍ＋The same applies. (d1-3) Components may be used individually or in combination of two or more.

[0446] The (D1) component may be any one of the above components (d1-1) to (d1-3), or two or more may be used in combination. When the resist composition contains the (D1) component, the content of the (D1) component in the resist composition is preferably 0.5 to 25 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 3 to 15 parts by mass, per 100 parts by mass of the (A1) component. When the content of the (D1) component is above the lower limit of the above preferred range, particularly good lithography characteristics and resist pattern shape are easily obtained. On the other hand, when it is below the upper limit of the above preferred range, good sensitivity can be maintained and throughput is also excellent.

[0447] Component (D1) preferably contains component (d1-1) as described above. The content of component (d1-1) in the total 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).

[0448] Method for producing component (D1): The methods for producing components (d1-1) and (d1-2) described above are not particularly limited and can be produced by known methods. The method for producing component (d1-3) is also not particularly limited and can be produced, for example, in the same manner as described in US2012-0149916.

[0449] Regarding component (D2): Component (D) may contain nitrogen-containing organic compound components 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 ammonia (NH) ３ Examples include amines (alkylamines or alkyl alcoholamines) or cyclic amines in which at least one hydrogen atom 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.

[0450] 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). Specific examples of aliphatic monocyclic amines include piperidine and piperazine. Aliphatic polycyclic amines with 6 to 10 carbon atoms are preferred, and specific 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.

[0451] 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.

[0452] Furthermore, an aromatic amine may be used as component (D2). Examples of aromatic amines include 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or derivatives thereof, tripenzylamine, 2,6-diisopropylaniline, N-tert-butoxycarbonylpyrrolidine, and 2,6-di-tert-butylpyridine.

[0453] The (D2) component may be used alone or in combination of two or more types. When the resist composition contains the (D2) component, the content of the (D2) component in the resist composition is usually in the range of 0.01 to 5 parts by mass per 100 parts by mass of the (A1) component. By using the above range, the resist pattern shape, settling stability over time, etc., are improved.

[0454] <<At least one compound (E) selected from the group consisting of organic carboxylic acids and 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)"). Specifically, examples of organic carboxylic acids include acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, etc., with salicylic acid being preferred among them. Examples of phosphorus oxoacids include phosphoric acid, phosphonic acid, phosphinic acid, etc., with phosphonic acid being particularly preferred among these.

[0455] In the resist composition of this embodiment, component (E) may be used alone or in combination of two or more types. When 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 (A1). By setting it within the above range, the lithography characteristics are further improved.

[0456] ≪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 as component (F), polymers having a constituent unit (f1) represented by the following general formula (f1-1) can be mentioned. The polymer is preferably a polymer (homopolymer) consisting only of a 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, a constituent unit derived from 1-methyl-1-adamantyl (meth)acrylate, and more preferably a constituent unit derived from 1-ethyl-1-cyclooctyl (meth)acrylate.

[0457] [In the formula, R is the same as above, 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. nf1 is an integer from 0 to 5, and Rf １０１ It is an organic group containing a fluorine atom.

[0458] In formula (f1-1), R bonded to the carbon atom at the α position is the same as described above. R is preferably a hydrogen atom or a methyl group. In formula (f1-1), Rf１０２ 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 Rf １０３ Specifically, examples of halogenated alkyl groups having 1 to 5 carbon atoms include groups 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 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), nf1 is an integer from 0 to 5, preferably an integer from 0 to 3, and more preferably 1 or 2.

[0459] In formula (f1-1), Rf １０１ The fluorine atom is an organic group containing a fluorine atom, and preferably a hydrocarbon group containing a fluorine atom. The hydrocarbon group containing a fluorine atom 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, it is preferable that 25% or more of the hydrogen atoms in the hydrocarbon group are fluorinated, more preferably 50% or more, and particularly preferable that 60% or more are fluorinated, as this increases the hydrophobicity of the resist film during immersion exposure. Among these, Rf １０１ More preferably, it is a fluorinated hydrocarbon group having 1 to 6 carbon atoms, a trifluoromethyl group, or -CH ２ -CF ３ ien-CH ２ -CF ２ -CF ３ ,-CH(CF ３ ) ２ ien-CH ２ -CH ２-CF ３ ien-CH ２ -CH ２ -CF ２ -CF ２ -CF ２ -CF ３ That is particularly preferable.

[0460] 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 the resist solvent 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 dispersion degree (Mw / Mn) of component (F) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.0 to 2.5.

[0461] In the resist composition of this embodiment, component (F) may be used alone or in combination of two or more types. When 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 (A1).

[0462] ≪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.

[0463] 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. A mixed solvent of at least one selected from PGMEA and EL and γ-butyrolactone is also preferred as component (S). In this case, the mixing ratio is preferably 70:30 to 95:5 in mass ratio. The amount of component (S) used is not particularly limited and is appropriately set according to the coating thickness at a concentration that can be applied to a substrate, etc. 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.

[0464] The resist composition of this embodiment may further contain, if desired, miscible additives such as additional resins to improve the performance of the resist film, dissolution inhibitors, plasticizers, stabilizers, colorants, anti-halation agents, dyes, etc.

[0465] The resist composition of this embodiment may be prepared by dissolving the resist material in component (S), and then removing impurities using a porous polyimide membrane, a porous polyamide-imide membrane, or the like. For example, the resist composition may be filtered using a filter made of a porous polyimide membrane, a filter made of a porous polyamide-imide membrane, or a filter made of a porous polyimide membrane and a porous polyamide-imide membrane. Examples of the porous polyimide membrane and the porous polyamide-imide membrane include those described in Japanese Patent Application Publication No. 2016-155121.

[0466] As described above, in the resist composition of this embodiment, a resin component (A1) having a constituent unit (a0) derived from a compound represented by general formula (a0-1) and a compound (B0) represented by general formula (b0) are combined. In the resin component (A1), the constituent unit (a0) is an aromatic hydrocarbon group (W ０２ ) has an alkoxy group (-O-Ra ０２ ) and acid-dissociable ester group (-Ya ０１ -C(=O)-O-Ra ０１) has an aromatic hydrocarbon group (W ０２ ) has a structure having the aforementioned acid-dissociable ester group, thus increasing its acid-dissociability (acid reactivity). In addition, it has an aromatic hydrocarbon group (W ０２ Furthermore, an alkoxy group (-O-Ra ０２ Because it has a structure having ), the acid dissociability (acid reactivity) is further enhanced. The acid generator component (B) contains a compound (B0) having an anionic portion having a specific bulky structure (a fused ring group containing one or more aromatic rings) and a functional group (Fab) that controls solubility in the developer and is bonded to this bulky structure. Because the anionic portion has a specific bulky structure, the uniformity of the dispersion of the acid generator in the resist film is enhanced. In addition, because the anionic portion has the functional group (Fab), the alkoxy group (-O-Ra) of the constituent unit (a0) ０２ This makes it easier to balance hydrophilicity and hydrophobicity, improves the solubility of the exposed resist film in the developer, and also improves the contrast between the exposed and unexposed areas of the resist film. Furthermore, it is presumed that the synergistic effect of the resin component (A1) and compound (B0) described above will result in a highly sensitive resist composition in the formation of the resist pattern, improved lithography characteristics such as dimensional uniformity, and better resolution, thereby further suppressing the occurrence of pattern defects.

[0467] (Method for forming a resist pattern) A resist pattern forming method according to a second aspect of the present invention is a resist pattern forming 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 forming method is, for example, a resist pattern forming method carried out as follows.

[0468] First, the resist composition of the above-described embodiment is applied onto a support using a spinner or the like, and a bake (post-apply 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) with a predetermined pattern formed on it, or by direct irradiation with an electron beam without a mask pattern, and then 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 development treatment. In the case of an alkaline development process, an alkaline developer is used, and in the case of a solvent development process, a developer containing an organic solvent (organic developer) is used.

[0469] After development, a rinsing treatment is preferably performed. In the case of an alkaline development process, a water rinse using pure water is preferred, and in the case of a solvent development process, a rinsing solution containing an organic solvent is preferred. In the case of a solvent development process, after the development or rinsing treatment, a treatment to remove the developer or rinsing solution adhering to the pattern may be performed using a supercritical fluid. After development or rinsing, drying is performed. In some cases, a bake treatment (post-bake) may be performed after the development treatment. In this way, a resist pattern can be formed.

[0470] 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.

[0471] The wavelength used for exposure is not particularly limited and can be an ArF excimer laser, KrF excimer laser, or F ２This can be carried out using radiation such as excimer lasers, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-rays, and soft X-rays. The resist composition of the above embodiment is highly useful for use with KrF excimer lasers, ArF excimer lasers, EB, or EUV, more so for use with ArF excimer lasers, EB, or EUV, and particularly useful for use with EB or EUV. In other words, the resist pattern formation method of this embodiment is particularly useful when the step of exposing the resist film includes an operation of exposing the resist film to EUV (extreme ultraviolet) or EB (electron beam).

[0472] 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. Liquid 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 filled in advance with a solvent (liquid immersion medium) having a refractive index greater than that of air, and exposure (immersion exposure) is performed in that state. The liquid immersion medium is preferably a solvent having a refractive index greater than that of air and smaller than that of the resist film to be exposed, and examples include water, fluorine-based inert liquids, silicon-based solvents, hydrocarbon-based solvents, etc. Water is preferably used as the liquid immersion medium.

[0473] Examples of alkaline developers used in the alkaline development process include 0.1 to 10% by mass of tetramethylammonium hydroxide (TMAH) aqueous solution. In the solvent development process, the content of the organic solvent in the organic developer used in the development process is usually 90% by mass or more, may be 95% by mass or more, 98% by mass or more, or 100% by mass, and preferably 100% by mass, based on the total amount of the organic developer. The organic solvent contained in such an organic developer can be any solvent that can dissolve 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.

[0474] 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.

[0475] Examples of nitrile solvents include acetonitrile, propionitrile, valeronitrile, and butyronitrile.

[0476] Organic developers may contain known additives as needed. Examples of such additives include surfactants. While the surfactant is not particularly limited, examples include ionic and nonionic fluorine-based and / or silicone-based surfactants. Nonionic surfactants are preferred, and nonionic fluorine-based surfactants or nonionic silicone-based surfactants are more preferred. When a surfactant is added, the amount is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass, relative to the total amount of the organic developer.

[0477] The development process can be carried out by known development methods, such as immersing the support in developer for a certain period of time (dip method), piling up developer on the surface of the support by surface tension and leaving it still for a certain period of time (paddle method), spraying developer onto the surface of the support (spray method), or continuously dispensing developer onto a support rotating at a constant speed while scanning the developer dispensing nozzle at a constant speed (dynamic dispensing method).

[0478] As the organic solvent contained in the rinsing solution used for rinsing after development in the solvent development process, for example, an organic solvent that does not easily dissolve the resist pattern can be appropriately selected and used from among the organic solvents listed as organic solvents used in the organic developer solution. Typically, at least one solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is used. Among these, at least one selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, and amide solvents is preferred, at least one selected from alcohol solvents and ester solvents is more preferred, and alcohol solvents are particularly preferred. The alcohol solvent used in the rinsing solution is preferably a monohydric alcohol having 6 to 8 carbon atoms, and the monohydric alcohol may be linear, branched, or cyclic. Specifically, examples include 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, and benzyl alcohol. Among these, 1-hexanol, 2-heptanol, and 2-hexanol are preferred, and 1-hexanol and 2-hexanol are more preferred. 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. However, considering the development characteristics, the amount of water in the rinse solution is preferably 30% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 3% by mass or less, based on the total amount of the rinse solution. Known additives may be added to the rinse solution as needed. Examples of such additives include surfactants. Examples of surfactants are those described above, with nonionic surfactants being preferred, and nonionic fluorine-based surfactants or nonionic silicone-based surfactants being more preferred. When a surfactant is included, the amount included is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass, relative to the total amount of the rinse solution.

[0479] 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).

[0480] As described above, the resist pattern formation method of this embodiment uses the above-mentioned resist composition, which allows for increased sensitivity in resist pattern formation, improved lithography characteristics such as dimensional uniformity, and better resolution, thereby further suppressing the occurrence of pattern defects.

[0481] 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 of 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 content of impurities 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).

[0482] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0483] <Preparation of Resist Compositions> (Examples 1-16, Comparative Examples 1-6) The resist compositions for each example were prepared by mixing and dissolving the components shown in Tables 1-2.

[0484]

[0485]

[0486] In Tables 1 and 2, each abbreviation has the following meaning. The numbers in brackets [ ] represent the amount (parts by mass) of the compound. (A)-1 to (A)-8: Polymer compounds (A)-1 to (A)-8, represented by the following chemical formulas (A)-1 to (A)-8.

[0487]

[0488]

[0489] For polymer compounds (A)-1 to (A)-8, the weight-average molecular weight (Mw), molecular weight dispersion (Mw / Mn), and molecular weight dispersion were determined by GPC measurement on a standard polystyrene basis. １３ The copolymerization composition ratio (the proportion (molar ratio) of constituent units derived from each monomer compound) of the polymer compound, as determined by C-NMR, is shown below.

[0490] For polymer compound (A)-1, Mw is 5400 and Mw / Mn is 1.57. Homopolymer (polymerization composition ratio l=100). For polymer compound (A)-2, Mw is 4900 and Mw / Mn is 1.66. Copolymerization composition ratio l / m = 60 / 40. For polymer compound (A)-3, Mw is 4700 and Mw / Mn is 1.63. Copolymerization composition ratio l / m = 60 / 40. For polymer compound (A)-4, Mw is 5000 and Mw / Mn is 1.60. Copolymerization composition ratio l / m = 60 / 40. For polymer compound (A)-5, Mw is 4800 and Mw / Mn is 1.67. Copolymerization composition ratio l / m = 60 / 40. For polymer compound (A)-6, Mw is 4700 and Mw / Mn is 1.64. The copolymerization ratio is l / m = 60 / 40. For polymer compound (A)-7, Mw is 4600 and Mw / Mn is 1.63. The copolymerization ratio is l / m = 60 / 40. For polymer compound (A)-8, Mw is 4400 and Mw / Mn is 1.62. The copolymerization ratio is l / m = 60 / 40.

[0491] (A)-9: Polymer compound (A)-9 represented by the following chemical formula (A)-9. For polymer compound (A)-9, Mw is 4500, and Mw / Mn is 1.64. The copolymerization ratio is l / m = 60 / 40.

[0492]

[0493] (B)-1 to (B)-9: Acid generators consisting of compounds represented by the following chemical formulas (B)-1 to (B)-9.

[0494]

[0495]

[0496] (B)-10: An acid generator consisting of a compound represented by the following chemical formula (B)-10.

[0497]

[0498] (D)-1: An acid diffusion control agent consisting of a compound represented by the following chemical formula (D)-1. (S)-1: A mixed solvent of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 60 / 40 (mass ratio).

[0499]

[0500] <Evaluation> Contact hole patterns were formed using the resist pattern formation method described below, and the sensitivity, in-plane uniformity of pattern dimensions (CDU), and pattern defects were evaluated.

[0501] ≪Formation of Resist Pattern≫ Each resist composition was applied to a 12-inch silicon substrate treated with hexamethyldisilazane (HMDS) using a spinner. A pre-bake (PAB) treatment was performed on a hot plate at 110°C for 60 seconds, and the substrate was dried to form a resist film with a thickness of 60 nm. Next, the resist film was exposed using an EUV scanner NXE3400 (NA 0.33, inner shiguma / outer shiguma = 0.67 / 0.95, quadruple pole illumination) (manufactured by ASML) to form a contact hole pattern (hereinafter referred to as "CH pattern") in which holes with a diameter of 20 nm were arranged at equal intervals (pitch 40 nm). After that, a post-exposure heating (PEB) treatment was performed at 90°C for 60 seconds. Next, alkaline development was performed at 23°C for 30 seconds using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) "NMD-3" (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.). After that, a water rinse treatment was performed with pure water for 15 seconds. As a result, a CH pattern was formed in all of the resist compositions, in which holes with a diameter of 20 nm were arranged at equal intervals (pitch of 40 nm).

[0502] [Sensitivity Evaluation] The optimal exposure dose Eop (mJ / cm²) for forming a CH pattern of the target size by the above <resist pattern formation> procedure. ２ We calculated this as "Eop(mJ / cm²)". ２ This is shown in Tables 3-4.

[0503] [Evaluation of In-Plane Uniformity of Pattern Dimensions (CDU)] For the CH patterns formed by the above-mentioned <Formation of Resist Patterns>, a total of 10,000 CH patterns were observed from above using a measuring SEM (Scanning Electron Microscope, accelerating voltage 500V, product name: CG6300, Hitachi High-Tech Corporation), and the hole diameter (nm) of each hole was measured. Then, three times the standard deviation (σ) calculated from the measurement results (3σ) was determined. The results are shown in Tables 3-4 as "CDU (nm)". The smaller the 3σ value obtained in this way, the higher the uniformity of the dimensions (CD) of the multiple holes formed in the resist film.

[0504] [Pattern Defect Evaluation] Of the 10,000 CH patterns observed in the CDU evaluation described above, defects with a hole diameter of 14 nm (70% of the target size) or less were defined as defects with insufficient aperture, and their number was measured. The results are shown in Tables 3-4 as "Number of Defects (pieces)".

[0505]

[0506]

[0507] The results shown in Tables 3-4 confirm that when the resist compositions of Examples 1-16 to which the present invention is applied are used, the sensitivity in resist pattern formation is improved, dimensional uniformity is enhanced, and the occurrence of pattern defects is further suppressed compared to when the resist compositions of Comparative Examples 1-6 are used.

[0508]

[0509] Table 5 summarizes the composition and evaluation results of the resist compositions of Example 8, Comparative Example 1, Comparative Example 6, and Comparative Example 2 in a single table. Comparison of Comparative Examples 1, 6, and 2 with Example 8: (A)-9, used as component (A), is a polymer compound that does not have a constituent unit (a0). (B)-10, used as component (B), is a compound that does not correspond to compound (B0). (A)-8, used as component (A), is a polymer compound that has a constituent unit (a0). (B)-1, used as component (B), is a compound that corresponds to compound (B0). The resist composition of Comparative Example 1 contains (A)-9 and (B)-10. The resist composition of Comparative Example 6, which contains (A)-8 and (B)-10 instead of (A)-9, has an Eop value of 8 (mJ / cm) higher than the resist composition of Comparative Example 1. ２ ), an improvement of 0.5 nm in the CDU value and 1603 in the defect count value was observed. The resist composition of Comparative Example 2, which contains (A)-9 and (B)-1 instead of (B)-10, showed an improvement of 6 mJ / cm² in the Eop value compared to the resist composition of Comparative Example 1. ２), an improvement of 0.3 nm in the CDU value and 1513 in the defect count value was observed. The resist composition of Example 8, which contains (A)-8 instead of (A)-9 and (B)-1 instead of (B)-10, showed an improvement of 14 mJ / cm² in the Eop value compared to the resist composition of Comparative Example 1. ２ A remarkable improvement was observed in the CDU value of 0.6 nm and in the number of defects of 2484. In other words, the synergistic effect of the combination of (A)-8 and (B)-1 was confirmed.

[0510]

[0511] Table 6 summarizes the composition and evaluation results of the resist compositions of Example 15, Comparative Example 1, Comparative Example 6, and Comparative Example 3 in a single table. Comparison of Comparative Examples 1, 6, and 3 with Example 15: (B)-8, used as component (B), is a compound corresponding to compound (B0). The resist composition of Comparative Example 1 contains (A)-9 and (B)-10. The resist composition of Comparative Example 6, which contains (A)-8 and (B)-10 instead of (A)-9, has an Eop value of 8 (mJ / cm) higher than the resist composition of Comparative Example 1. ２ ), an improvement of 0.5 nm in the CDU value and 1603 in the defect count value was observed. The resist composition of Comparative Example 3, which contains (A)-9 and (B)-8 instead of (B)-10, showed an improvement of 4 mJ / cm² in the Eop value compared to the resist composition of Comparative Example 1. ２ ), an improvement of 0.5 nm in the CDU value and 1614 defects in the defect count value was observed. The resist composition of Example 15, which contains (A)-8 instead of (A)-9 and (B)-8 instead of (B)-10, showed an improvement of 19 mJ / cm² in the Eop value compared to the resist composition of Comparative Example 1. ２ A remarkable improvement was observed in the CDU value of 1.5 nm and the defect count of 2942. In other words, the synergistic effect of the combination of (A)-8 and (B)-8 was confirmed.

[0512]

[0513] Table 7 summarizes the compositions and evaluation results of the resist compositions of Example 16, Comparative Example 1, Comparative Example 6, and Comparative Example 4 in a single table. Comparison of Comparative Examples 1, 6, and 4 with Example 16: (B)-9, used as component (B), is a compound corresponding to compound (B0). The resist composition of Comparative Example 1 contains (A)-9 and (B)-10. The resist composition of Comparative Example 6, which contains (A)-8 and (B)-10 instead of (A)-9, has an Eop value of 8 (mJ / cm) higher than the resist composition of Comparative Example 1. ２ ), an improvement of 0.5 nm in the CDU value and 1603 in the defect count value was observed. The resist composition of Comparative Example 4, which contains (A)-9 and (B)-9 instead of (B)-10, showed an improvement of 5 mJ / cm² in the Eop value compared to the resist composition of Comparative Example 1. ２ ), an improvement of 0.6 nm in CDU value and 1579 in defect count value was observed. The resist composition of Example 16, which contains (A)-8 instead of (A)-9 and (B)-9 instead of (B)-10, showed an improvement of 17 mJ / cm² in Eop value compared to the resist composition of Comparative Example 1. ２ A remarkable improvement was observed in the CDU value of 1.4 nm and the defect count of 2809. In other words, the synergistic effect of the combination of (A)-8 and (B)-9 was confirmed.

[0514] Although preferred embodiments of the present invention have been described above, the present invention is not limited to these embodiments. Additions, omissions, substitutions, and other modifications to the configuration are possible without departing from the spirit of the present invention. The present invention is not limited by the foregoing description and is limited only by the appended claims.

Claims

A resist composition that generates acid upon exposure and whose solubility in a developer changes due to the action of the acid, It contains a resin component (A1) whose solubility in the developer changes due to the action of acid, and an acid-generating agent component (B) that generates acid upon exposure. The aforementioned resin component (A1) has a constituent unit derived from a compound represented by the following general formula (a0-1), The acid generator component (B) is a resist composition comprising a compound (B0) represented by the following general formula (b0). [In the formula, W ０１ This is a polymerizable group-containing group. ０２ This is an aromatic hydrocarbon group which may have substituents. ０１ This is a divalent linking group or a single bond. Ra ０１ Ra is an acid-dissociable group. ０２ [p] is a chain hydrocarbon group which may have substituents, or an alicyclic hydrocarbon group which may have substituents. [p] is an integer of 1 or more. [q] is an integer of 1 or more. [wherein, Rb ０ is a condensed ring group containing a condensed ring having one or more aromatic rings. The condensed ring group has, as a substituent, a functional group (Fab) that controls solubility in a developer. Yb ０ is a divalent linking group or a single bond. Vb ０ is an alkylene group, a fluorinated alkylene group or a single bond. R ０ is a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom. M ｍ＋ is an m-valent organic cation. m is an integer of 1 or more. ] The resist composition according to claim 1, wherein the compound (B0) is a compound represented by the following general formula (b0-1). [In the formula, Rx １ ~Rx ４ Each of these independently represents a hydrocarbon group or hydrogen atom which may have substituents, or two or more may be bonded to each other to form a ring structure. １ ~Ry ２ Each of these elements independently represents a hydrocarbon group or hydrogen atom which may have substituents, or they may be bonded to each other to form a ring structure. It is either a double bond or a single bond. Rz １ ~Rz ４ Each of these independently represents a hydrocarbon group or hydrogen atom that may have substituents, provided the valence is permissible, or two or more may be bonded to each other to form a ring structure. However, Rx １ ~Rx ４ Two or more of the following, １ ~Ry ２ , or Rz １ ~Rz ４ At least one of the two or more of these is bonded to each other to form an aromatic ring. Also, Rx １ ~Rx ４ , Ry １ ~Ry ２ and Rz １ ~Rz ４ At least one of them has an anionic group represented by the following general formula (b0-r-an1), and the entire anionic part forms an n-valent anion. Also, Rx １ ~Rx ４ , Ry １ ~Ry ２ and Rz １ ~Rz ４ At least one of them has the functional group (Fab). n is an integer of 1 or more. ｍ＋ [where m is an m-valent organic cation, and m is an integer greater than or equal to 1] [In the formula, Yb ０ Vb is a divalent linking group or a single bond. ０ R is an alkylene group, a fluorinated alkylene group, or a single bond. ０ This is a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom. * indicates a bond. 　 The resist composition according to claim 1 or 2, wherein the functional group (Fab) is an acid-degradable group that decomposes upon the action of an acid to produce a polar group. 　 The resist composition according to claim 1 or 2, wherein the functional group (Fab) is a base-degradable group that has the ability to degrade by the action of a base, thereby cleaving at least some of the bonds in the structure. 　 Ra in the above general formula (a0-1) ０１ The resist composition according to claim 1 or 2, wherein the acid-dissociable group in is a cyclic group. 　 The resist composition according to claim 1 or 2, wherein the resin component (A1) further comprises a constituent unit represented by the following general formula (a10-1). [In the formula, R is an alkyl group having 1 to 5 carbon atoms, an alkyl halide having 1 to 5 carbon atoms, or a hydrogen atom. Ya ｘ１ This is a divalent linking group or a single bond. Wa ｘ１ n is an aromatic hydrocarbon group which may have substituents. ａｘ１ [ is an integer greater than or equal to 1.] A method for forming a resist pattern, comprising the steps of: forming a resist film on a support using the resist composition described in claim 1 or 2; exposing the resist film; and developing the exposed resist film to form a resist pattern.

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