Resist composition, method of forming resist pattern, compound, and acid diffusion controlling agent

Abstract

A resist composition comprising a listed component (A) and a compound (D0) represented by the general formula (d0). In the formula, Rd0 is a condensed cyclic group comprising a condensed ring containing one or more aromatic rings. The condensed cyclic group has, as a substituent, an acid-degradable group that decomposes upon the action of an acid to produce a polar group. Yd0 is a divalent linker or a single bond. Mm+ represents an organic cation of m. m is an integer of 1 or more. [Chemical Formula 1]

Description

Technology Field

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

[0002] The present application claims priority based on Japanese patent application No. 2021-087105 filed in Japan on May 24, 2021, and incorporates the contents thereof herein. Background Technology

[0003] Recently, in the manufacturing of semiconductor devices and liquid crystal display devices, pattern miniaturization is progressing rapidly due to advancements in lithography technology. As a method for miniaturization, the wavelength (higher energy) of the exposure light source is generally being shortened.

[0004] Resist materials require lithography characteristics such as sensitivity to these exposure light sources and resolution capable of reproducing patterns of fine dimensions.

[0005] As a resist material satisfying such requirements, a chemically amplified resist composition is conventionally used, comprising a substrate component whose solubility in a developer changes due to the action of an acid, and an acid-generating agent component that generates acid upon exposure.

[0006] In the formation of resist patterns, the behavior of acids generated from acid-generating components by exposure is a factor that significantly influences lithography characteristics.

[0007] In this regard, a chemically amplified resist composition has been proposed that, together with an acid generating agent, contains an acid diffusion control agent that controls the diffusion of acid generated from the acid generating agent by exposure.

[0008] For example, Patent Document 1 discloses an acid generating agent and an acid diffusion control agent having a specific bulky structure (bicyclooctane backbone) in which the anion part is mainly composed of hydrocarbons and has relatively high hydrophobicity. In the invention described in Patent Document 1, the means mainly involves employing a compound having an anion part with relatively high hydrophobicity in the acid generating agent, and it is disclosed that, according to a resist composition containing said compound, high sensitivity can be achieved in the formation of a resist pattern, and a resist pattern of good shape with high resolution and reduced roughness can be formed. Prior art literature

[0009] Japanese Patent Publication No. 2018-92159 The problem to be solved

[0010] With further advancements in lithography technology and the increasing miniaturization of resist patterns, for example, in lithography using EUV or EB, the goal is to form fine patterns of tens of nanometers. As the dimensions of the resist pattern become smaller, there is a need for a resist composition capable of forming a resist pattern with good in-plane uniformity (CDU) and resolution.

[0011] However, in the resist composition containing an acid diffusion control agent having a bulky structure as described in Patent Document 1 above, although the uniformity of the acid diffusion control agent in the resist film can be improved by enhancing hydrophobicity, the affinity for the developer is reduced, and there is room for improvement regarding the compatibility of CDU and resolution.

[0012] The present invention, made in consideration of the above circumstances, aims to provide a resist composition capable of forming a CDU and a resist pattern with good resolution, a method for forming a resist pattern using said resist composition, a novel compound useful as an acid generator for said resist composition, and an acid generator using said compound. means of solving the problem

[0013] To solve the above problem, the present invention adopts the following configuration.

[0014] That is, the first aspect of the present invention is a resist composition that generates acid upon exposure and changes solubility in a developer solution upon the action of the acid, comprising a substrate component (A) that changes solubility in a developer solution upon the action of the acid, an acid generating agent component (B) that generates acid upon exposure, and an acid diffusion controlling agent component (D) that controls the diffusion of acid generated from the acid generating agent component (B) upon exposure, wherein the acid diffusion controlling agent component (D) comprises a compound (D0) represented by the following general formula (d0).

[0015] [Chemical Formula 1]

[0016]

[0017] [In the middle of the meal, Rd 0 Yd is a condensed cyclic group comprising a condensed ring containing one or more aromatic rings. The condensed cyclic group has, as a substituent, an acid-degrading group that decomposes upon the action of an acid to generate a polar group. 0 It is a 2-valent connector or single bond. M m＋ represents an organic cation of valence m. m is an integer greater than or equal to 1.

[0018] A second aspect of the present invention is a method for forming a resist pattern, comprising the steps of: forming a resist film on a support using a resist composition related to the first aspect; exposing the resist film to light; and developing the resist film after exposure to form a resist pattern.

[0019] A third aspect of the present invention is a compound represented by the following general formula (d0).

[0020] [Chemical Formula 2]

[0021]

[0022] [In the middle of the meal, Rd 0 Yd is a condensed cyclic group comprising a condensed ring containing one or more aromatic rings. The condensed cyclic group has, as a substituent, an acid-degrading group that decomposes upon the action of an acid to generate a polar group. 0 It is a 2-valent connector or single bond. M m＋ represents an organic cation of valence m. m is an integer greater than or equal to 1.

[0023] A fourth aspect of the present invention is an acid diffusion control agent comprising a compound related to the third aspect. Effects of the invention

[0024] According to the present invention, a resist composition capable of forming a CDU and a resist pattern with good resolution, a method for forming a resist pattern using said resist composition, a novel compound useful as an acid generator of said resist composition, and an acid generator using said compound can be provided. Specific details for implementing the invention

[0025] In this specification and the claims, "aliphatic" is defined as a concept relative to aromatic, meaning a group, compound, etc., that does not possess aromaticity.

[0026] Unless otherwise specified, the “alkyl group” shall include monovalent saturated hydrocarbon groups of straight-chain, branched-chain, and cyclic forms. The same applies to the alkyl groups in the alkoxy groups.

[0027] Unless otherwise specifically mentioned, the “alkylene group” shall include divalent saturated hydrocarbon groups of straight-chain, branched-chain, and cyclic forms.

[0028] Examples of "halogen atoms" include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0029] "Constituent unit" means a monomer unit (monomer unit) that constitutes a polymer compound (resin, polymer, copolymer).

[0030] When stating "substituents may be used," it includes both cases where a hydrogen atom (-H) is substituted with a monovalent group and where a methylene group (-CH2-) is substituted with a divalent group.

[0031] "Exposure" is a concept that encompasses the entire process of radiation irradiation.

[0032] "An acid-degradable group" is a group having acid degradability in which at least some of the bonds in the structure of the acid-degradable group can be cleaved by the action of acid.

[0033] Acid-decomposing groups whose polarity increases due to the action of acid include, for example, groups that are decomposed by the action of acid to produce polar groups.

[0034] Examples of polar groups include carboxyl groups, hydroxyl groups, amino groups, sulfonyl groups (-SO3H), etc.

[0035] More specifically as an acid-decomposing group, the above-mentioned polar group may be protected by an acid-dissociating group (for example, a group in which a hydrogen atom of an OH-containing polar group is protected by an acid-dissociating group).

[0036] "Acid dissociable group" refers to both of the following: (i) a group having acid dissociability in which the bond between said acid dissociable group and an atom adjacent to said acid dissociable group can be ruptured by the action of an acid, or (ii) a group in which, after some bonds are ruptured by the action of an acid, an additional decarboxylation reaction occurs, thereby rupturing the bond between said acid dissociable group and an atom adjacent to said acid dissociable group.

[0037] The acid dissociable group constituting the acid dissociable group must be a group with lower polarity than the polar group generated by the dissociation of said acid dissociable group. Thus, when the acid dissociable group is dissociated by the action of an acid, a polar group with higher polarity than said acid dissociable group is generated, thereby increasing polarity. As a result, the polarity of the entire component (A1) increases. As polarity increases, the solubility in the developer changes relatively; if the developer is an alkaline developer, solubility increases, and if the developer is an organic developer, solubility decreases.

[0038] "Base component" refers to an organic compound having film-forming ability. Organic compounds used as base components are broadly classified into nonpolymers and polymers. Nonpolymers typically have a molecular weight of 500 or more and less than 4000. Hereinafter, when referred to as "low molecular weight compound," a nonpolymer with a molecular weight of 500 or more and less than 4000 is used. Polymers typically have a molecular weight of 1000 or more. Hereinafter referred to as "resin," "high molecular weight compound," or "polymer," a polymer with a molecular weight of 1000 or more is used. The molecular weight of the polymer shall be the weight-average molecular weight calculated as polystyrene by GPC (gel permeation chromatography).

[0039] "Induced constituent unit" means a constituent unit formed by the cleavage of multiple bonds between carbon atoms, for example, ethylenetic double bonds.

[0040] In the "acrylic acid ester," the hydrogen atom bonded to the carbon atom at the α position may be substituted with a substituent. The substituent (R) that substitutes the hydrogen atom bonded to the carbon atom at the α position αx ) is an atom or group other than a hydrogen atom. Also, a substituent (R αx an itaconic acid diester substituted with a substituent containing an ester bond, or a substituent (R αx ) is also included in α-hydroxyacrylates in which ) is substituted with a hydroxyalkyl group or a group modifying the hydroxyl group. In addition, the carbon atom at the α position of the acrylic acid ester is, unless otherwise specifically mentioned, the carbon atom to which the carbonyl group of acrylic acid is bonded.

[0041] Below, an acrylic acid ester in which a hydrogen atom bonded to a carbon atom at the α position is substituted with a substituent is sometimes referred to as an α-substituted acrylic acid ester.

[0042] The term "derivative" is a concept that includes a target compound in which the hydrogen atom at the α-position is substituted with another substituent, such as an alkyl group or an alkyl halide group, and their derivatives. Examples of such derivatives include a target compound in which the hydrogen atom of a hydroxyl group, which may be substituted with a substituent at the α-position, is substituted with an organic group; and a target compound in which a substituent other than a hydroxyl group is bonded to which the hydrogen atom at the α-position may be substituted with a substituent. Furthermore, unless otherwise specified, the α-position refers to the first carbon atom adjacent to the functional group.

[0043] As a substituent for the hydrogen atom at the α position of hydroxystyrene, R αx The same can be cited as an example.

[0044] In the scope of this specification and claims, depending on the structure represented by the chemical formula, there may be an asymmetric carbon and an enantiomer or a diastereomer. In such cases, the isomers are represented by a single chemical formula. The isomers may be used individually or as a mixture.

[0045] (Resist composition)

[0046] The resist composition of the present embodiment generates acid upon exposure to light, and its solubility in the developer changes due to the action of the acid.

[0047] The resist composition comprises a substrate component (A) (hereinafter also referred to as “Component (A)”) whose solubility in a developer changes due to the action of an acid, an acid generating agent component (B) (hereinafter also referred to as “Component (B)”) which generates acid upon exposure, and an acid diffusion controlling agent component (D) (hereinafter also referred to as “Component (D)”) which controls the diffusion of acid generated from Component (B) upon exposure.

[0048] When a resist film is formed using the resist composition of the present embodiment and selective exposure is performed on the resist film, acid is generated from component (B) in the exposed portion of the resist film and the solubility of component (A) in the developer changes due to the action of the acid, whereas the solubility of component (A) in the developer does not change in the unexposed portion of the resist film, thus a difference in solubility in the developer occurs between the exposed portion and the unexposed portion. Therefore, when the resist film is developed, if the resist composition is of the positive type, the exposed portion of the resist film is dissolved and removed to form a positive type resist pattern, and if the resist composition is of the negative type, the unexposed portion of the resist film is dissolved and removed to form a negative type resist pattern.

[0049] In this specification, a resist composition in which the exposed portion of the resist film is dissolved and removed to form a positive-type resist pattern is referred to as a positive-type resist composition, and a resist composition in which the unexposed portion of the resist film is dissolved and removed to form a negative-type resist pattern is referred to as a negative-type resist composition. The resist composition of the present embodiment may be a positive-type resist composition or a negative-type resist composition. Furthermore, the resist composition of the present embodiment may be for an alkaline development process in which an alkaline developer is used for the development treatment when forming a resist pattern, or for a solvent development process in which a developer containing an organic solvent (organic developer) is used for the development treatment.

[0050] <(A) Ingredient>

[0051] In the resist composition of the present embodiment, it is preferable that component (A) includes a resin component (A1) (hereinafter also referred to as “component (A1)”) whose solubility in the developer changes due to the action of an acid. By using component (A1), the polarity of the substrate component changes before and after exposure, so good development contrast can be obtained not only in the alkaline development process but also in the solvent development process.

[0052] (A) As for the component, other high molecular weight compounds and / or low molecular weight compounds may be used in combination with the (A1) component.

[0053] When applying an alkali development process, the substrate component containing component (A1) is insoluble in the alkali developer before exposure, and, for example, if an acid is generated from component (B) by exposure, the polarity increases due to the action of the acid, and the solubility in the alkali developer increases. Therefore, in forming a resist pattern, when the resist film obtained by applying the resist composition onto a support is selectively exposed, the exposed portion of the resist film changes from insoluble to soluble in the alkali developer, while the unexposed portion of the resist film remains insoluble in the alkali and does not change, so a positive type resist pattern is formed by alkali development.

[0054] Meanwhile, when a solvent development process is applied, the substrate component containing the component (A1) has high solubility with respect to the organic developer before exposure. For example, if an acid is generated from the component (B) by exposure, the polarity increases due to the action of the acid, and the solubility with respect to the organic developer decreases. Therefore, in the formation of a resist pattern, when the resist film obtained by applying the resist composition onto a support is selectively exposed, the exposed portion of the resist film changes from soluble to insoluble with respect to the organic developer, while the unexposed portion of the resist film remains soluble and does not change. Thus, by developing with an organic developer, contrast can be provided between the exposed portion and the unexposed portion, and a negative type resist pattern is formed.

[0055] In the resist composition of the present embodiment, component (A) may be used alone or two or more types may be used in combination.

[0056] · (A1) Regarding the component

[0057] (A1) The component is a resin component whose solubility in the developer changes due to the action of acid.

[0058] (A1) As a component, it is preferable to have a constituent unit (a1) that includes an acid-degrading group whose polarity is increased by the action of an acid.

[0059] (A1) The component may have other constituent units in addition to the constituent unit (a1) as needed.

[0060] ≪Constituent Unit (a1)≫

[0061] The constituent unit (a1) is a constituent unit containing an acid-degrading group whose polarity is increased by the action of an acid.

[0062] As for acid dissociable groups, examples include those that have been proposed so far as acid dissociable groups of base resins for chemically amplified resist compositions.

[0063] Specifically, the acid dissociable groups proposed for base resins for chemically amplified resist compositions include the “acetal-type acid dissociable groups,” “tertiary alkyl ester-type acid dissociable groups,” and “tertiary alkyloxycarbonyl acid dissociable groups” described below.

[0064] Acetyl-type acid dissociation group:

[0065] Among the above polar groups, an acid dissociable group that protects a carboxyl group or a hydroxyl group may be, for example, an acid dissociable group represented by the following general formula (a1-r-1) (hereinafter referred to as an "acetal-type acid dissociable group").

[0066] [Chemical Formula 3]

[0067]

[0068] [During the meal, Ra' 1 , Ra' 2 is a hydrogen atom or an alkyl group. Ra' 3 As a hydrocarbon group, Ra' 3 Eun, Ra' 1 , Ra' 2 It may be combined with any of the following to form a ring.

[0069] In equation (a1-r-1), Ra' 1 and Ra' 2 It is preferable that at least one of them is a hydrogen atom, and it is more preferable that both are hydrogen atoms.

[0070] Ra' 1 or Ra' 2 When the alkyl group is an alkyl group, the alkyl group may be the same as the alkyl group exemplified as a substituent that may be bonded to the carbon atom at the α position in the description of the α-substituted acrylic acid ester above, and an alkyl group having 1 to 5 carbon atoms is preferred. Specifically, a straight-chain or branched-chain alkyl group may be preferred. More specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, etc. may be preferred, and a methyl group or an ethyl group is more preferred, and a methyl group is particularly preferred.

[0071] In equation (a1-r-1), Ra' 3 Examples of hydrocarbon groups include straight-chain or branched-chain alkyl groups or cyclic hydrocarbon groups.

[0072] The straight-chain 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, n-pentyl groups, etc. Among these, methyl groups, ethyl groups, or n-butyl groups are preferred, and methyl groups or ethyl groups are more preferred.

[0073] The branched chain type alkyl group preferably has 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specifically, examples include isopropyl groups, isobutyl groups, tert-butyl groups, isopentyl groups, neopentyl groups, 1,1-diethylpropyl groups, 2,2-dimethylbutyl groups, etc., and it is preferred to be an isopropyl group.

[0074] Ra' 3 In the case where this becomes a cyclic hydrocarbon group, the hydrocarbon group can be an aliphatic hydrocarbon or an aromatic hydrocarbon, and can also be a polycyclic or monocyclic group.

[0075] As for the monocyclic aliphatic hydrocarbon group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferred. As for the monocycloalkane, one having 3 to 6 carbon atoms is preferred, and specifically, examples include cyclopentane and cyclohexane.

[0076] As for the polycyclic aliphatic hydrocarbon group, a polycycloalkane with one hydrogen atom removed is preferred, and the polycycloalkane is preferred to have 7 to 12 carbon atoms, and specifically, examples include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.

[0077] Ra' 3 When the cyclic hydrocarbon group becomes an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.

[0078] 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.

[0079] Specifically, aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic complex rings in which some of the carbon atoms constituting the aromatic hydrocarbon rings are substituted with heteroatoms. Examples of heteroatoms in aromatic complex rings include oxygen atoms, sulfur atoms, and nitrogen atoms. Specifically, aromatic complex rings include pyridine rings and thiophene rings.

[0080] Ra' 3 Specifically, the aromatic hydrocarbon group in the above example may be a group (aryl group or heteroaryl group) from which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic complex ring; a group from which one hydrogen atom has been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); or a group in which one hydrogen atom of the aromatic hydrocarbon ring or aromatic complex ring is substituted with an alkylene group (e.g., benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc., arylalkyl group, etc.). The number of carbon atoms of the alkylene group bonded to the aromatic hydrocarbon ring or aromatic complex ring is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0081] Ra' 3 The cyclic hydrocarbon group in [formation] may have a substituent. Examples of such substituents include -R P1 , -R P2 -OR P1 , -R P2 -CO-R P1 , -R P2 -CO-OR P1 , -R P2 -O-CO-R P1 , -R P2 -OH, -R P2 -CN or -R P2-COOH (hereinafter, these substituents are combined to form "Ra x5 Examples include 」 (also called ).

[0082] Here, R P1 It is a monovalent chain-type 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 is a single bond, a divalent chain-type saturated hydrocarbon group having 1 to 10 carbon atoms, a divalent aliphatic cyclic-type saturated hydrocarbon group having 3 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms. provided that R P1 and R P2 Some or all of the hydrogen atoms in the chain-type saturated hydrocarbon group, the aliphatic cyclic saturated hydrocarbon group, and the aromatic hydrocarbon group may be substituted with fluorine atoms. The aliphatic cyclic hydrocarbon group may have one or more of the substituents as a single type, or may have one or more of the multiple types of substituents each.

[0083] Examples of monovalent chain-type saturated hydrocarbon groups having 1 to 10 carbon atoms include, for instance, methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, decyl groups, etc.

[0084] Examples of monocyclic aliphatic saturated hydrocarbon groups having 3 to 20 carbon atoms include monocyclic aliphatic saturated hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, and cyclododecyl group; polycyclic aliphatic saturated hydrocarbon groups such as bicyclo[2.2.2]octanyl group, tricyclo[5.2.1.02,6]decanyl group, tricyclo[3.3.1.13,7]decanyl group, tetracyclo[6.2.1.13,6.02,7]dodecanyl group, and adamantyl group.

[0085] 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.

[0086] Ra' 3 This Ra' 1 , Ra' 2 When forming a ring by combining with any of the above, the ring group is preferably a 4 to 7-membered ring, and more preferably a 4 to 6-membered ring. Specific examples of the ring group include tetrahydropyranyl groups, tetrahydrofuranyl groups, etc.

[0087] Tertiary alkyl ester type acid dissociable group:

[0088] Among the above polar groups, acid-dissociable groups that protect the carboxyl group can be, for example, acid-dissociable groups represented by the following general formula (a1-r-2).

[0089] In addition, among the acid dissociable groups represented by the following formula (a1-r-2), those composed of alkyl groups may be referred to as "tertiary alkyl ester-type acid dissociable groups" for convenience.

[0090] [Chemical Formula 4]

[0091]

[0092] [During the meal, Ra' 4 ~ Ra' 6 Each is a hydrocarbon group, Ra' 5 , Ra' 6 They may combine with each other to form a ring.

[0093] Ra' 4 Examples of hydrocarbon groups include straight-chain or branched-chain alkyl groups, chain-type or cyclic alkenyl groups, or cyclic hydrocarbon groups.

[0094] Ra' 4The straight-chain or branched-chain alkyl group and cyclic hydrocarbon group (single-ring aliphatic hydrocarbon group, polycyclic aliphatic hydrocarbon group, aromatic hydrocarbon group) in the above Ra' 3 One can cite the same thing as.

[0095] Ra' 4 In this case, the chain-type or ring-type alkenyl group is preferably an alkenyl group having 2 to 10 carbon atoms.

[0096] Ra' 5 , Ra' 6 As for the hydrocarbon group of, the above Ra' 3 One can cite the same thing as.

[0097] Ra' 5 Wa Ra' 6 When these combine to form a ring, groups represented by the following general formula (a1-r2-1), the following general formula (a1-r2-2), and the following general formula (a1-r2-3) can be preferably cited.

[0098] Meanwhile, Ra' 4 ~ Ra' 6 In the case where they are independent hydrocarbon groups that are not bonded to each other, groups represented by the following general formula (a1-r2-4) can be preferably cited.

[0099] [Chemical Formula 5]

[0100]

[0101] [Equation (a1-r2-1), Ra' 10 It represents a straight-chain or branched-chain alkyl group having 1 to 12 carbon atoms, where some parts may be substituted with halogen atoms or heteroatom-containing groups. Ra' 11 Ra' 10It represents 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 is independently a hydrogen atom, a monovalent chain-type 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 chain-type saturated hydrocarbon groups and aliphatic cyclic saturated hydrocarbon groups may be substituted. Ra 101 ~ Ra 103 Two or more of may be bonded to each other to form a ring structure. In formula (a1-r2-3), Yaa is a carbon atom. Xaa is a group that forms an aliphatic ring group together with Yaa. Ra 104 is an aromatic hydrocarbon group that may have substituents. In formula (a1-r2-4), Ra' 12 and Ra' 13 Each is independently a monovalent chain-type saturated hydrocarbon group having 1 to 10 carbon atoms. Some or all of the hydrogen atoms in this chain-type saturated hydrocarbon group may be substituted. Ra' 14 is a hydrocarbon group that may have substituents. * indicates a bond loss.]

[0102] In the above equation (a1-r2-1), Ra' 10 It is a straight-chain or branched-chain alkyl group having 1 to 12 carbon atoms, which may be partially substituted with halogen atoms or heteroatom-containing groups.

[0103] Ra' 10 The straight-chain alkyl group in the above has 1 to 12 carbon atoms, 1 to 10 carbon atoms is preferred, and 1 to 5 carbon atoms is particularly preferred.

[0104] Ra' 10 As for the branched chain type alkyl group in [the above], the Ra' 3 One can cite the same thing as.

[0105] Ra' 10 In the above, a portion of the alkyl group may be substituted with a halogen atom or a heteroatom-containing group. For example, a portion of the hydrogen atoms constituting the alkyl group may be substituted with a halogen atom or a heteroatom-containing group. Also, a portion of the carbon atoms (such as methylene groups) constituting the alkyl group may be substituted with a heteroatom-containing group.

[0106] Examples of heteroatoms mentioned here include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of heteroatom-containing groups include (-O-), -C(=O)-O-, -OC(=O)-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -S-, -S(=O)2-, -S(=O)2-O-, etc.

[0107] In equation (a1-r2-1), Ra' 11 (Ra' 10 The aliphatic cyclic group formed together with this bonded carbon atom is Ra' in formula (a1-r-1). 3 A group exemplified as an aliphatic hydrocarbon group (alicyclic hydrocarbon group) that is a monocyclic or polycyclic group is preferred. Among these, a monocyclic alicyclic hydrocarbon group is preferred, and specifically, a cyclopentyl group and a cyclohexyl group are more preferred.

[0108] In formula (a1-r2-2), the cyclic hydrocarbon group formed by Xa together with Ya is Ra' in formula (a1-r1). 3 Examples include a group in which one or more hydrogen atoms have been additionally removed from a cyclic monovalent hydrocarbon group (aliphatic hydrocarbon group).

[0109] The cyclic hydrocarbon group formed by Xa together with Ya may have a substituent. As this substituent, the above Ra' 3 Examples include the same substituents that the cyclic hydrocarbon group in this case may have.

[0110] In equation (a1-r2-2), Ra 101 ~ Ra 103 Examples of monovalent chain-type saturated hydrocarbon groups having 1 to 10 carbon atoms include, for instance, methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, decyl groups, etc.

[0111] Ra 101 ~ Ra 103 Examples of monocyclic aliphatic saturated hydrocarbon groups having 3 to 20 carbon atoms include monocyclic aliphatic saturated hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, and cyclododecyl group; polycyclic aliphatic saturated hydrocarbon groups such as bicyclo[2.2.2]octanyl group, tricyclo[5.2.1.02,6]decanyl group, tricyclo[3.3.1.13,7]decanyl group, tetracyclo[6.2.1.13,6.02,7]dodecanyl group, and adamantyl group.

[0112] Ra 101 ~ Ra 103 Among them, from the perspective of ease of synthesis, a hydrogen atom and a monovalent chain-type saturated hydrocarbon group having 1 to 10 carbon atoms are preferred, among which a hydrogen atom, a methyl group, and an ethyl group are more preferred, and a hydrogen atom is particularly preferred.

[0113] The above Ra 101 ~ Ra 103 As substituents for the chain-type saturated hydrocarbon group represented by, or the aliphatic cyclic-type saturated hydrocarbon group, are, for example, the Ra described above. x5 It can hold the same energy as.

[0114] Ra101 ~ Ra 103 Examples of groups containing carbon-carbon double bonds formed by two or more of these bonding together to form a ring structure include, for instance, cyclopentenyl groups, cyclohexenyl groups, methylcyclopentenyl groups, methylcyclohexenyl groups, cyclopentylideneethenyl groups, cyclohexylideneethenyl groups, etc. Among these, cyclopentenyl groups, cyclohexenyl groups, and cyclopentylideneethenyl groups are preferred from the perspective of ease of synthesis.

[0115] In formula (a1-r2-3), the aliphatic cyclic group formed by Xaa together with Yaa is Ra' in formula (a1-r-1). 3 The group exemplified as an aliphatic hydrocarbon group that is a monocyclic or polycyclic group is preferred.

[0116] In equation (a1-r2-3), Ra 104 Examples of aromatic hydrocarbon groups 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 A group having one or more hydrogen atoms removed from an aromatic hydrocarbon ring having 6 to 15 carbon atoms is preferred, a group having one or more hydrogen atoms removed from benzene, naphthalene, anthracene, or phenanthrene is more preferred, a group having one or more hydrogen atoms removed from benzene, naphthalene, or anthracene is even more preferred, a group having one or more hydrogen atoms removed from benzene or naphthalene is particularly preferred, and a group having one or more hydrogen atoms removed from benzene is most preferred.

[0117] Ra in equation (a1-r2-3) 104 Substituents that may be present include, for example, methyl groups, ethyl groups, propyl groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups (methoxy groups, ethoxy groups, propoxy groups, butoxy groups, etc.), alkyloxycarbonyl groups, etc.

[0118] In equation (a1-r2-4), Ra' 12 and Ra' 13 Each is independently a monovalent chain-type saturated hydrocarbon group having 1 to 10 carbon atoms. Ra' 12 and Ra' 13 As for the monovalent chain-type saturated hydrocarbon group having 1 to 10 carbon atoms in the above, Ra 101 ~ Ra 103 Examples include chain-type saturated hydrocarbon groups having 1 to 10 carbon atoms. Some or all of the hydrogen atoms in this chain-type saturated hydrocarbon group may be substituted.

[0119] Ra' 12 and Ra' 13 Among these, a hydrogen atom and an alkyl group having 1 to 5 carbon atoms are preferred, an alkyl group having 1 to 5 carbon atoms is more preferred, a methyl group and an ethyl group are even more preferred, and a methyl group is particularly preferred.

[0120] Ra' above 12 and Ra' 13 In the case where a chain-type saturated hydrocarbon group represented by is substituted, the substituent is, for example, the Ra described above. x5 It can hold the same energy as.

[0121] In equation (a1-r2-4), Ra' 14 is a hydrocarbon group that may have substituents. Ra' 14 Examples of hydrocarbon groups in this include straight-chain or branched-chain alkyl groups or cyclic hydrocarbon groups.

[0122] Ra' 14In the case of the straight-chain alkyl group, it is preferable that the number of carbon atoms be 1 to 5, more preferable that it be 1 to 4, and even more preferable that it be 1 or 2. Specifically, examples include methyl groups, ethyl groups, n-propyl groups, n-butyl groups, n-pentyl groups, etc. Among these, methyl groups, ethyl groups, or n-butyl groups are preferred, and methyl groups or ethyl groups are more preferred.

[0123] Ra' 14 In the case of the branched chain type alkyl group, it is preferable that the number of carbon atoms be 3 to 10, and more preferable that it be 3 to 5. Specifically, examples include isopropyl groups, isobutyl groups, tert-butyl groups, isopentyl groups, neopentyl groups, 1,1-diethylpropyl groups, 2,2-dimethylbutyl groups, etc., and it is preferable that it be an isopropyl group.

[0124] Ra' 14 When a hydrocarbon group is formed as a cyclic hydrocarbon group, that hydrocarbon group may be an aliphatic hydrocarbon or an aromatic hydrocarbon, and may also be a polycyclic or monocyclic group.

[0125] As for the monocyclic aliphatic hydrocarbon group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferred. As for the monocycloalkane, one having 3 to 6 carbon atoms is preferred, and specifically, examples include cyclopentane and cyclohexane.

[0126] As for the polycyclic aliphatic hydrocarbon group, a polycycloalkane with one hydrogen atom removed is preferred, and the polycycloalkane is preferred to have 7 to 12 carbon atoms, and specifically, examples include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.

[0127] Ra' 14 As for the aromatic hydrocarbon group in , Ra 104 Examples include those identical to the aromatic hydrocarbon groups in [the case]. Among them, Ra' 14A group having one or more hydrogen atoms removed from an aromatic hydrocarbon ring having 6 to 15 carbon atoms is preferred, a group having one or more hydrogen atoms removed from benzene, naphthalene, anthracene, or phenanthrene is more preferred, a group having one or more hydrogen atoms removed from benzene, naphthalene, or anthracene is even more preferred, a group having one or more hydrogen atoms removed from naphthalene or anthracene is particularly preferred, and a group having one or more hydrogen atoms removed from naphthalene is most preferred.

[0128] Ra' 14 As for the substituents that may be present, Ra 104 Examples of substituents that can be present include those identical to the one that is allowed.

[0129] Ra' in equation (a1-r2-4) 14 In the case where it is a naphthyl group, the position bonded to the tertiary carbon atom in the above formula (a1-r2-4) may be either the 1st position or the 2nd position of the naphthyl group.

[0130] Ra' in equation (a1-r2-4) 14 In the case where α is an anthryl group, the position bonded to the tertiary carbon atom in the above formula (a1-r2-4) may be any of the 1st, 2nd, or 9th positions of the anthryl group.

[0131] Specific examples of the group represented by the above formula (a1-r2-1) are given below.

[0132] [Chemical Formula 6]

[0133]

[0134] [Chemical Formula 7]

[0135]

[0136] [Chemical Formula 8]

[0137]

[0138] Specific examples of the group represented by the above formula (a1-r2-2) are given below.

[0139] [Chemical Formula 9]

[0140]

[0141] [Chemical Formula 10]

[0142]

[0143] [Chemical Formula 11]

[0144]

[0145] Specific examples of the group represented by the above formula (a1-r2-3) are given below.

[0146] [Chemical Formula 12]

[0147]

[0148] Specific examples of the group represented by the above formula (a1-r2-4) are given below.

[0149] [Chemical Formula 13]

[0150]

[0151] Tertiary alkyloxycarbonyl acid dissociable group:

[0152] Among the above polar groups, an acid dissociable group that protects the hydroxyl group can be, for example, an acid dissociable group represented by the following general formula (a1-r-3) (hereinafter referred to as a "tertiary alkyloxycarbonyl acid dissociable group" for convenience).

[0153] [Chemical Formula 14]

[0154]

[0155] [During the meal, Ra' 7 ~ Ra' 9 Each is an alkyl group.

[0156] In equation (a1-r-3), Ra' 7 ~ Ra' 9Each is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.

[0157] In addition, the total number of carbon atoms of each alkyl group is preferably 3 to 7, more preferably 3 to 5, and most preferably 3 to 4.

[0158] Examples of constituent units (a1) include a constituent unit derived from an acrylic acid ester in which a hydrogen atom bonded to a carbon atom at the α position may be substituted with a substituent, a constituent unit derived from an acrylamide, a constituent unit in which at least a portion of the hydrogen atom in the hydroxyl group of a constituent unit derived from hydroxystyrene or a hydroxystyrene derivative is protected by a substituent containing the acid-degrading group, and a constituent unit in which at least a portion of the hydrogen atom in the -C(=O)-OH of a constituent unit derived from vinylbenzoic acid or a vinylbenzoic acid derivative is protected by a substituent containing the acid-degrading group.

[0159] Among the above, a constituent unit (a1) is preferably a constituent unit derived from an acrylic acid ester in which a hydrogen atom bonded to a carbon atom at the α position may be substituted with a substituent.

[0160] Preferred specific examples of such a constituent unit (a1) include a constituent unit represented by the following general formula (a1-1) or (a1-2).

[0161] [Chemical Formula 15]

[0162]

[0163] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. Va 1 It is a divalent hydrocarbon group that may have ether bonds. a1 is an integer from 0 to 2. Ra1 is an acid-dissociable group represented by the above general formula (a1-r-1) or (a1-r-2). Wa 1 is n a2 It is a hydrocarbon group with +1 valence, and n a2 is an integer from 1 to 3, and Ra 2 is an acid-dissociable group represented by the above general formula (a1-r-1) or (a1-r-3).

[0164] In the above formula (a1-1), the alkyl group of R having 1 to 5 carbon atoms is preferably a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms, and specifically, examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, etc. The alkyl halide 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 a halogen atom. As for the halogen atom, a fluorine atom is particularly preferred.

[0165] As for R, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms is preferred, and a hydrogen atom or a methyl group is most preferred for industrial availability.

[0166] In the above equation (a1-1), Va 1 The divalent hydrocarbon group in this case can be an aliphatic hydrocarbon or an aromatic hydrocarbon.

[0167] Va 1 The aliphatic hydrocarbon group as the divalent hydrocarbon group in the above may be saturated or unsaturated, and is generally preferred to be saturated.

[0168] Examples of such aliphatic hydrocarbon groups include, more specifically, straight-chain or branched-chain aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups containing a ring in their structure.

[0169] The above straight-chain 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.

[0170] As for the straight-chain aliphatic hydrocarbon groups, straight-chain alkylene groups are preferred, and specifically, examples include methylene groups [-CH2-], ethylene groups [-(CH2)2-], trimethylene groups [-(CH2)3-], tetramethylene groups [-(CH2)4-], pentamethylene groups [-(CH2)5-], etc.

[0171] The branched-chain type aliphatic hydrocarbon group is preferably 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.

[0172] As for branched-chain aliphatic hydrocarbon groups, branched-chain alkylene groups are preferred, and specifically, alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-; alkylalkylene groups such as -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2-; and alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2CH2-. As for the alkyl group in the alkylalkylene group, a straight-chain alkyl group having 1 to 5 carbon atoms is preferred.

[0173] Examples of aliphatic hydrocarbon groups containing a ring among the above structures include alicyclic hydrocarbon groups (groups in which two hydrogen atoms are removed from an aliphatic hydrocarbon ring), groups in which alicyclic hydrocarbon groups are bonded to the ends of straight-chain or branched-chain aliphatic hydrocarbon groups, and groups in which alicyclic hydrocarbon groups are interposed in the middle of straight-chain or branched-chain aliphatic hydrocarbon groups. Examples of straight-chain or branched-chain aliphatic hydrocarbon groups include those identical to the straight-chain aliphatic hydrocarbon groups or the branched-chain aliphatic hydrocarbon groups.

[0174] The above-mentioned alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms.

[0175] The above alicyclic hydrocarbon group may be polycyclic or monocyclic. As for the monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferred. The monocycloalkane is preferably one having 3 to 6 carbon atoms, and specifically examples include cyclopentane and cyclohexane. As for the polycyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a polycycloalkane is preferred, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, and specifically examples include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane.

[0176] Va 1 The aromatic hydrocarbon group as a divalent hydrocarbon group in this case is a hydrocarbon group having an aromatic ring.

[0177] The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 12. However, the number of carbon atoms does not include the number of carbon atoms in the substituents.

[0178] Specifically, aromatic rings having an aromatic hydrocarbon group include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene; and aromatic complex rings in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Examples of heteroatoms in an aromatic complex ring include oxygen atoms, sulfur atoms, nitrogen atoms, etc.

[0179] Specifically, the aromatic hydrocarbon group may include a group (arylene group) in which two hydrogen atoms have been removed from the aromatic hydrocarbon ring; a group in which one hydrogen atom of a group (aryl group) in which one hydrogen atom has been removed from the aromatic hydrocarbon ring is substituted with an alkylene group (e.g., a group in which one additional hydrogen atom has been removed from an aryl group in an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, etc.). The number of carbon atoms of the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0180] In the above equation (a1-1), Ra 1 is an acid-dissociable group represented by the above formula (a1-r-1) or (a1-r-2).

[0181] Among the above equation (a1-2), Wa 1 n in a2The hydrocarbon group of +1 may be an aliphatic hydrocarbon or an aromatic hydrocarbon. The aliphatic hydrocarbon group refers to a hydrocarbon group that does not have aromaticity, and may be saturated or unsaturated, but is generally preferred to be saturated. Examples of the above aliphatic hydrocarbon group include a straight-chain or branched-chain aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in its structure, or a group combining a straight-chain or branched-chain aliphatic hydrocarbon group and an aliphatic hydrocarbon group containing a ring in its structure.

[0182] The above n a2 + 1 is preferable, 2 to 4 is preferable, and 2 or 3 is more preferable.

[0183] In the above equation (a1-2), Ra 2 is an acid-dissociable group represented by the above general formula (a1-r-1) or (a1-r-3).

[0184] Specific examples of the constituent unit represented by the above formula (a1-1) are shown below. Among each of the following formulas, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0185] [Chemical Formula 16]

[0186]

[0187] [Chemical Formula 17]

[0188]

[0189] [Chemical Formula 18]

[0190]

[0191] [Chemical Formula 19]

[0192]

[0193] [Chemical Formula 20]

[0194]

[0195] [Chemical Formula 21]

[0196]

[0197] [Chemical Formula 22]

[0198]

[0199] [Chemical Formula 23]

[0200]

[0201] (A1) The constituent unit (a1) of the component may be one type or two or more types.

[0202] As for the constituent unit (a1), the constituent unit represented by the above formula (a1-1) is more preferable because the characteristics (sensitivity, shape, etc.) of the lithography by electron beam or EUV tend to be higher.

[0203] Among these, it is particularly desirable to include a constituent unit (a1) represented by the following general formula (a1-1-1).

[0204] [Chemical Formula 24]

[0205]

[0206] [During food, Ra 1 " is an acid-dissociable group represented by the general formulas (a1-r2-1), (a1-r2-3), or (a1-r2-4).

[0207] In the above equation (a1-1-1), R, Va 1 and n a1 is R, Va in the above equation (a1-1). 1 and n a1 It is identical to.

[0208] The description of the acid dissociable group represented by the general formulas (a1-r2-1), (a1-r2-3), or (a1-r2-4) is as described above. Among these, it is desirable to select a cyclic acid dissociable group in order to increase reactivity for EB or EUV applications.

[0209] In the above equation (a1-1-1), Ra1 Among the above, it is preferable that the group is an acid-dissociable group represented by the general formula (a1-r2-1).

[0210] The proportion of the constituent unit (a1) in the component (A1) is preferably 5 to 95 mol% with respect to the total sum (100 mol%) of the constituent units of the component (A1), more preferably 10 to 90 mol%, even more preferably 30 to 70 mol%, and particularly preferably 40 to 60 mol%.

[0211] By making the ratio of the constituent unit (a1) greater than or equal to the lower limit of the above-mentioned desirable range, lithography characteristics such as sensitivity, resolution, and roughness are improved. On the other hand, if it is less than or equal to the upper limit of the above-mentioned desirable range, a balance with other constituent units can be achieved, and various lithography characteristics are improved.

[0212] Other constituent units

[0213] (A1) The component may have other constituent units as needed in addition to the constituent unit (a1) described above.

[0214] Other constituent units may include, for example, a constituent unit (a10) represented by the general formula (a10-1) described below; a constituent unit (a2) containing a lactone-containing cyclic group, a -SO2- containing cyclic group or a carbonate-containing cyclic group; a constituent unit (a3) ​​containing a polar group-containing aliphatic hydrocarbon group; a constituent unit (a4) containing an acid-undissolvable aliphatic cyclic group; and a constituent unit (st) derived from styrene or a styrene derivative.

[0215] For the constituent unit (a10):

[0216] The constituent unit (a10) is a constituent unit represented by the following general formula (a10-1).

[0217] [Chemical Formula 25]

[0218]

[0219] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. Ya x1 Silver is a single bond or a divalent connector. Wa x1 is an aromatic hydrocarbon group that may have substituents. ax1 is an integer greater than or equal to 1.

[0220] In the above formula (a10-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide having 1 to 5 carbon atoms.

[0221] The alkyl group having 1 to 5 carbon atoms in R is preferably a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms, and specifically, examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, etc.

[0222] The alkyl halide group having 1 to 5 carbon atoms in R 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. As for the halogen atoms, fluorine atoms are particularly preferred.

[0223] As for R, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms is preferred, and for 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 methyl group is particularly preferred.

[0224] In the above equation (a10-1), Ya x1 It is a single bond or a two-linked connector.

[0225] Among the above chemical formulas, Ya x1The divalent linker in this case is not particularly limited, but may include a divalent hydrocarbon group having a substituent, a divalent linker containing a heteroatom, etc., as preferred examples.

[0226] · Divalent hydrocarbon groups that may have substituents:

[0227] Ya x1 In the case of a divalent hydrocarbon group that may have this substituent, the hydrocarbon group may be an aliphatic hydrocarbon or an aromatic hydrocarbon.

[0228] ·· Ya x1 Aliphatic hydrocarbon groups in

[0229] An aliphatic hydrocarbon group refers to a hydrocarbon group that does not have aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is generally preferred to be saturated.

[0230] Examples of the above-mentioned aliphatic hydrocarbon groups include straight-chain or branched-chain aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups containing a ring in their structure.

[0231] ··· Straight-chain or branched-chain aliphatic hydrocarbon groups

[0232] The straight-chain 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.

[0233] As for the straight-chain aliphatic hydrocarbon groups, straight-chain alkylene groups are preferred, and specifically, examples include methylene groups [-CH2-], ethylene groups [-(CH2)2-], trimethylene groups [-(CH2)3-], tetramethylene groups [-(CH2)4-], pentamethylene groups [-(CH2)5-], etc.

[0234] The branched chain type 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.

[0235] As for branched-chain aliphatic hydrocarbon groups, branched-chain alkylene groups are preferred, and specifically, alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-; alkylalkylene groups such as -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2-; and alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2CH2-. As for the alkyl group in the alkylalkylene group, a straight-chain alkyl group having 1 to 5 carbon atoms is preferred.

[0236] The above straight-chain or branched-chain aliphatic hydrocarbon group may or may not have a substituent. Examples of such substituents include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, a carbonyl group, etc.

[0237] ··· Aliphatic hydrocarbon groups containing a ring in their structure

[0238] Examples of aliphatic hydrocarbon groups containing a ring in the structure include a cyclic aliphatic hydrocarbon group that may include a substituent containing a heteroatom in the ring structure (a group in which two hydrogen atoms have been removed from an aliphatic hydrocarbon ring), a group in which the cyclic aliphatic hydrocarbon group is bonded to the end of a straight-chain or branched-chain aliphatic hydrocarbon group, and a group in which the cyclic aliphatic hydrocarbon group is interposed in the middle of a straight-chain or branched-chain aliphatic hydrocarbon group. Examples of the straight-chain or branched-chain aliphatic hydrocarbon group may be the same as those above.

[0239] The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms.

[0240] The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. As for the monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferred. The monocycloalkane is preferably one having 3 to 6 carbon atoms, and specifically examples include cyclopentane and cyclohexane. As for the polycyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a polycycloalkane is preferred, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, and specifically examples include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane.

[0241] The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, etc.

[0242] As for the alkyl group as the above substituent, an alkyl group having 1 to 5 carbon atoms is preferred, and more preferably a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group.

[0243] As for the alkoxy group as the above substituent, an alkoxy group having 1 to 5 carbon atoms is preferred, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group are more preferred, and a methoxy group and an ethoxy group are even more preferred.

[0244] As the halogen atom serving as the above substituent, a fluorine atom is preferred.

[0245] Examples of alkyl halide groups as the above substituents include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with the halogen atoms.

[0246] In the cyclic aliphatic hydrocarbon group, some of the carbon atoms constituting the ring structure may be substituted with substituents containing heteroatoms. Preferably, the substituents containing heteroatoms are -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0247] ·· Ya x1 Aromatic hydrocarbons in

[0248] The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.

[0249] 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. However, the number of carbon atoms does not include the number of carbon atoms in the substituents.

[0250] Specifically, aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic complex rings in which some of the carbon atoms constituting the aromatic hydrocarbon rings are substituted with heteroatoms. Examples of heteroatoms in aromatic complex rings include oxygen atoms, sulfur atoms, and nitrogen atoms. Specifically, aromatic complex rings include pyridine rings and thiophene rings.

[0251] Specifically, aromatic hydrocarbon groups include a group (arylene group or heteroarylene group) from which two hydrogen atoms have been removed from the aromatic hydrocarbon ring or aromatic complex ring; a group from which two hydrogen atoms have been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and a group in which one hydrogen atom of the group (aryl group or heteroaryl group) from which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic complex ring is substituted with an alkylene group (e.g., a group in which one additional hydrogen atom has been removed from an aryl alkyl group such as a benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms of 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.

[0252] The above aromatic hydrocarbon group may have a hydrogen atom of the said aromatic hydrocarbon group substituted with a substituent. For example, a hydrogen atom bonded to the aromatic ring in the said aromatic hydrocarbon group may be substituted with a substituent. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, etc.

[0253] As for the alkyl group as the above substituent, an alkyl group having 1 to 5 carbon atoms is preferred, and more preferably a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group.

[0254] Examples of the alkoxy group, halogen atom, and alkyl halide group as the above substituents include those that substitute for a hydrogen atom of the cyclic aliphatic hydrocarbon group.

[0255] · Divalent linker containing heteroatoms:

[0256] Ya x1 In the case of a divalent linker containing this heteroatom, preferred as the linker are -O-, -C(=O)-O-, -OC(=O)-, -C(=O)-, -OC(=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 -OY 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 -, -[Y 21 -C(=O)-O] m" -Y 22 -, -Y 21 -OC(=O)-Y 22 - or -Y 21 -S(=O)2-OY 22 - represented by [among the formulas, Y 21 and Y 22 Examples include: , which are divalent hydrocarbon groups that may each independently have a substituent, O, which is an oxygen atom, and m", which is an integer from 0 to 3.

[0257] In the case where the divalent linker containing the above heteroatom is -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, or -NH-C(=NH)-, the H may be substituted with a substituent such as an alkyl group or an acyl group. 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.

[0258] General formula -Y 21 -OY 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 -, -[Y 21 -C(=O)-O] m" -Y 22 -, -Y 21 -OC(=O)-Y 22 - or -Y 21 -S(=O)2-OY 22 - Middle, Y 21 and Y 22 Each is a divalent hydrocarbon group that may have a substituent, independently. As for the divalent hydrocarbon group, the above Ya x1 Examples include the same as the (a divalent hydrocarbon group that may have a substituent) exemplified in the explanation as a linker in divalent.

[0259] Y 21 A straight-chain aliphatic hydrocarbon group is preferred, a straight-chain alkylene group is more preferred, a straight-chain alkylene group having 1 to 5 carbon atoms is even more preferred, and a methylene group or an ethylene group is particularly preferred.

[0260] Y 22The aliphatic hydrocarbon group is preferably a straight-chain or branched-chain type, and more preferably a methylene group, an ethylene group, or an alkylmethylene group. Among the alkylmethylene groups, the alkyl group is preferably a straight-chain type alkyl group having 1 to 5 carbon atoms, more preferably a straight-chain type alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.

[0261] Formula -[Y 21 -C(=O)-O] m" -Y 22 - In the expression represented by -, m" is an integer from 0 to 3, preferably an integer from 0 to 2, more preferably 0 or 1, and particularly preferably 1. In short, Equation -[Y 21 -C(=O)-O] m" -Y 22 - As represented by -, the equation -Y 21 -C(=O)-OY 22 - It is particularly desirable to represent it as such. Among them, the formula -(CH2) a' -C(=O)-O-(CH2) b' - It is preferable to represent it as such. Among the expressions, 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.

[0262] Among the above, Ya x1 It is preferable that the bond be a single bond, an ester bond [-C(=O)-O-, -OC(=O)-], an ether bond (-O-), a straight-chain or branched-chain alkylene group, or a combination thereof, and a single bond or an ester bond [-C(=O)-O-, -OC(=O)-] is more preferable.

[0263] In the above equation (a10-1), Wax1 It is an aromatic hydrocarbon group that may have substituents.

[0264] Wa x1 As for the aromatic hydrocarbon group in , from an aromatic ring that may have a substituent (n ax1 + 1) A group with hydrogen atoms removed may be used. The aromatic ring here is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and may be monocyclic or polycyclic. It is preferable that the number of carbon atoms in the aromatic ring be 5 to 30, more preferable that the number of carbon atoms be 5 to 20, even more preferable that the number of carbon atoms be 6 to 15, and particularly preferable that the number of carbon atoms be 6 to 12. Specifically, examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic complex rings in which some of the carbon atoms constituting the above aromatic hydrocarbon ring are substituted with heteroatoms. Examples of heteroatoms in the aromatic complex ring include oxygen atoms, sulfur atoms, nitrogen atoms, etc. Specifically, examples of aromatic complex rings include pyridine rings and thiophene rings.

[0265] Also, Wa x1 The aromatic hydrocarbon group in [the example] is from an aromatic compound containing an aromatic ring that may have two or more substituents (e.g., biphenyl, fluorene, etc.) (n ax1 + 1) Can be heard of a prayer with 1 hydrogen atom removed.

[0266] Among the above, Wa x1 From, from benzene, naphthalene, anthracene, or biphenyl (n ax1 A group from which 1) hydrogen atoms have been removed is preferred, and from benzene or naphthalene (n ax1 A group from which 1) hydrogen atoms have been removed is more desirable, and from benzene (n ax1 + 1) A group with hydrogen atoms removed is more desirable.

[0267] Wa x1 The aromatic hydrocarbon group in [the example] may or may not have a substituent. Examples of the substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halide groups, etc. As for the alkyl groups, alkoxy groups, halogen atoms, and alkyl halide groups as the substituents, Ya x1 Examples of substituents for the cyclic aliphatic hydrocarbon group in [the example] may be the same as those exemplified. The substituent is preferably a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms, more preferably a straight-chain or branched-chain alkyl group having 1 to 3 carbon atoms, even more preferably an ethyl group or a methyl group, and particularly preferably a methyl group. Wa x1 It is preferable that the aromatic hydrocarbon group in this case does not have a substituent.

[0268] In the above equation (a10-1), n ax1 ...is an integer greater than or equal to 1, 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.

[0269] A specific example of the constituent unit (a10) represented by the above formula (a10-1) is shown below.

[0270] Among each of the following formulas, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0271] [Chemical Formula 26]

[0272]

[0273] [Chemical Formula 27]

[0274]

[0275] [Chemical Formula 28]

[0276]

[0277] (A1) The constituent unit (a10) of the component may be one type or two or more types.

[0278] When component (A1) has a constituent unit (a10), the proportion of the constituent unit (a10) in component (A1) is preferably 5 to 95 mol% with respect to the total sum of constituent units (100 mol%) constituting component (A1), more preferably 10 to 90 mol%, even more preferably 30 to 70 mol%, and particularly preferably 40 to 60 mol%.

[0279] By making the ratio of the constituent unit (a10) higher than the lower limit, it becomes easier to increase sensitivity. On the other hand, by making it lower than the upper limit, it becomes easier to balance with other constituent units.

[0280] For the constituent unit (a2):

[0281] (A1) The component may have, in addition to the constituent unit (a1), additionally a constituent unit (a2) comprising a lactone-containing cyclic group, a -SO2- containing cyclic group or a carbonate-containing cyclic group (except for those corresponding to constituent unit (a1)).

[0282] The lactone-containing cyclic group, -SO2- containing cyclic group, or carbonate-containing cyclic group of the constituent unit (a2) is effective in increasing the adhesion of the resist film to the substrate when the component (A1) is used to form the resist film. In addition, by having the constituent unit (a2), the lithography characteristics are improved through effects such as, for example, appropriately adjusting the acid diffusion length, increasing the adhesion of the resist film to the substrate, and appropriately adjusting the solubility during development.

[0283] "Lactone-containing cyclic group" refers to a cyclic group containing a ring (lactone ring) containing -OC(=O)- in its ring backbone. 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 additional 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.

[0284] The lactone-containing cyclic group in the constituent unit (a2) is not particularly limited and any one can be used. Specifically, groups represented by the following general formulas (a2-r-1) to (a2-r-7), respectively, can be used.

[0285] [Chemical Formula 29]

[0286]

[0287] [During the meal, Ra' 21 Each is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, an alkyl halide 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, a carbonate-containing cyclic group, or a -SO2- containing cyclic group; A" is an alkylene group having 1 to 5 carbon atoms, an oxygen atom, or a sulfur atom, which may contain an oxygen atom (-O-) or a sulfur atom (-S-); n' is an integer from 0 to 2; and m' is 0 or 1.

[0288] Among the above general formulas (a2-r-1) ~ (a2-r-7), Ra' 21As for the alkyl group, an alkyl group having 1 to 6 carbon atoms is preferred. The alkyl group is preferably of the straight-chain or branched-chain type. Specifically, examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a hexyl group, etc. Among these, a methyl group or an ethyl group is preferred, and a methyl group is particularly preferred.

[0289] Ra' 21 As for the alkoxy group in the above, an alkoxy group having 1 to 6 carbon atoms is preferred. The alkoxy group is preferably of the straight chain type or the branched chain type. Specifically, the above Ra' 21 Examples of alkyl groups include the alkyl group exemplified above and a group in which an oxygen atom (-O-) is connected.

[0290] Ra' 21 As for the halogen atom, a fluorine atom is preferred.

[0291] Ra' 21 As for the alkyl halide group in the above, Ra' 21 Examples include a group in which some or all of the hydrogen atoms of the alkyl group are substituted with the halogen atom. As for the alkyl halide group, a fluorinated alkyl group is preferred, and a perfluoroalkyl group is particularly preferred.

[0292] Ra' 21 In -COOR" and -OC(=O)R", R" is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or a -SO2- containing cyclic group.

[0293] The alkyl group in R" may be any of a straight chain type, a branched chain type, or a cyclic type, and the number of carbon atoms is preferably 1 to 15.

[0294] When R" is a straight-chain or branched-chain alkyl group, it is preferable that the number of carbon atoms is 1 to 10, more preferable that the number of carbon atoms is 1 to 5, and particularly preferable that it is a methyl group or an ethyl group.

[0295] When R" is a cyclic alkyl group, it is preferable that the number of carbon atoms be 3 to 15, more preferable that the number of carbon atoms be 4 to 12, and most preferable that the number of carbon atoms be 5 to 10. Specifically, examples include a group obtained by removing one or more hydrogen atoms from a monocycloalkane that may or may not be substituted with a fluorine atom or a fluorinated alkyl group; a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as a bicycloalkane, tricycloalkane, or tetracycloalkane. More specifically, examples include a group obtained by removing one or more hydrogen atoms from a monocycloalkane such as cyclopentane or cyclohexane; a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane.

[0296] Examples of lactone-containing cyclic groups in R" include those identical to the groups represented by the general formulas (a2-r-1) to (a2-r-7), respectively.

[0297] The carbonate-containing cyclic group in R" is identical to the carbonate-containing cyclic group described later, and specifically, groups represented by the general formulas (ax3-r-1) to (ax3-r-3), respectively.

[0298] The -SO2- containing cyclic groups in R" are the same as the -SO2- containing cyclic groups described later, and specifically, groups represented by general formulas (a5-r-1) to (a5-r-4), respectively.

[0299] Ra' 21In the case of the hydroxyalkyl group, it is preferable that the number of carbon atoms is 1 to 6, and specifically, the above Ra' 21 Examples include groups in which at least one hydrogen atom of the alkyl group is substituted with a hydroxyl group.

[0300] Ra' 21 Among the above, it is preferable that each be independently a hydrogen atom or a cyano group.

[0301] Among the general formulas (a2-r-2), (a2-r-3), and (a2-r-5) above, the alkylene group having 1 to 5 carbon atoms in A" is preferably a straight-chain or branched-chain alkylene group, and examples include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, etc. When the alkylene group includes an oxygen atom or a sulfur atom, specific examples include a group in which -O- or -S- is interposed between the terminals or carbon atoms of the alkylene group, and examples include -O-CH2-, -CH2-O-CH2-, -S-CH2-, -CH2-S-CH2-, etc. As for A", an alkylene group having 1 to 5 carbon atoms or -O- is preferred, an alkylene group having 1 to 5 carbon atoms is more preferred, and a methylene group is most preferred.

[0302] Specific examples of groups represented by the general formulas (a2-r-1) to (a2-r-7) are given below.

[0303] [Chemical Formula 30]

[0304]

[0305] [Chemical Formula 31]

[0306]

[0307] "-SO2- containing cyclic group" refers to a cyclic group containing a ring containing -SO2- within its ring skeleton, and specifically, it is a cyclic group in which a sulfur atom (S) in -SO2- forms part of the ring skeleton of the cyclic group. The ring containing -SO2- within the ring skeleton is counted as the first ring, and if it is only that ring, it is called a monocyclic group, and if it has additional ring structures, it is called a polycyclic group regardless of the structure. A -SO2- containing cyclic group may be a monocyclic group or a polycyclic group.

[0308] It is preferable that the cyclic group containing -SO2- be, in particular, a cyclic group containing -O-SO2- in the ring backbone, that is, a cyclic group containing a sultone ring in which -OS- in -O-SO2- forms part of the ring backbone.

[0309] As cyclic groups containing -SO2-, more specifically, groups represented by the following general formulas (a5-r-1) to (a5-r-4) can be cited.

[0310] [Chemical Formula 32]

[0311]

[0312] [During the meal, Ra' 51 Each is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, an alkyl halide 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, a carbonate-containing cyclic group, or a -SO2- containing cyclic group; A" is an alkylene group having 1 to 5 carbon atoms, an oxygen atom, or a sulfur atom, which may contain an oxygen atom or a sulfur atom, and n' is an integer from 0 to 2.

[0313] Among the above general formulas (a5-r-1) to (a5-r-2), A" is identical to A" in the above general formulas (a2-r-2), (a2-r-3), and (a2-r-5).

[0314] Ra' 51 In the above, the alkyl group, alkoxy group, halogen atom, alkyl halide group, -COOR", -OC(=O)R", and hydroxyalkyl group are each Ra' in the above general formulas (a2-r-1) to (a2-r-7). 21 The same as those exemplified in the explanation can be cited.

[0315] Specific examples of groups represented by the general formulas (a5-r-1) to (a5-r-4), respectively, are given below. In the formulas, "Ac" represents an acetyl group.

[0316] [Chemical Formula 33]

[0317]

[0318] [Chemical Formula 34]

[0319]

[0320] [Chemical Formula 35]

[0321]

[0322] "Carbonate-containing cyclic group" refers to a cyclic group containing a ring (carbonate ring) containing -OC(=O)-O- in its ring backbone. The carbonate ring is counted as the first ring; if it consists only of carbonate rings, it is called a monocyclic group, and if it has additional ring structures, it is called a polycyclic group regardless of the structure. A carbonate-containing cyclic group may be a monocyclic group or a polycyclic group.

[0323] As for the cyclic group containing a carbonate ring, any one can be used without being particularly limited. Specifically, groups represented by the following general formulas (ax3-r-1) to (ax3-r-3), respectively, can be used.

[0324] [Chemical Formula 36]

[0325]

[0326] [During the meal, Ra' x31 Each is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, an alkyl halide 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, a carbonate-containing cyclic group, or a -SO2- containing cyclic group; A" is an alkylene group having 1 to 5 carbon atoms, an oxygen atom, or a sulfur atom, which may contain an oxygen atom or a sulfur atom; p' is an integer from 0 to 3; and q' is 0 or 1.

[0327] Among the above general formulas (ax3-r-2) to (ax3-r-3), A" is identical to A" in the above general formulas (a2-r-2), (a2-r-3), and (a2-r-5).

[0328] Ra' x31 In the above, the alkyl group, alkoxy group, halogen atom, alkyl halide group, -COOR", -OC(=O)R", and hydroxyalkyl group are each Ra' in the above general formulas (a2-r-1) to (a2-r-7). 21 The same as those exemplified in the explanation can be cited.

[0329] Specific examples of groups represented by the general formulas (ax3-r-1) to (ax3-r-3) are given below.

[0330] [Chemical Formula 37]

[0331]

[0332] Among the constituent units (a2), a constituent unit derived from an acrylic acid ester, wherein the hydrogen atom bonded to the carbon atom at the α position may be substituted with a substituent, is preferred.

[0333] It is preferable that such a constituent unit (a2) be a constituent unit represented by the following general formula (a2-1).

[0334] [Chemical Formula 38]

[0335]

[0336] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. Ya 21 is a single bond or a divalent connector. La 21 is -O-, -COO-, -CON(R')-, -OCO-, -CONHCO-, or -CONHCS-, where R' represents a hydrogen atom or a methyl group. However, La 21 In this case, Ya 21 -CO- does not become Ra 21 It is a lactone-containing cyclic group, a carbonate-containing cyclic group, or a -SO2- containing cyclic group.

[0337] In the above formula (a2-1), R is the same as above. As for R, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms is preferred, and a hydrogen atom or a methyl group is particularly preferred for industrial availability.

[0338] In the above equation (a2-1), Ya 21 The divalent linker in the above is not particularly limited, but preferably includes a divalent hydrocarbon group that may have a substituent, a divalent linker containing a heteroatom, etc.

[0339] · Divalent hydrocarbon groups that may have substituents:

[0340] Ya 21 In the case of a divalent hydrocarbon group that may have this substituent, the hydrocarbon group may be an aliphatic hydrocarbon or an aromatic hydrocarbon.

[0341] ·· Ya 21 Aliphatic hydrocarbon groups in

[0342] An aliphatic hydrocarbon group refers to a hydrocarbon group that does not have aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is generally preferred to be saturated.

[0343] Examples of the above-mentioned aliphatic hydrocarbon groups include straight-chain or branched-chain aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups containing a ring in their structure.

[0344] ··· Straight-chain or branched-chain aliphatic hydrocarbon groups

[0345] The straight-chain 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.

[0346] As for the straight-chain aliphatic hydrocarbon groups, straight-chain alkylene groups are preferred, and specifically, examples include methylene groups [-CH2-], ethylene groups [-(CH2)2-], trimethylene groups [-(CH2)3-], tetramethylene groups [-(CH2)4-], pentamethylene groups [-(CH2)5-], etc.

[0347] The branched chain type 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.

[0348] As for branched-chain aliphatic hydrocarbon groups, branched-chain alkylene groups are preferred, and specifically, alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-; alkylalkylene groups such as -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2-; and alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2CH2-. As for the alkyl group in the alkylalkylene group, a straight-chain alkyl group having 1 to 5 carbon atoms is preferred.

[0349] The above straight-chain or branched-chain aliphatic hydrocarbon group may or may not have a substituent. Examples of such substituents include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, a carbonyl group, etc.

[0350] ··· Aliphatic hydrocarbon groups containing a ring in their structure

[0351] Examples of aliphatic hydrocarbon groups containing a ring in the structure include a cyclic aliphatic hydrocarbon group that may include a substituent containing a heteroatom in the ring structure (a group in which two hydrogen atoms have been removed from an aliphatic hydrocarbon ring), a group in which the cyclic aliphatic hydrocarbon group is bonded to the end of a straight-chain or branched-chain aliphatic hydrocarbon group, and a group in which the cyclic aliphatic hydrocarbon group is interposed in the middle of a straight-chain or branched-chain aliphatic hydrocarbon group. Examples of the straight-chain or branched-chain aliphatic hydrocarbon group may be the same as those above.

[0352] The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms.

[0353] The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. As for the monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferred. The monocycloalkane is preferably one having 3 to 6 carbon atoms, and specifically examples include cyclopentane and cyclohexane. As for the polycyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a polycycloalkane is preferred, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, and specifically examples include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane.

[0354] The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, etc.

[0355] As for the alkyl group as the above substituent, an alkyl group having 1 to 5 carbon atoms is preferred, and more preferably a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group.

[0356] As for the alkoxy group as the above substituent, an alkoxy group having 1 to 5 carbon atoms is preferred, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group are more preferred, and a methoxy group and an ethoxy group are even more preferred.

[0357] As the halogen atom serving as the above substituent, a fluorine atom is preferred.

[0358] Examples of alkyl halide groups as the above substituents include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with the halogen atoms.

[0359] In the cyclic aliphatic hydrocarbon group, some of the carbon atoms constituting the ring structure may be substituted with substituents containing heteroatoms. Preferably, the substituents containing heteroatoms are -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0360] ·· Ya 21 Aromatic hydrocarbons in

[0361] The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.

[0362] 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. However, the number of carbon atoms does not include the number of carbon atoms in the substituents.

[0363] Specifically, aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic complex rings in which some of the carbon atoms constituting the aromatic hydrocarbon rings are substituted with heteroatoms. Examples of heteroatoms in aromatic complex rings include oxygen atoms, sulfur atoms, and nitrogen atoms. Specifically, aromatic complex rings include pyridine rings and thiophene rings.

[0364] Specifically, aromatic hydrocarbon groups include a group (arylene group or heteroarylene group) from which two hydrogen atoms have been removed from the aromatic hydrocarbon ring or aromatic complex ring; a group from which two hydrogen atoms have been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and a group in which one hydrogen atom of the group (aryl group or heteroaryl group) from which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic complex ring is substituted with an alkylene group (e.g., a group in which one additional hydrogen atom has been removed from an aryl alkyl group such as a benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms of 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.

[0365] The above aromatic hydrocarbon group may have a hydrogen atom of the said aromatic hydrocarbon group substituted with a substituent. For example, a hydrogen atom bonded to the aromatic ring in the said aromatic hydrocarbon group may be substituted with a substituent. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, etc.

[0366] As for the alkyl group as the above substituent, an alkyl group having 1 to 5 carbon atoms is preferred, and more preferably a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group.

[0367] Examples of the alkoxy group, halogen atom, and alkyl halide group as the above substituents include those that substitute for a hydrogen atom of the cyclic aliphatic hydrocarbon group.

[0368] · Divalent linker containing heteroatoms:

[0369] Ya 21In the case of a divalent linker containing this heteroatom, preferred as the linker are -O-, -C(=O)-O-, -OC(=O)-, -C(=O)-, -OC(=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 -OY 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 -, -[Y 21 -C(=O)-O] m" -Y 22 -, -Y 21 -OC(=O)-Y 22 - or -Y 21 -S(=O)2-OY 22 - represented by [among the formulas, Y 21 and Y 22 Examples include: , which are divalent hydrocarbon groups that may each independently have a substituent, O, which is an oxygen atom, and m", which is an integer from 0 to 3.

[0370] In the case where the divalent linker containing the above heteroatom is -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, or -NH-C(=NH)-, the H may be substituted with a substituent such as an alkyl group or an acyl group. 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.

[0371] General formula -Y 21 -OY 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 -, -[Y 21 -C(=O)-O] m" -Y 22 -, -Y21 -OC(=O)-Y 22 - or -Y 21 -S(=O)2-OY 22 - Middle, Y 21 and Y 22 Each is a divalent hydrocarbon group that may have a substituent, independently. As for the divalent hydrocarbon group, the above Ya 21 Examples include the same as the (a divalent hydrocarbon group that may have a substituent) exemplified in the explanation as a linker in divalent.

[0372] Y 21 A straight-chain aliphatic hydrocarbon group is preferred, a straight-chain alkylene group is more preferred, a straight-chain alkylene group having 1 to 5 carbon atoms is even more preferred, and a methylene group or an ethylene group is particularly preferred.

[0373] Y 22 The aliphatic hydrocarbon group is preferably a straight-chain or branched-chain type, and more preferably a methylene group, an ethylene group, or an alkylmethylene group. Among the alkylmethylene groups, the alkyl group is preferably a straight-chain type alkyl group having 1 to 5 carbon atoms, more preferably a straight-chain type alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.

[0374] Formula -[Y 21 -C(=O)-O] m" -Y 22 - In the expression represented by -, m" is an integer from 0 to 3, preferably an integer from 0 to 2, more preferably 0 or 1, and particularly preferably 1. In short, Equation -[Y 21 -C(=O)-O] m" -Y 22 - As represented by -, the equation -Y 21 -C(=O)-OY 22 - It is particularly desirable to represent it as such. Among them, the formula -(CH2) a' -C(=O)-O-(CH2) b'- It is preferable to represent it as such. Among the expressions, 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.

[0375] Among the above, Ya 21 It is preferable that the group be a single bond, an ester bond [-C(=O)-O-], an ether bond (-O-), a straight-chain or branched-chain alkylene group, or a combination thereof.

[0376] In the above equation (a2-1), Ra 21 It is a lactone-containing cyclic group, a -SO2- containing cyclic group, or a carbonate-containing cyclic group.

[0377] Ra 21 In this case, the lactone-containing cyclic group, the -SO2- containing cyclic group, and the carbonate-containing cyclic group can preferably be the groups represented by the aforementioned general formulas (a2-r-1) to (a2-r-7), the groups represented by the general formulas (a5-r-1) to (a5-r-4), and the groups represented by the general formulas (ax3-r-1) to (ax3-r-3).

[0378] Among these, a lactone-containing cyclic group or a -SO2- containing cyclic group is preferred, a group represented by the general formulas (a2-r-1), (a2-r-2), (a2-r-6), or (a5-r-1), respectively, is more preferred, and a group represented by the general formulas (a2-r-2) or (a5-r-1), respectively, is even more preferred. Specifically, any group represented by the chemical formulas (r-lc-1-1) to (r-lc-1-7), (r-lc-2-1) to (r-lc-2-18), (r-lc-6-1), (r-sl-1-1), and (r-sl-1-18) is preferred, any group represented by the chemical formulas (r-lc-2-1) to (r-lc-2-18) and (r-sl-1-1) is more preferred, and any group represented by the chemical formulas (r-lc-2-1), (r-lc-2-12), and (r-sl-1-1) is even more preferred.

[0379] (A1) The constituent unit (a2) of the component may be one type or two or more types.

[0380] When component (A1) has a constituent unit (a2), the ratio of the constituent unit (a2) is preferably 5 to 60 mol% with respect to the total sum (100 mol%) of all constituent units constituting component (A1), more preferably 10 to 60 mol%, even more preferably 20 to 60 mol%, and particularly preferably 30 to 60 mol%.

[0381] If the ratio of the constituent unit (a2) is set above a desirable lower limit, the effect of including the constituent unit (a2) is sufficiently obtained due to the aforementioned effect, and if it is below an upper limit, a balance with other constituent units can be achieved, and various lithography characteristics are improved.

[0382] For the constituent unit (a3):

[0383] (A1) The component may have, in addition to the constituent unit (a1), a constituent unit (a3) ​​containing a polar group-containing aliphatic hydrocarbon group (except for those corresponding to constituent unit (a1) or constituent unit (a2)). By having the constituent unit (a3) ​​of the (A1) component, the hydrophilicity of the (A) component is increased, contributing to the improvement of resolving power. Also, the acid diffusion length can be appropriately adjusted.

[0384] Examples of polar groups include hydroxyl groups, cyano groups, carboxyl groups, and hydroxyalkyl groups in which some of the hydrogen atoms of an alkyl group are substituted with fluorine atoms, and hydroxyl groups are particularly preferred.

[0385] Examples of aliphatic hydrocarbon groups include straight-chain or branched-chain hydrocarbon groups having 1 to 10 carbon atoms (preferably alkylene groups) or cyclic aliphatic hydrocarbon groups (cyclic groups). The cyclic group may be a monocyclic group or a polycyclic group, and, for example, in a resin for a resist composition for an ArF excimer laser, it can be appropriately selected and used from among those proposed in many ways.

[0386] When the cyclic group is a monocyclic group, it is more preferable that the number of carbon atoms be 3 to 10. Among these, a constituent unit derived from an acrylic acid ester containing an aliphatic monocyclic group containing a hydroxyalkyl group in which some of the hydrogen atoms of a hydroxyl group, cyano group, carboxyl group, or alkyl group are substituted with fluorine atoms is more preferable. Examples of such monocyclic groups include a group obtained by removing two or more hydrogen atoms from a monocycloalkane. Specifically, examples include a group obtained by removing two or more hydrogen atoms from a monocycloalkane such as cyclopentane, cyclohexane, or cyclooctane. Among these monocyclic groups, a group obtained by removing two or more hydrogen atoms from cyclopentane or a group obtained by removing two or more hydrogen atoms from cyclohexane is industrially preferred.

[0387] When the cyclic group is a polycyclic group, it is more preferable that the number of carbon atoms in the polycyclic group be 7 to 30. Among these, a constituent unit derived from an acrylic acid ester containing an aliphatic polycyclic group containing a hydroxyalkyl group in which some of the hydrogen atoms of a hydroxyl group, cyano group, carboxyl group, or alkyl group are substituted with fluorine atoms is more preferable. Examples of the polycyclic group include a group obtained by removing two or more hydrogen atoms from bicycloalkanes, tricycloalkanes, tetracycloalkanes, etc. Specifically, examples include a group obtained by removing two or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. Among these polycyclic groups, a group obtained by removing two or more hydrogen atoms from adamantane, a group obtained by removing two or more hydrogen atoms from norbornane, and a group obtained by removing two or more hydrogen atoms from tetracyclododecane is industrially preferred.

[0388] As for the constituent unit (a3), any one is not particularly limited as long as it contains a polar group-containing aliphatic hydrocarbon group.

[0389] As for the constituent unit (a3), it is preferable to have a constituent unit derived from an acrylic acid ester in which a hydrogen atom bonded to a carbon atom at the α position may be substituted with a substituent, and the constituent unit containing a polar group-containing aliphatic hydrocarbon group.

[0390] As for the constituent unit (a3), when the hydrocarbon group in the polar group-containing aliphatic hydrocarbon group is a straight-chain or branched-chain hydrocarbon group having 1 to 10 carbon atoms, a constituent unit derived from hydroxyethyl ester of acrylic acid is preferred.

[0391] In addition, regarding the constituent unit (a3), when the hydrocarbon group in the polar group-containing aliphatic hydrocarbon group is a polycyclic group, the constituent unit represented by the following formula (a3-1), the constituent unit represented by the formula (a3-2), and the constituent unit represented by the formula (a3-3) may be preferred; when it is a monocyclic group, the constituent unit represented by the formula (a3-4) may be preferred.

[0392] [Chemical Formula 39]

[0393]

[0394] [In the equation, R is the same as above, j is an integer from 1 to 3, k is an integer from 1 to 3, t' is an integer from 1 to 3, l is an integer from 0 to 5, and s is an integer from 1 to 3.]

[0395] In formula (a3-1), j is preferably 1 or 2, and more preferably 1. When j is 2, it is preferable that the hydroxyl group is bonded to the 3rd and 5th positions of the adamantyl group. When j is 1, it is preferable that the hydroxyl group is bonded to the 3rd position of the adamantyl group.

[0396] It is preferable that j is 1, and it is particularly preferable that the hydroxyl group is bonded to the 3rd position of the adamantyl group.

[0397] In formula (a3-2), it is preferable that k is 1. It is preferable that the cyano group is bonded to the 5th or 6th position of the norbornyl group.

[0398] In formula (a3-3), t' is preferably 1. l is preferably 1. s is preferably 1. In these, a 2-norbornyl group or a 3-norbornyl group is preferably bonded to the terminal of the carboxyl group of the acrylic acid. The fluorinated alkyl alcohol is preferably bonded to the 5 or 6 position of the norbornyl group.

[0399] In formula (a3-4), t' is preferably 1 or 2. l is preferably 0 or 1. s is preferably 1. The fluorinated alkyl alcohol is preferably bonded to the 3rd or 5th position of the cyclohexyl group.

[0400] (A1) The constituent unit (a3) ​​of the component may be one type or two or more types.

[0401] When component (A1) has a constituent unit (a3), the ratio of the constituent unit (a3) ​​is preferably 1 to 30 mol% with respect to the total sum (100 mol%) of all constituent units constituting the component (A1), more preferably 2 to 25 mol%, and even more preferably 5 to 20 mol%.

[0402] By making the ratio of the constituent unit (a3) ​​greater than or equal to a desirable lower limit, the effect of including the constituent unit (a3) ​​is sufficiently obtained due to the aforementioned effect, and if it is less than or equal to a desirable upper limit, a balance with other constituent units can be achieved, and various lithography characteristics are improved.

[0403] For the constituent unit (a4):

[0404] (A1) The component may have, in addition to the constituent unit (a1), additionally, a constituent unit (a4) containing an acid-undissolvable aliphatic cyclic group.

[0405] By having component (A1) a constituent unit (a4), the dry etching resistance of the formed resist pattern is improved. Also, the hydrophobicity of component (A) is increased. The improvement in hydrophobicity contributes to the improvement of resolution, resist pattern shape, etc., especially in the case of the solvent development process.

[0406] The “acid-nondissociating cyclic group” in the constituent unit (a4) is a cyclic group that remains in the constituent unit without dissociating when acid is generated in the resist composition by exposure (for example, when acid is generated from the constituent unit that generates acid by exposure or from component (B)).

[0407] As for the constituent unit (a4), for example, a constituent unit derived from an acrylic acid ester containing an acid-undissolvable aliphatic cyclic group is preferred. The cyclic group may be one of many that have been conventionally known as being used in the resin component of a resist composition for an ArF excimer laser, a KrF excimer laser (preferably for an ArF excimer laser), etc.

[0408] The cyclic group is preferably at least one selected from tricyclodecyl, adamantyl, tetracyclododecyl, isobornyl, and norbornyl groups, in that it is readily available industrially. These polycyclic groups may have a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms as a substituent.

[0409] As a constituent unit (a4), specifically, constituent units represented by the following general formulas (a4-1) to (a4-7) can be exemplified.

[0410] [Chemical Formula 40]

[0411]

[0412] [In the middle of the meal, R α is the same as above.]

[0413] (A1) The constituent unit (a4) of the component may be one type or two or more types.

[0414] When component (A1) has a constituent unit (a4), the ratio of the constituent unit (a4) is preferably 1 to 40 mol% with respect to the total sum (100 mol%) of all constituent units constituting the component (A1), and more preferably 5 to 20 mol%.

[0415] By making the ratio of the constituent unit (a4) greater than or equal to a desirable lower limit, the effect of including the constituent unit (a4) is sufficiently obtained, while by making it less than or equal to a desirable upper limit, it becomes easier to balance with other constituent units.

[0416] For the constituent unit (st):

[0417] The constituent unit (st) is a constituent unit derived from styrene or a styrene derivative. "Constituent unit derived from styrene" means a constituent unit formed by the cleavage of an ethylenetic double bond of styrene. "Constituent unit derived from a styrene derivative" means a constituent unit formed by the cleavage of an ethylenetic double bond of a styrene derivative.

[0418] "Styrene derivative" means a compound in which at least some of the hydrogen atoms of styrene are substituted with substituents. Examples of styrene derivatives include those in which the hydrogen atom at the α position of styrene is substituted with a substituent, those in which one or more hydrogen atoms of the benzene ring of styrene are substituted with substituents, and those in which the hydrogen atom at the α position of styrene and one or more hydrogen atoms of the benzene ring are substituted with substituents.

[0419] Substituents that substitute the hydrogen atom at the α position of styrene include alkyl groups having 1 to 5 carbon atoms or alkyl halide groups having 1 to 5 carbon atoms.

[0420] The above alkyl group having 1 to 5 carbon atoms is preferably a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms, and specifically, examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, etc.

[0421] The above alkyl halide 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. Among the halogen atoms, fluorine atoms are particularly preferred.

[0422] As a substituent for the hydrogen atom at the α position of styrene, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms is preferred, an alkyl group having 1 to 3 carbon atoms or a fluorinated alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group is even more preferred due to industrial availability.

[0423] Substituents that substitute for hydrogen atoms of the benzene ring of styrene include, for example, alkyl groups, alkoxy groups, halogen atoms, alkyl halide groups, etc.

[0424] As for the alkyl group as the above substituent, an alkyl group having 1 to 5 carbon atoms is preferred, and more preferably a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group.

[0425] As for the alkoxy group as the above substituent, an alkoxy group having 1 to 5 carbon atoms is preferred, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group are more preferred, and a methoxy group and an ethoxy group are even more preferred.

[0426] As the halogen atom serving as the above substituent, a fluorine atom is preferred.

[0427] Examples of alkyl halide groups as the above substituents include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with the halogen atoms.

[0428] As a substituent for a hydrogen atom of the benzene ring of styrene, an alkyl group having 1 to 5 carbon atoms is preferred, a methyl group or an ethyl group is more preferred, and a methyl group is even more preferred.

[0429] As for the constituent unit (st), it is preferable to have a constituent unit derived from styrene, or a constituent unit derived from a styrene derivative in which a hydrogen atom at the α position of styrene is substituted with an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms; more preferable to have a constituent unit derived from styrene, or a constituent unit derived from a styrene derivative in which a hydrogen atom at the α position of styrene is substituted with a methyl group; and even more preferable to have a constituent unit derived from styrene.

[0430] (A1) The constituent unit (st) of the component may be one type or two or more types.

[0431] (A1) When a component has a constituent unit (st), the ratio of the constituent unit (st) is preferably 1 to 30 mol% with respect to the total sum (100 mol%) of the constituent units of the (A1) component, and more preferably 3 to 20 mol%.

[0432] The (A1) component contained in the resist composition may be used alone or in combination with two or more types.

[0433] In the resist composition of the present embodiment, the (A1) component may be a polymer compound having a repeating structure of a constituent unit (a1), and preferably a polymer compound having a repeating structure of a constituent unit (a1) and a constituent unit (a10).

[0434] (A1) Among the above, a polymer compound consisting of a repeating structure of a constituent unit (a1) and a constituent unit (a10) can be preferably cited as a component.

[0435] In a polymer compound having a repeating structure of a constituent unit (a1) and a constituent unit (a10), the proportion of the constituent unit (a1) is preferably 10 to 90 mol% with respect to the total sum of all constituent units (100 mol%) constituting the polymer compound, more preferably 20 to 80 mol%, even more preferably 30 to 70 mol%, and particularly preferably 40 to 60 mol%.

[0436] In addition, the proportion of the constituent unit (a10) in the polymer compound is preferably 10 to 90 mol% with respect to the total sum of the constituent units (100 mol%) constituting the polymer compound, more preferably 20 to 80 mol%, even more preferably 30 to 70 mol%, and particularly preferably 40 to 60 mol%.

[0437] The molar ratio of the constituent unit (a1) and the constituent unit (a10) in the polymer compound (constituent unit (a1) : constituent unit (a10)) is preferably 2 : 8 : 8 : 2, more preferably 3 : 7 : 7 : 3, and even more preferably 4 : 6 : 6 : 4.

[0438] These (A1) components can be prepared by dissolving monomers that derive each constituent unit in a polymerization solvent and polymerizing them by adding a radical polymerization initiator, such as azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyronic acid (e.g., V-601).

[0439] Alternatively, such a (A1) component can be prepared by dissolving a monomer that induces a constituent unit (a1) and, if necessary, a monomer that induces a constituent unit other than (a1) (e.g., a constituent unit (a10)) in a polymerization solvent, adding a radical polymerization initiator as described above to the mixture to polymerize it, and then carrying out a deprotection reaction.

[0440] In addition, during polymerization, a chain transfer agent such as HS-CH2-CH2-CH2-C(CF3)2-OH may be used in combination to introduce a -C(CF3)2-OH group to the terminal. In this way, a copolymer in which a hydroxyalkyl group is introduced in which some of the hydrogen atoms of the alkyl group are substituted with fluorine atoms is effective for reducing development defects or LER (line edge roughness: uneven roughness of the line sidewall).

[0441] (A1) The weight average molecular weight (Mw) of the component (based on polystyrene equivalent by gel permeation chromatography (GPC)) is not particularly limited, but is preferably 1000 to 50000, more preferably 2000 to 30000, and even more preferably 3000 to 20000.

[0442] (A1) If the Mw of the component is below the upper limit of this range, it has sufficient solubility in the resist solvent to be used as a resist, and if it is above the lower limit of this range, it has good dry etching resistance and a good cross-sectional shape of the resist pattern.

[0443] (A1) The degree of dispersion (Mw / Mn) of the component is not particularly limited, but is preferably 1.0 to 4.0, more preferably 1.0 to 3.0, and particularly preferably 1.0 to 2.0. Also, Mn represents the number average molecular weight.

[0444] · (A2) Regarding the component

[0445] The resist composition of the present embodiment may use, as component (A), a base component whose solubility in a developer changes due to the action of an acid, which does not correspond to the above (A1) component (hereinafter referred to as “(A2) component”).

[0446] (A2) The component is not particularly limited and may be arbitrarily selected from a number of conventionally known components for chemically amplified resist compositions.

[0447] (A2) The component may be one type of high molecular weight compound or low molecular weight compound, or two or more types may be used in combination.

[0448] The proportion of component (A1) among component (A) is preferably 25 mass% or more with respect to the total mass of component (A), more preferably 50 mass% or more, even more preferably 75 mass% or more, and may be 100 mass%. If the proportion is 25 mass% or more, it is easy to form a resist pattern with excellent various lithography characteristics such as high sensitivity, resolution, and roughness improvement.

[0449] In the resist composition of the present embodiment, the content of component (A) can be adjusted according to the thickness of the resist film to be formed, etc.

[0450] <Acid-generating agent component (B)>

[0451] The resist composition of the present embodiment contains, in addition to component (A), an acid generating agent component (B) that generates acid upon exposure.

[0452] (B) The component is not particularly limited and any acid-generating agent that has been proposed so far for chemically amplified resist compositions may be used.

[0453] Examples of such acid generating agents include onium salt-based acid generating agents such as iodonium salts or sulfonium salts; oximesulfonate-based acid generating agents; diazomethane-based acid generating agents such as bisalkyl or bisarylsulfonyl diazomethanes and poly(bissulfonyl)diazomethanes; nitrobenzylsulfonate-based acid generating agents, iminosulfonate-based acid generating agents, and disulfone-based acid generating agents.

[0454] Examples of onium salt-based acid-generating agents include, for instance, a compound represented by the following general formula (b-1) (hereinafter also referred to as the “(b-1) component”), a compound represented by the general formula (b-2) (hereinafter also referred to as the “(b-2) component”), or a compound represented by the general formula (b-3) (hereinafter also referred to as the “(b-3) component”).

[0455] [Chemical Formula 41]

[0456]

[0457] [In the middle of the meal, R 101 and R 104 ~ R 108 R is, respectively, a cyclic group that may have substituents, a chain-type alkyl group that may have substituents, or a chain-type alkenyl group that may have substituents. 104 and R 105 They may be combined with each other to form a ring structure. R 102 is a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom. Y 101 It is a divalent linker or single bond containing silver and oxygen atoms. V 101 ~ V 103 Each is independently a single bond, an alkylene group, or a fluorinated alkylene group. L 101 ~ L 102 Each is, independently, a single bond or an oxygen atom. L 103 ~ L 105 is, respectively, a single bond, -CO- or -SO2-. m is an integer greater than or equal to 1, where M m＋is an onium cation of the m valence.

[0458] {Anionbu}

[0459] · (b-1) Anion in the component

[0460] In Equation (b-1), R 101 It is a cyclic group that may have substituents, a chain-type alkyl group that may have substituents, or a chain-type alkenyl group that may have substituents.

[0461] Cyclic groups that may have substituents:

[0462] The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. An aliphatic hydrocarbon group refers to a hydrocarbon group that does not have aromaticity. In addition, the aliphatic hydrocarbon group may be saturated or unsaturated, and is generally preferred to be saturated.

[0463] R 101 The aromatic hydrocarbon group in the above is a hydrocarbon group having an aromatic ring. The number of carbon atoms of 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, the number of carbon atoms does not include the number of carbon atoms in the substituents.

[0464] R 101 Specifically, aromatic rings of the aromatic hydrocarbon group in the above examples include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic complex rings in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms. Examples of heteroatoms in the aromatic complex rings include oxygen atoms, sulfur atoms, nitrogen atoms, etc.

[0465] R 101Specifically, the aromatic hydrocarbon group in the above may be a group in which one hydrogen atom has been removed from the aromatic ring (aryl group: e.g., phenyl group, naphthyl group, etc.), a group in which one hydrogen atom of the aromatic ring is substituted with an alkylene group (e.g., benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc., arylalkyl group, etc.). The number of carbon atoms of the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0466] R 101 Examples of cyclic aliphatic hydrocarbon groups include aliphatic hydrocarbon groups that contain a ring in their structure.

[0467] Examples of ring-containing aliphatic hydrocarbon groups in this structure include alicyclic hydrocarbon groups (groups from which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which alicyclic hydrocarbon groups are bonded to the ends of straight-chain or branched-chain aliphatic hydrocarbon groups, and groups in which alicyclic hydrocarbon groups are interposed in the middle of straight-chain or branched-chain aliphatic hydrocarbon groups.

[0468] The above-mentioned alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.

[0469] The above alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. As for the monocyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from a monocycloalkane is preferred. The monocycloalkane is preferably one having 3 to 6 carbon atoms, and specifically, examples include cyclopentane and cyclohexane. As for the polycyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from a polycycloalkane is preferred, and the polycycloalkane is preferably one having 7 to 30 carbon atoms. Among these, the polycycloalkane is a polycycloalkane having a cross-linked polycyclic skeleton such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; Polycycloalkanes having a polycyclic skeleton of a condensed ring system, such as a cyclic group having a steroid backbone, are more preferable.

[0470] Among them, R 101 As for the cyclic aliphatic hydrocarbon group in the above, a group from which one or more hydrogen atoms have been removed from a monocycloalkane or a polycycloalkane is preferred, a group from which one hydrogen atom has been removed from a polycycloalkane is more preferred, an adamantyl group or a norbornyl group is even more preferred, and an adamantyl group is particularly preferred.

[0471] The straight-chain aliphatic hydrocarbon group that may be bonded to the alicyclic hydrocarbon group is preferably 1 to 10 carbon atoms, more preferably 1 to 6, even more preferably 1 to 4, and most preferably 1 to 3. As for the straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferred, and specifically, examples include a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], a pentamethylene group [-(CH2)5-], etc.

[0472] The branched-chain aliphatic hydrocarbon group that 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. As for the branched-chain aliphatic hydrocarbon group, a branched-chain alkylene group is preferred, specifically, alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-; Examples include alkyltrimethylene groups such as -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-; alkylalkylene groups such as alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2CH2-. Among the alkyl groups, a straight-chain alkyl group having 1 to 5 carbon atoms is preferred.

[0473] Also, R 101 The cyclic hydrocarbon group in the above may include heteroatoms, such as complex rings. Specifically, examples include lactone-containing cyclic groups represented by the above general formulas (a2-r-1) to (a2-r-7), -SO2-containing cyclic groups represented by the above general formulas (a5-r-1) to (a5-r-4), and other complex cyclic groups represented by the following chemical formulas (r-hr-1) to (r-hr-16). In the formulas, * represents Y in formula (b-1). 101 It represents the bonding hand that joins to.

[0474] [Chemical Formula 42]

[0475]

[0476] R 101Examples of substituents for the cyclic group include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, nitro groups, etc.

[0477] As for the alkyl group as a substituent, an alkyl group having 1 to 5 carbon atoms is preferred, and a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group is most preferred.

[0478] As for the alkoxy group as a substituent, an alkoxy group having 1 to 5 carbon atoms is preferred, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group are more preferred, and a methoxy group and an ethoxy group are most preferred.

[0479] Examples of halogen atoms serving as substituents include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., and fluorine atoms are preferred.

[0480] Examples of alkyl halide groups 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.

[0481] The carbonyl group as a substituent is a group that substitutes for the methylene group (-CH2-) constituting the cyclic hydrocarbon group.

[0482] R 101The cyclic hydrocarbon group in the above may be a condensed ring group comprising a condensed ring formed by the condensation of an aliphatic hydrocarbon ring and an aromatic ring. Examples of the above condensed ring include, for instance, a polycycloalkane having a polycyclic backbone of a cross-linked cyclic system in which one or more aromatic rings are condensed. Specific examples of the above cross-linked cyclic polycycloalkane include bicycloalkanes such as bicyclo[2.2.1]heptane (norbornane) and bicyclo[2.2.2]octane. Regarding the above condensed ring group, a group comprising a condensed ring formed by the condensation of two or three aromatic rings to a bicycloalkane is preferred, and a group comprising a condensed ring formed by the condensation of two or three aromatic rings to a bicyclo[2.2.2]octane is more preferred. R 101 Specific examples of the condensation ring-shaped group in this case include those represented by the following formulas (r-br-1) to (r-br-2). In the formulas, * represents Y in formula (b-1). 101 It represents the bonding hand that joins to.

[0483] [Chemical Formula 43]

[0484]

[0485] R 101 Examples of substituents that the condensed cyclic group may have include, for instance, alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, nitro groups, aromatic hydrocarbon groups, alicyclic hydrocarbon groups, etc.

[0486] The alkyl group, alkoxy group, halogen atom, and alkyl halide group as substituents of the above condensed cyclic group are the above R 101 The same as those exemplified as substituents of the cyclic group in this case can be cited.

[0487] Examples of aromatic hydrocarbon groups as substituents for the above-mentioned condensed cyclic groups include a group in which one hydrogen atom has been removed from the aromatic ring (aryl group: e.g., phenyl group, naphthyl group, etc.), a group in which one hydrogen atom of the above-mentioned aromatic ring is substituted with an alkylene group (e.g., benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.), and complex cyclic groups represented by the above formulas (r-hr-1) to (r-hr-6), respectively.

[0488] Examples of alicyclic hydrocarbon groups as substituents for the above-mentioned condensed cyclic groups include: a group obtained by removing one hydrogen atom from monocycloalkanes such as cyclopentane and cyclohexane; a group obtained by removing one hydrogen atom from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; a lactone-containing cyclic group represented by the above-mentioned general formulas (a2-r-1) to (a2-r-7); a -SO2- containing cyclic group represented by the above-mentioned general formulas (a5-r-1) to (a5-r-4); and complex cyclic groups represented by the above-mentioned formulas (r-hr-7) to (r-hr-16).

[0489] Chain-type alkyl groups that may have substituents:

[0490] R 101 The chain-type alkyl group may be either a straight chain type or a branched chain type.

[0491] As for the straight-chain alkyl group, it is preferable that the number of carbon atoms is 1 to 20, more preferable that it is 1 to 15, and most preferable that it is 1 to 10.

[0492] As for the branched chain type alkyl group, it is preferable that the number of carbon atoms is 3 to 20, more preferable that it is 3 to 15, and most preferable that it is 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, 4-methylpentyl group, etc.

[0493] Chain-type alkenyl groups that may have substituents:

[0494] R 101 The chain-type alkenyl group may be either a straight chain type or a branched chain type, and it is preferable that the number of carbon atoms be 2 to 10, more preferable that it be 2 to 5, even more preferable that it be 2 to 4, and particularly preferable that it be 3. Examples of straight-chain alkenyl groups include vinyl groups, propphenyl groups (allyl groups), butynyl groups, etc. Examples of branched-chain alkenyl groups include 1-methylvinyl groups, 2-methylvinyl groups, 1-methylpropenyl groups, 2-methylpropenyl groups, etc.

[0495] Among the chain-type alkenyl groups, a straight-chain type alkenyl group is preferred, a vinyl group and a propenyl group are more preferred, and a vinyl group is particularly preferred.

[0496] R 101 As substituents in the chain-type alkyl or alkenyl group of, for example, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and the above R 101 Examples include ring-shaped devices in this regard.

[0497] Among the above, R 101 A cyclic group that may have substituents is preferable, and a cyclic hydrocarbon group that may have substituents is more preferable.

[0498] As a cyclic hydrocarbon group, more specifically, it is preferable to be a condensed cyclic group comprising a polycycloalkane from which one or more hydrogen atoms have been removed or a condensed ring formed by the condensation of an aliphatic hydrocarbon ring and an aromatic ring, more preferable to be an adamantyl group, a group represented by the formula (r-br-1), or a group represented by the formula (r-br-2), and even more preferable to be an adamantyl group, or a group represented by the formula (r-br-1).

[0499] In Equation (b-1), Y 101 It is a divalent linker containing a single bond or an oxygen atom.

[0500] Y 101 In the case of a divalent linker containing this oxygen atom, its Y 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.

[0501] Examples of divalent linkers containing an oxygen atom include, for instance, non-hydrocarbon oxygen-containing linkers such as an oxygen atom (ether bond: -O-), an ester bond (-C(=O)-O-), an oxycarbonyl group (-OC(=O)-), an amide bond (-C(=O)-NH-), a carbonyl group (-C(=O)-), and a carbonate bond (-OC(=O)-O-); and combinations of such non-hydrocarbon oxygen-containing linkers and alkylene groups. A sulfonyl group (-SO2-) may additionally be connected to this combination. Examples of such divalent linkers containing an oxygen atom include linkers represented by the following general formulas (y-al-1) to (y-al-7), respectively. Furthermore, in the following general formulas (y-al-1) to (y-al-7), R in the above formula (b-1) 101 Combining with is V' in the following general formulas (y-al-1) ~ (y-al-7). 101 am.

[0502] [Chemical Formula 44]

[0503]

[0504] [During the meal, V' 101 is a single bond or an alkylene group having 1 to 5 carbon atoms, and V' 102 is a divalent saturated hydrocarbon group with 1 to 30 carbon atoms.

[0505] V' 102 The divalent saturated hydrocarbon group in the above 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.

[0506] V' 101 and V' 102 The alkylene group in this case may be a straight-chain alkylene group or a branched-chain alkylene group, and a straight-chain alkylene group is preferred.

[0507] V' 101 and V' 102 As for the alkylene group in the above, specifically, methylene group [-CH2-]; alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-; ethylene group [-CH2CH2-]; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-; trimethylene group (n-propylene group) [-CH2CH2CH2-]; alkyltrimethylene groups such as -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-; tetramethylene group [-CH2CH2CH2CH2-]; Examples include alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2CH2-, and pentamethylene groups [-CH2CH2CH2CH2CH2-].

[0508] Also, V'101 or V' 102 In the above, some of the methylene groups in the alkylene groups may be substituted with divalent aliphatic cyclic groups having 5 to 10 carbon atoms. The aliphatic cyclic group is Ra' in the above formula (a1-r-1). 3 A divalent group obtained by removing one additional hydrogen atom from a cyclic aliphatic hydrocarbon group (monocyclic aliphatic hydrocarbon group, polycyclic aliphatic hydrocarbon group) is preferred, and a cyclohexylene group, a 1,5-adamantylene group, or a 2,6-adamantylene group is more preferred.

[0509] Y 101 A divalent linker containing an ester bond or a divalent linker containing an ether bond is preferred, and a linker represented by each of the formulas (y-al-1) to (y-al-5) is more preferred.

[0510] In equation (b-1), V 101 It is a single bond, an alkylene group, or a fluorinated alkylene group. V 101 In the above, the alkylene group and the fluorinated alkylene group preferably have 1 to 4 carbon atoms. V 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 substituted with fluorine atoms. Among these, V 101 It is preferable that it be a single bond, or a fluorinated alkylene group having 1 to 4 carbon atoms.

[0511] In Equation (b-1), R 102 is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. R 102 It is preferable that it be a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and more preferable that it be a fluorine atom.

[0512] Specific examples of the anon part represented by the above formula (b-1) include, for example, Y 101In the case where this single bond is formed, examples include fluorinated alkylsulfonate anions such as trifluoromethanesulfonate anions or perfluorobutanesulfonate anions; Y 101 In the case of a divalent linker containing this oxygen atom, an anion represented by any of the following formulas (an-1) to (an-3) can be cited.

[0513] [Chemical Formula 45]

[0514]

[0515] [In the middle of the meal, R" 101 R is an aliphatic cyclic group that may have substituents, a monovalent complex cyclic group represented by the chemical formulas (r-hr-1) to (r-hr-6), respectively, a condensed cyclic group represented by the formulas (r-br-1) and (r-br-2), or a chain-type alkyl group that may have substituents. 102 is an aliphatic cyclic group that may have substituents, a condensed cyclic group represented by the above formulas (r-br-1) and (r-br-2), a lactone-containing cyclic group represented by the above general formulas (a2-r-1), (a2-r-3) to (a2-r-7), respectively, or a -SO2-containing cyclic group represented by the above general formulas (a5-r-1) to (a5-r-4), respectively. 103 It is an aromatic cyclic group that may have substituents, an aliphatic cyclic group that may have substituents, or a chain-type alkenyl group that may have substituents. V" 101 It is a single bond, an alkylene group having 1 to 4 carbon atoms, or a fluorinated alkylene group having 1 to 4 carbon atoms. R 102 is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. v" is each independently an integer from 0 to 3, q" is each independently an integer from 0 to 20, and n" is 0 or 1.

[0516] R" 101 , R" 102 and R" 103The aliphatic cyclic group that may have a substituent is R in the above formula (b-1). 101 It is preferable that the cyclic aliphatic hydrocarbon group exemplified in [formula] be the group. As the substituent, R in formula (b-1) is 101 Examples of substituents that can substitute for the cyclic aliphatic hydrocarbon group in this case include those identical to the cyclic aliphatic hydrocarbon group.

[0517] R" 103 The aromatic cyclic group that may have a substituent in is R in the above formula (b-1). 101 It is preferable that the aromatic hydrocarbon group exemplified in the cyclic hydrocarbon group is the one in question. As the substituent, R in the above formula (b-1) is 101 Examples of substituents that can substitute the aromatic hydrocarbon group in that case include the same.

[0518] R" 101 The chain-type alkyl group that may have a substituent in is R in the above formula (b-1). 101 It is preferable that the chain-type alkyl group exemplified in this be the one.

[0519] R" 103 The chain-type alkenyl group that may have a substituent in is R in the above formula (b-1). 101 It is preferable that the group exemplified as a chain-type alkenyl group in this case be the one.

[0520] · (b-2) Anion in the component

[0521] In Equation (b-2), R 104 , R 105 is, each independently, a cyclic group that may have substituents, a chain-type alkyl group that may have substituents, or a chain-type alkenyl group that may have substituents, and each is R in formula (b-1). 101 The same as can be cited. However, R 104 , R 105 They may combine with each other to form a ring.

[0522] R 104 , R 105 A chain-type alkyl group that may have a substituent is preferred, and a straight-chain or branched-chain alkyl group, or a straight-chain or branched-chain fluorinated alkyl group is more preferred.

[0523] The number of carbon atoms in the chain-type alkyl group is preferably 1 to 10, more preferably 1 to 7, and even more preferably 1 to 3. R 104 , R 105 The number of carbon atoms in the chain-type alkyl group is preferably smaller within the above range of carbon atoms, for reasons such as good solubility in the solvent for the resist. Also, R 104 , R 105 In the case of the chain-type alkyl group, it is desirable that the greater the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid strength becomes and the transparency to high-energy light or electron beams of 250 nm or less is improved. The ratio of fluorine atoms in the chain-type 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.

[0524] In equation (b-2), V 102 , V 103 Each is independently a single bond, an alkylene group, or a fluorinated alkylene group, and each is V in formula (b-1). 101 One can cite the same thing as.

[0525] In formula (b-2), L 101 , L 102 Each is independently a single bond or an oxygen atom.

[0526] · (b-3) Anion in the component

[0527] In Equation (b-3), R 106 ~ R 108Each is independently a cyclic group that may have substituents, a chain-type alkyl group that may have substituents, or a chain-type alkenyl group that may have substituents, and each is R in formula (b-1). 101 One can cite the same thing as.

[0528] In formula (b-3), L 103 ~ L 105 Each is independently a single bond, -CO- or -SO2-.

[0529] Among the above, as for the anion part of component (B), the anion in component (b-1) is preferred. Among these, the anion represented by any one of the general formulas (an-1) to (an-3) is more preferred, the anion represented by either general formula (an-1) or (an-2) is even more preferred, and the anion represented by general formula (an-2) is particularly preferred.

[0530] {Kationbu}

[0531] Among the above equations (b-1), (b-2), and (b-3), M m＋ represents an onium cation of m. Among these, sulfonium cation and iodonium cation are preferred.

[0532] m is an integer greater than or equal to 1.

[0533] Desirable cationic part ((M m＋ ) 1 / m Examples of ) include organic cations represented by the following general formulas (ca-1) to (ca-5), respectively.

[0534] [Chemical Formula 46]

[0535]

[0536] [In the middle of the meal, R 201 ~ R 207 , and R 211 ~ R 212 represents an aryl group, alkyl group, or alkenyl group that may each independently have a substituent. R 201~ R 203 , R 206 ~ R 207 , R 211 ~ R 212 They may combine with each other to form a ring together with the sulfur atom in the formula. R 208 ~ R 209 Each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms independently. R 210 It is an aryl group that may have substituents, an alkyl group that may have substituents, an alkenyl group that may have substituents, or an SO2-containing cyclic group that may have substituents. L 201 represents -C(=O)- or -C(=O)-O-. Y 201 Each represents an arylene group, an alkylene group, or an alkenylene group, independently. x is 1 or 2. W 201 represents the connector of (x + 1).

[0537] Among the above general formulas (ca-1) ~ (ca-5), R 201 ~ R 207 , and R 211 ~ R 212 Examples of aryl groups include unsubstituted aryl groups having 6 to 20 carbon atoms, and phenyl groups and naphthyl groups are preferred.

[0538] R 201 ~ R 207 , and R 211 ~ R 212 The alkyl group in the above is preferably a chain-type or cyclic alkyl group having 1 to 30 carbon atoms.

[0539] R 201 ~ R 207 , and R 211 ~ R 212 In the case of the alkenyl group, it is preferable that the number of carbon atoms be 2 to 10.

[0540] R 201 ~ R 207 , and R 210 ~ R 212Substituents that may be present include, for example, 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).

[0541] [Chemical Formula 47]

[0542]

[0543] [In the middle of the meal, R' 201 Each is independently a hydrogen atom, a cyclic group that may have substituents, a chain-type alkyl group that may have substituents, or a chain-type alkenyl group that may have substituents.

[0544] Cyclic groups that may have substituents:

[0545] The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. An aliphatic hydrocarbon group refers to a hydrocarbon group that does not have aromaticity. In addition, the aliphatic hydrocarbon group may be saturated or unsaturated, and is generally preferred to be saturated.

[0546] R' 201 The aromatic hydrocarbon group in the above is a hydrocarbon group having an aromatic ring. The number of carbon atoms of 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, the number of carbon atoms does not include the number of carbon atoms in the substituents.

[0547] R' 201Specifically, aromatic rings of the aromatic hydrocarbon group in the above examples include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic complex rings in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms. Examples of heteroatoms in the aromatic complex rings include oxygen atoms, sulfur atoms, nitrogen atoms, etc.

[0548] R' 201 Specifically, the aromatic hydrocarbon group in the above may be a group in which one hydrogen atom has been removed from the aromatic ring (aryl group: e.g., phenyl group, naphthyl group, etc.), a group in which one hydrogen atom of the aromatic ring is substituted with an alkylene group (e.g., benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc., arylalkyl group, etc.). The number of carbon atoms of the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0549] R' 201 Examples of cyclic aliphatic hydrocarbon groups include aliphatic hydrocarbon groups that contain a ring in their structure.

[0550] Examples of ring-containing aliphatic hydrocarbon groups in this structure include alicyclic hydrocarbon groups (groups from which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which alicyclic hydrocarbon groups are bonded to the ends of straight-chain or branched-chain aliphatic hydrocarbon groups, and groups in which alicyclic hydrocarbon groups are interposed in the middle of straight-chain or branched-chain aliphatic hydrocarbon groups.

[0551] The above-mentioned alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.

[0552] The above alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. As for the monocyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from a monocycloalkane is preferred. The monocycloalkane is preferably one having 3 to 6 carbon atoms, and specifically, examples include cyclopentane and cyclohexane. As for the polycyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from a polycycloalkane is preferred, and the polycycloalkane is preferably one having 7 to 30 carbon atoms. Among these, the polycycloalkane is a polycycloalkane having a cross-linked polycyclic skeleton such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; Polycycloalkanes having a polycyclic skeleton of a condensed ring system, such as a cyclic group having a steroid backbone, are more preferable.

[0553] Among them, R' 201 As for the cyclic aliphatic hydrocarbon group in the above, a group from which one or more hydrogen atoms have been removed from a monocycloalkane or polycycloalkane is preferred, a group from which one hydrogen atom has been removed from a polycycloalkane is more preferred, an adamantyl group and a norbornyl group are particularly preferred, and an adamantyl group is most preferred.

[0554] A straight-chain or branched-chain aliphatic hydrocarbon group that may be bonded to an 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.

[0555] As for the straight-chain aliphatic hydrocarbon groups, straight-chain alkylene groups are preferred, and specifically, examples include methylene groups [-CH2-], ethylene groups [-(CH2)2-], trimethylene groups [-(CH2)3-], tetramethylene groups [-(CH2)4-], pentamethylene groups [-(CH2)5-], etc.

[0556] As for branched-chain aliphatic hydrocarbon groups, branched-chain alkylene groups are preferred, and specifically, alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-; alkylalkylene groups such as -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2-; and alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2CH2-. As for the alkyl group in the alkylalkylene group, a straight-chain alkyl group having 1 to 5 carbon atoms is preferred.

[0557] Also, R' 201 The cyclic hydrocarbon group in the above may include heteroatoms, such as complex rings. Specifically, examples include lactone-containing cyclic groups represented by the above general formulas (a2-r-1) to (a2-r-7), -SO2- containing cyclic groups represented by the above general formulas (a5-r-1) to (a5-r-4), and other complex cyclic groups represented by the above chemical formulas (r-hr-1) to (r-hr-16).

[0558] R' 201 Examples of substituents for the cyclic group include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, nitro groups, etc.

[0559] As for the alkyl group as a substituent, an alkyl group having 1 to 5 carbon atoms is preferred, and a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group is most preferred.

[0560] As for the alkoxy group as a substituent, an alkoxy group having 1 to 5 carbon atoms is preferred, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group are more preferred, and a methoxy group and an ethoxy group are most preferred.

[0561] As a halogen atom serving as a substituent, a fluorine atom is preferred.

[0562] Examples of alkyl halide groups 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.

[0563] The carbonyl group as a substituent is a group that substitutes for the methylene group (-CH2-) constituting the cyclic hydrocarbon group.

[0564] Chain-type alkyl groups that may have substituents:

[0565] R' 201 The chain-type alkyl group may be either a straight chain type or a branched chain type.

[0566] As for the straight-chain alkyl group, it is preferable that the number of carbon atoms is 1 to 20, more preferable that the number of carbon atoms is 1 to 15, and most preferable that the number of carbon atoms is 1 to 10.

[0567] As for the branched chain type alkyl group, it is preferable that the number of carbon atoms is 3 to 20, more preferable that the number of carbon atoms is 3 to 15, and most preferable that the number of carbon atoms is 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, 4-methylpentyl group, etc.

[0568] Chain-type alkenyl groups that may have substituents:

[0569] R'201 The chain-type alkenyl group may be either a straight chain type or a branched chain type, and it is preferable that the number of carbon atoms be 2 to 10, more preferable that the number of carbon atoms be 2 to 5, even more preferable that the number of carbon atoms be 2 to 4, and particularly preferable that the number of carbon atoms be 3. Examples of straight-chain alkenyl groups include vinyl groups, propenyl groups (allyl groups), butynyl groups, etc. Examples of branched-chain alkenyl groups include 1-methylvinyl groups, 2-methylvinyl groups, 1-methylpropenyl groups, 2-methylpropenyl groups, etc.

[0570] Among the chain-type alkenyl groups, a straight-chain type alkenyl group is preferred, a vinyl group and a propenyl group are more preferred, and a vinyl group is particularly preferred.

[0571] R' 201 As substituents in the chain-type alkyl or alkenyl group, for example, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and the above R' 201 Examples include ring-shaped devices in this regard.

[0572] R' 201 In addition to those described above, the cyclic group that may have a substituent, the chain-type alkyl group that may have a substituent, or the chain-type alkenyl group that may have a substituent may be the same as the acid dissociable group represented by the formula (a1-r-2) described above, as a cyclic group that may have a substituent or a chain-type alkyl group that may have a substituent.

[0573] Among them, R' 201A cyclic group that may have substituents is preferred, and a cyclic hydrocarbon group that may have substituents is more preferred. More specifically, for example, a group obtained by removing one or more hydrogen atoms from a phenyl group, a naphthyl group, or a polycycloalkane; a lactone-containing cyclic group represented by the general formulas (a2-r-1) to (a2-r-7), respectively; and a -SO2- containing cyclic group represented by the general formulas (a5-r-1) to (a5-r-4), respectively, are preferred.

[0574] Among the above general formulas (ca-1) ~ (ca-5), R 201 ~ R 203 , R 206 ~ R 207 , R 211 ~ R 212 When bonded to form a ring with a sulfur atom in the formula, heteroatoms such as sulfur atoms, oxygen atoms, nitrogen atoms, carbonyl groups, -SO-, -SO2-, -SO3-, -COO-, -CONH-, or -N(R N )- (that R N It may be bonded by interposing a functional group such as an alkyl group having 1 to 5 carbon atoms. As for the ring formed, it is preferable that one ring containing a sulfur atom in the formula is a 3 to 10-membered ring containing a sulfur atom, and particularly preferable that it is a 5 to 7-membered ring. Specific examples of the ring formed include, for instance, a thiophene ring, a thiazole ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthen ring, a thioxantone ring, a thianthrene ring, a phenoxathine ring, a tetrahydrothiophenium ring, a tetrahydrothiopyranium ring, etc.

[0575] R 208 ~ R 209Each of the alkyl groups 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, and when they are alkyl groups, they may bond with each other to form a ring.

[0576] R 210 It is an aryl group that may have substituents, an alkyl group that may have substituents, an alkenyl group that may have substituents, or an SO2-containing cyclic group that may have substituents.

[0577] R 210 Examples of aryl groups include unsubstituted aryl groups having 6 to 20 carbon atoms, and phenyl groups and naphthyl groups are preferred.

[0578] R 210 The alkyl group in the above is preferably a chain-type or cyclic alkyl group having 1 to 30 carbon atoms.

[0579] R 210 In the case of the alkenyl group, it is preferable that the number of carbon atoms be 2 to 10.

[0580] R 210 Among the SO2-containing cyclic groups that may have substituents, a "-SO2-containing polycyclic group" is preferred, and the group represented by the general formula (a5-r-1) is more preferred.

[0581] Y 201 Each represents, independently, an arylene group, an alkylene group, or an alkenylene group.

[0582] Y 201 The arylene group in this case is R in the formula (b-1) described above. 101 An example of an aromatic hydrocarbon group in this case is a group in which one hydrogen atom has been removed from the aryl group exemplified therein.

[0583] Y 201 The alkylene group and alkenylene group in this case are R in the formula (b-1) described above. 101Examples include chain-type alkyl groups and chain-type alkenyl groups from which one hydrogen atom has been removed.

[0584] In the above equation (ca-4), x is 1 or 2.

[0585] W 201 is a connector for (x + 1), that is, 2 or 3.

[0586] W 201 As for the divalent linker in this case, a divalent hydrocarbon group that may have a substituent is preferred, and Ya in the general formula (a2-1) described above 21 Examples of divalent hydrocarbon groups that may have substituents identical to W can be given. 201 The linker of the two groups in this case may be of the straight-chain type, branched-chain type, or cyclic type, and is preferably of the cyclic type. Among these, a group in which two carbonyl groups are combined at both ends of the arylene group is preferred. Examples of arylene groups include phenylene groups and naphthylene groups, and phenylene groups are particularly preferred.

[0587] W 201 As for the 3-fold connector in , the above W 201 Examples include a group in which one hydrogen atom is removed from a divalent linker, and a group in which an additional divalent linker is bonded to the divalent linker. W 201 As for the trivalent linker in this case, a group in which two carbonyl groups are bonded to an arylene group is preferred.

[0588] Specifically, as a preferred cation represented by the above formula (ca-1), examples include cations represented by the following chemical formulas (ca-1-1) to (ca-1-72), respectively.

[0589] [Chemical Formula 48]

[0590]

[0591] [Chemical Formula 49]

[0592]

[0593] [Chemical Formula 50]

[0594]

[0595] [In the expression, g1, g2, and g3 represent the number of repetitions, g1 is an integer from 1 to 5, g2 is an integer from 0 to 20, and g3 is an integer from 0 to 20.]

[0596] [Chemical Formula 51]

[0597]

[0598] [Chemical Formula 52]

[0599]

[0600] [Chemical Formula 53]

[0601]

[0602] [Chemical Formula 54]

[0603]

[0604] [In the middle of the meal, R" 201 is a hydrogen atom or a substituent, and the substituent is the above R 201 ~ R 207 , and R 210 ~ R 212 It is identical to the example given as a substituent that may be present.]

[0605] Specifically, preferred cations represented by the above formula (ca-2) include diphenyliodonium cations, bis(4-tert-butylphenyl)iodonium cations, etc.

[0606] Specifically, as desirable cations represented by the above formula (ca-3), cations represented by the following formulas (ca-3-1) to (ca-3-6), respectively, can be cited.

[0607] [Chemical Formula 55]

[0608]

[0609] Specifically, as desirable cations represented by the above formula (ca-4), cations represented by the following formulas (ca-4-1) to (ca-4-2), respectively, may be cited.

[0610] [Chemical Formula 56]

[0611]

[0612] Specifically, as desirable cations represented by the above formula (ca-5), cations represented by the following general formulas (ca-5-1) to (ca-5-3), respectively, can be cited.

[0613] [Chemical Formula 57]

[0614]

[0615] Among the above, the cationic part ((M m＋ ) 1 / m ) is preferably a cation represented by the general formula (ca-1).

[0616] In the resist composition of the present embodiment, component (B) may be used alone or two or more types may be used in combination.

[0617] In the resist composition of the present embodiment, the content of component (B) is preferably less than 40 parts by mass with respect to 100 parts by mass of component (A), more preferably 1 to 30 parts by mass, and even more preferably 5 to 30 parts by mass.

[0618] (B) By setting the content of the component to the above-mentioned preferred range, pattern formation is sufficiently carried out. In addition, it is desirable because when each component of the resist composition is dissolved in an organic solvent, a uniform solution is easily obtained and the preservation stability as a resist composition is improved.

[0619] <Acid Diffusion Control Agent Ingredient (D)>

[0620] The resist composition of the present embodiment contains, in addition to component (A) and component (B), an acid diffusion control agent component (D).

[0621] (D) The component includes a compound (D0) represented by the following general formula (d0) (hereinafter also referred to as “component (D0)”).

[0622] [Chemical Formula 58]

[0623]

[0624] [In the middle of the meal, Rd 0 Yd is a condensed cyclic group comprising a condensed ring containing one or more aromatic rings. The condensed cyclic group has, as a substituent, an acid-degrading group that decomposes upon the action of an acid to generate a polar group. 0 It is a 2-valent connector or single bond. M m＋ represents an organic cation of valence m. m is an integer greater than or equal to 1.

[0625] {(D0) Anionic part of the component}

[0626] In the above equation (d0), Rd 0 The condensed ring is a condensed ring type group having an acid-degrading group and containing one or more aromatic rings. Specifically, the aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic complex rings in which some of the carbon atoms constituting the aromatic hydrocarbon rings are substituted with heteroatoms. Examples of heteroatoms in the aromatic complex rings include oxygen atoms, sulfur atoms, nitrogen atoms, etc. Specifically, examples of aromatic complex rings include pyridine rings and thiophene rings.

[0627] Rd 0 The condensed ring type in the above may be a polycyclic aromatic ring type in which the aromatic rings are condensed together, or an aromatic ring-aliphatic hydrocarbon ring condensed ring type in which the aromatic rings and the aliphatic hydrocarbon rings are condensed.

[0628] Examples of polycyclic aromatic ring groups include, specifically, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic complex rings in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms. Examples of heteroatoms in aromatic complex rings include oxygen atoms, sulfur atoms, nitrogen atoms, etc.

[0629] Rd 0 Specifically, polycyclic aromatic ring groups in the above may include a group in which one hydrogen atom has been removed from the aromatic ring (aryl group: e.g., naphthyl group, etc.), a group in which one hydrogen atom of the aromatic ring is substituted with an alkylene group (e.g., phenylyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc., arylalkyl groups, etc.). The number of carbon atoms of the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0630] Rd 0 Examples of the aromatic ring-aliphatic hydrocarbon ring condensation cyclic groups include fluorene; and polycycloalkanes having a polycyclic backbone of a cross-linked ring system in which one or more aromatic rings are condensed. Specific examples of the above-mentioned cross-linked polycycloalkanes include bicyclo[2.2.1]heptane (norbornane) and bicyclo[2.2.2]octane.

[0631] As for the above aromatic ring-aliphatic hydrocarbon ring condensation ring type group, a group comprising a condensation ring in which two or three aromatic rings are condensed to a bicycloalkane is preferred, and a group comprising a condensation ring in which two or three aromatic rings are condensed to a bicyclo[2.2.2]octane is more preferred. Rd 0Specific examples of the condensation ring-shaped group in this case include the group represented by the formulas (r-br-1) to (r-br-2) described above. In this case, * in the formulas (r-br-1) to (r-br-2) described above is Yd in formula (d0). 0 It represents the bonding hand that joins to.

[0632] In the above equation (d0), Rd 0 Among the above, the condensed ring type group is preferably an aromatic ring-aliphatic hydrocarbon ring condensed ring type group, more preferably a group comprising a condensed ring in which two or three aromatic rings are condensed to a bicycloalkane, even more preferably a group comprising a condensed ring in which two or three aromatic rings are condensed to a bicyclo[2.2.2]octane, and even more preferably a group represented by the formulas (r-br-1) to (r-br-2) described above.

[0633] In the above equation (d0), Rd 0 The condensed cyclic group in this case has an acid-dissociating group as a substituent that decomposes upon the action of an acid to produce a polar group. Specifically, examples of acid-dissociating groups constituting the acid-dissociating group include "acetal-type acid-dissociating groups," "tertiary alkyl ester-type acid-dissociating groups," and "tertiary alkyloxycarbonyl acid-dissociating groups." Examples of the polar groups include, for instance, carboxyl groups, hydroxyl groups, amino groups, and sulfonate groups (-SO3H).

[0634] Acetyl-type acid dissociation group:

[0635] Acid dissociable groups that protect the hydroxyl group include, for example, acid dissociable groups represented by the following general formula (a1-r-1).

[0636] [Chemical Formula 59]

[0637]

[0638] [During the meal, Ra' 1 , Ra' 2is a hydrogen atom or an alkyl group. Ra' 3 As a hydrocarbon group, Ra' 3 Eun, Ra' 1 , Ra' 2 It may be combined with any of the following to form a ring.

[0639] Tertiary alkyl ester type acid dissociable group:

[0640] Acid dissociable groups that protect the carboxyl group include, for example, acid dissociable groups represented by the following general formula (a1-r-2).

[0641] [Chemical Formula 60]

[0642]

[0643] [During the meal, Ra' 4 ~ Ra' 6 Each is a hydrocarbon group, Ra' 5 , Ra' 6 They may combine with each other to form a ring.

[0644] Tertiary alkyloxycarbonyl acid dissociable group:

[0645] Acid dissociable groups that protect the hydroxyl group include, for example, acid dissociable groups represented by the following general formula (a1-r-3).

[0646] [Chemical Formula 61]

[0647]

[0648] [During the meal, Ra' 7 ~ Ra' 9 Each is an alkyl group.

[0649] The “acetal-type acid dissociable group,” “tertiary alkyl ester-type acid dissociable group,” and “tertiary alkyloxycarbonyl acid dissociable group” may be the same as the “acetal-type acid dissociable group,” “tertiary alkyl ester-type acid dissociable group,” and “tertiary alkyloxycarbonyl acid dissociable group” described in the constituent unit (a1) of component (A) described above.

[0650] Rd0 The acid dissociable group constituting the acid decomposable group of the condensed cyclic group in the above is not particularly limited and may be an acid dissociable group other than the "acetal-type acid dissociable group," "tertiary alkyl ester-type acid dissociable group," and "tertiary alkyloxycarbonyl acid dissociable group."

[0651] Rd 0 Among the above, the acid-decomposing group having a condensed cyclic group is preferably an acid-decomposing group represented by the following general formula (pg-1).

[0652] [Chemical Formula 62]

[0653]

[0654] [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 bonding hand.]

[0655] [Chemical Formula 63]

[0656]

[0657] [In equation (pg-r-1), Rd 1 ~ Rd 3 Rd, each independently, as a hydrocarbon group 1 and Rd 2 They may combine with each other to form a ring.

[0658] In equation (pg-r-2), Rd 001 Yd is a straight-chain or branched-chain aliphatic hydrocarbon group. 002 is a single coupling or a two-way connector. Rd 002 is a hydrogen atom or a substituent. Ar is a benzene ring or a naphthalene ring. Rm 01 n01 is a substituent. n01 is an integer from 1 to 4.

[0659] In formula (pg-r-3), Xd is a secondary carbon atom. X is an alicyclic hydrocarbon ring that may have substituents. Ar is a benzene ring or a naphthalene ring. Rm 02 is a substituent. n02 is an integer from 1 to 4.

[0660] In equation (pg-r-4), Rd' 1 , Rd' 2 is a hydrogen atom or an alkyl group. Rd' 3 As a hydrocarbon group, Rd' 3 Eun, Rd' 1 , Rd' 2 It may be combined with any of them to form a ring.

[0661] * indicates the bond loss with the oxygen atom (-O-) in the above general formula (pg-1).

[0662] The acid dissociable group represented by the above general formula (pg-r-1) is identical to the acid dissociable group represented by the above general formula (a1-r-2) in the constituent unit (a1) of component (A) described above.

[0663] That is, Rd in the above general formula (pg-r-1). 1 and Ra' in the above general formula (a1-r-2) 4 , Rd in the above general formula (pg-r-1) 2 and Ra' in the above general formula (a1-r-2) 5 , Rd in the above general formula (pg-r-1) 3 and Ra' in the above general formula (a1-r-2) 6 Each can be cited as having the same thing.

[0664] In the acid dissociable group represented by the above general formula (pg-r-1), Rd 1 and Rd 2In the case where they combine to form a ring, groups represented by the following general formula (a1-r2-1), groups represented by the following general formula (a1-r2-2), and groups represented by the following general formula (a1-r2-3) can be preferably cited.

[0665] Meanwhile, Rd 1 ~ Rd 3 In the case where they are independent hydrocarbon groups that are not bonded to each other, groups represented by the following general formula (a1-r2-4) can be preferably cited.

[0666] [Chemical Formula 64]

[0667]

[0668] [Equation (a1-r2-1), Ra' 10 It represents a straight-chain or branched-chain alkyl group having 1 to 12 carbon atoms, where some parts may be substituted with halogen atoms or heteroatom-containing groups. Ra' 11 Ra' 10 It represents 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 is independently a hydrogen atom, a monovalent chain-type 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 chain-type saturated hydrocarbon groups and aliphatic cyclic saturated hydrocarbon groups may be substituted. Ra 101 ~ Ra 103 Two or more of may be bonded to each other to form a ring structure. In formula (a1-r2-3), Yaa is a carbon atom. Xaa is a group that forms an aliphatic ring group together with Yaa. Ra 104is an aromatic hydrocarbon group that may have substituents. In formula (a1-r2-4), Ra' 12 and Ra' 13 Each is independently a monovalent chain-type saturated hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. Some or all of the hydrogen atoms in this chain-type saturated hydrocarbon group may be substituted. Ra' 14 is a hydrocarbon group that may have substituents. * indicates a bond loss.]

[0669] The group represented by the general formula (a1-r2-1) ~ (a1-r2-4) is identical to the group represented by the general formula (a1-r2-1) ~ (a1-r2-4) in the constituent unit (a1) of component (A) described above.

[0670] Among the above general formula (pg-r-2), Rd 001 It is a straight-chain or branched-chain aliphatic hydrocarbon group.

[0671] Rd 001 The straight-chain or branched-chain aliphatic hydrocarbon group in the above is preferably a straight-chain alkyl group having 1 to 10 carbon atoms or a branched-chain alkyl group having 3 to 20 carbon atoms, more preferably a methyl group, ethyl group, propyl group, 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, and even more preferably a methyl group.

[0672] Among the above general formula (pg-r-2), Yd 002 is a single bond or a two-valent connector. Yd 002 As for the 2-valent connector in , Ya in the constituent unit (a10) of the component (A) described above x1 Examples of the same can be cited. Specifically, divalent hydrocarbon groups that may have substituents, divalent linkers containing heteroatoms, etc., can be cited as desirable.

[0673] Yd 002Among the above, a single bond or a straight-chain or branched-chain aliphatic hydrocarbon group is preferred, a single bond or a straight-chain aliphatic hydrocarbon group is more preferred, a single bond or a methylene group [-CH2-] or an ethylene group [-(CH2)2-] is even more preferred, a single bond or a methylene group [-CH2-] is particularly preferred, and a single bond is most preferred.

[0674] Among the above general formula (pg-r-2), Rd 002 is a hydrogen atom, or a substituent. Rd 002 Examples of substituents in the above include carboxyl groups, hydroxyl groups, amino groups, sulfonate groups, halogen atoms, alkyl halide groups, alkoxy groups, alkyloxycarbonyl groups, nitro groups, etc., and among these, hydroxyl groups are preferred.

[0675] Rd 002 Among the above, it is preferable that it be a hydrogen atom or a hydroxyl group, and more preferable that it be a hydrogen atom.

[0676] In the above general formula (pg-r-2), Ar is a benzene ring or a naphthalene ring, preferably a benzene ring.

[0677] Among the above general formula (pg-r-2), Rm 01 Specifically, as substituents in the above, examples include carboxyl groups, hydroxyl groups, amino groups, sulfonate groups, halogen atoms, alkyl halide groups, alkoxy groups, alkyloxycarbonyl groups, nitro groups, etc., and among these, hydroxyl groups are preferred.

[0678] Among the above general formula (pg-r-2), Rm 01 It is preferable that it be a hydrogen atom.

[0679] In the above general formula (pg-r-2), n01 is an integer from 1 to 4, preferably 1 or 2.

[0680] In the above general formula (pg-r-3), X is an alicyclic hydrocarbon ring that may have a substituent. The alicyclic hydrocarbon ring is preferably an alicyclic hydrocarbon ring having 4 to 20 carbon atoms, more preferably an alicyclic hydrocarbon ring having 5 to 15 carbon atoms, and even more preferably an alicyclic hydrocarbon ring 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.

[0681] In the above general formula (pg-r-3), Ar is a benzene ring or a naphthalene ring, preferably a benzene ring.

[0682] Among the above general formula (pg-r-3), Rm 02 Specifically, as substituents in the above, examples include carboxyl groups, hydroxyl groups, amino groups, sulfonate groups, halogen atoms, alkyl halide groups, alkoxy groups, alkyloxycarbonyl groups, nitro groups, etc., and among these, hydroxyl groups are preferred.

[0683] In the above general formula (pg-r-3), n02 is an integer from 1 to 4, preferably 1 or 2.

[0684] The acid dissociable group represented by the above general formula (pg-r-4) is identical to the acid dissociable group represented by the formula (a1-r-1) in the constituent unit (a1) of component (A) described above.

[0685] That is, Rd' in the above general formula (pg-r-4). 1 and Ra' in the above general formula (a1-r-1) 1 , Rd' in the above general formula (pg-r-4) 2 and Ra' in the above general formula (a1-r-1) 2 , Rd' in the above general formula (pg-r-4) 3and Ra' in the above general formula (a1-r-1) 3 Each can be cited as having the same thing.

[0686] Among the above, Rpg in the acid dissociative group represented by the general formula (pg-1) is preferably a cyclic acid dissociative group to further improve acid dissociation ability, an acid dissociative group represented by any one of the general formulas (pg-r-1) to (pg-r-3) is more preferable, and an acid dissociative group represented by the general formula (pg-r-1) is even more preferable.

[0687] More specifically, it is preferable that Rpg is an acid-dissociable group represented by the general formula (a1-r2-1).

[0688] In the case where Rpg in the acid-degrading group represented by the above general formula (pg-1) is an acid-dissociating group represented by the above general formula (a1-r2-1), Ra' in the above general formula (a1-r2-1) 10 A straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms is preferred, and a straight-chain alkyl group having 1 to 5 carbon atoms is more preferred.

[0689] Also, Ra' in the above general formula (a1-r2-1). 11 (Ra' 10 The aliphatic cyclic group formed together with the bonded carbon atom is preferably a single-ring alicyclic hydrocarbon group, and specifically, a cyclopentyl group or a cyclohexyl group is more preferable.

[0690] In the above equation (d0), Rd 0 The condensed cyclic group in the above may have a substituent other than the acid-degradable group described above. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, nitro groups, carbonyl groups, etc.

[0691] As for the alkyl group as a substituent, an alkyl group having 1 to 5 carbon atoms is preferred, and a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group is most preferred.

[0692] As for the alkoxy group as a substituent, an alkoxy group having 1 to 5 carbon atoms is preferred, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group are more preferred, and a methoxy group and an ethoxy group are most preferred.

[0693] As a halogen atom serving as a substituent, a fluorine atom is preferred.

[0694] Examples of alkyl halide groups 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.

[0695] The carbonyl group as a substituent is a group that substitutes for the methylene group (-CH2-) constituting the cyclic hydrocarbon group.

[0696] Among the above equation (d0), Yd 0 It represents a 2-ga connector or single connection.

[0697] Yd 0 As for the divalent linker in this case, a divalent linker containing an oxygen atom can be preferably cited.

[0698] Yd 0 In the case of a divalent linker containing this oxygen atom, its Yd 0 It may include atoms other than oxygen atoms. Examples of atoms other than oxygen atoms include carbon atoms, hydrogen atoms, sulfur atoms, nitrogen atoms, etc.

[0699] Examples of divalent linkers containing an oxygen atom include, for instance, non-hydrocarbon oxygen atom-containing linkers such as an oxygen atom (ether bond: -O-), an ester bond (-C(=O)-O-), an oxycarbonyl group (-OC(=O)-), an amide bond (-C(=O)-NH-), a carbonyl group (-C(=O)-), and a carbonate bond (-OC(=O)-O-); combinations of such non-hydrocarbon oxygen atom-containing linkers and alkylene groups. A sulfonyl group (-SO2-) may additionally be connected to this combination.

[0700] Yd 0 As for the linker, a divalent linker containing an ester link or a divalent linker containing an ether link is preferred, and a linker represented by the following general formula (y-d0-1) or (y-d0-2) is more preferred.

[0701] [Chemical Formula 65]

[0702]

[0703] [In the middle of the meal, Yd 001 and Yd 002 Each is independently an aliphatic hydrocarbon group having 1 to 4 carbon atoms. * is Rd in the above general formula (d0). 0 [Represents the bond loss with. ** represents the bond loss with the carbon atom of the carbonyl group in the above general formula (d0).]

[0704] Yd in the above general formula (y-d0-1) 001 and Yd in the above general formula (y-d0-2) 002 Each is an aliphatic hydrocarbon group having 1 to 4 carbon atoms, independently.

[0705] Examples of the aliphatic hydrocarbon groups include alkylene groups, alkenylene groups, alkadienylene groups, alkatrienylene groups, alkynylene groups, or combinations of these groups.

[0706] · Alkylene group having 1 to 4 carbon atoms

[0707] Examples of straight-chain alkylene groups with 1 to 4 carbon atoms include methylene groups, ethylene groups [-(CH2)2-], trimethylene groups [-(CH2)3-], and tetramethylene groups [-(CH2)4-].

[0708] Examples of branched chain alkylene groups having 2 to 4 carbon atoms include alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-; and alkylalkylene groups such as -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-.

[0709] · Alkenylene group with 2 to 4 carbon atoms

[0710] The alkenylene group having 2 to 4 carbon atoms can be a straight-chain alkenylene group or a branched-chain alkenylene group.

[0711] Examples of straight-chain alkenylene groups having 2 to 4 carbon atoms include the ethanylene group (vinylene group), 1-propenylene group, 2-propenylene group, and butynylene group.

[0712] Examples of branched-chain alkenylene groups having 3 or 4 carbon atoms include 1-methylvinylene groups, 1-methylpropenylene groups, and 2-methylpropenylene groups.

[0713] · Alkadienylene group, Alkatrienylene group

[0714] Examples of alkadienylene groups having 3 or 4 carbon atoms include propadienylene groups and butadienylene groups, and examples of alkatrienylene groups having 4 carbon atoms include butatrienylene groups.

[0715] · Alkynylene group with 2 to 4 carbon atoms

[0716] Examples of alkynylene groups with 2 to 4 carbon atoms include the ethynylene group (-C≡C-).

[0717] As for the combination of alkylene groups, alkenylene groups, alkadienylene groups, alkatrienylene groups, and alkynylene groups, for example, a combination of alkylene groups and alkynylene groups is preferred. Specifically, a -CH2-C≡C- group is preferred.

[0718] Yd in the above general formula (y-d0-1) 001 and Yd in the above general formula (y-d0-2) 002 Among the above, each independently, an alkylene group having 1 to 4 carbon atoms, or a combination of an alkylene group and an alkynylene group having a total of 1 to 4 carbon atoms, is preferred, and an alkylene group having 1 or 2 carbon atoms, or a -CH2-C≡C- group is more preferred.

[0719] In this embodiment, the anion portion of component (D0) is preferably an anion represented by the following general formula (d0-an0) in terms of CDU and resolution improvement.

[0720] [Chemical Formula 66]

[0721]

[0722] [In the food, Rx 1 ~ Rx 4 Each may independently represent a hydrocarbon group or hydrogen atom that may have a substituent, or two or more may be bonded together to form a ring structure. Ry 1 ~ Ry 2 Each may independently represent a hydrocarbon group or a hydrogen atom that may have a substituent, or they may be bonded to each other to form a ring structure.

[0723] [Chemical Formula 67]

[0724]

[0725] is a double bond or a single bond. Rz 1 ~ Rz 4Each may independently represent a hydrocarbon group or a hydrogen atom that may have a substituent, provided that the valence allows, or two or more may be bonded together to form a ring structure. However, Rx 1 ~ Rx 4 2 or more of, Ry 1 ~ Ry 2 , or Rz 1 ~ Rz 4 Two or more of combine with each other to form a directional ring. Also, Rx 1 ~ Rx 4 , Ry 1 ~ Ry 2 and Rz 1 ~ Rz 4 At least one of them has an anion group represented by the following general formula (d0-r-an1), and the entire anion part becomes an anion of value n. Also, Rx 1 ~ Rx 4 , Ry 1 ~ Ry 2 and Rz 1 ~ Rz 4 At least one of them has an acid-degrading group. n is an integer greater than or equal to 1.

[0726] [Chemical Formula 68]

[0727]

[0728] [In the middle of the meal, Yd 0 is a 2-gauge connector or single bond. * indicates a bond loss.]

[0729] In the equation (d0-an0), Rx 1 ~ Rx 4 Each may independently represent a hydrocarbon group or a hydrogen atom that may have a substituent, or two or more may be bonded together to form a ring structure.

[0730] Ry 1 ~ Ry 2Each may independently represent a hydrocarbon group or a hydrogen atom that may have a substituent, or may be bonded to each other to form a ring structure.

[0731] Rz 1 ~ Rz 4 Each may independently represent a hydrocarbon group or a hydrogen atom that may have a substituent, provided that the valence allows it, or two or more may be bonded together to form a ring structure.

[0732] Rx 1 ~ Rx 4 , Ry 1 ~ Ry 2 , Rz 1 ~ Rz 4 The hydrocarbon groups in this case may each be aliphatic hydrocarbons and aromatic hydrocarbons, cyclic hydrocarbons and chain hydrocarbons.

[0733] For example, Rx 1 ~ Rx 4 , Ry 1 ~ Ry 2 , Rz 1 ~ Rz 4 Examples of hydrocarbon groups that may have substituents include cyclic groups that may have substituents, chain-type alkyl groups that may have substituents, or chain-type alkenyl groups that may have substituents.

[0734] Cyclic groups that may have substituents:

[0735] The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. An aliphatic hydrocarbon group refers to a hydrocarbon group that does not possess aromaticity. Furthermore, the aliphatic hydrocarbon group may be saturated or unsaturated, and is generally preferred to be saturated. Also, Rx 1 ~ Rx 4 , Ry 1 ~ Ry 2 , Rz 1~ Rz 4 The cyclic hydrocarbon group in this case may include heteroatoms, such as complex rings.

[0736] Rx 1 ~ Rx 4 , Ry 1 ~ Ry 2 , Rz 1 ~ Rz 4 The aromatic hydrocarbon group in the above 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, the number of carbon atoms does not include the number of carbon atoms in the substituents.

[0737] Rx 1 ~ Rx 4 , Ry 1 ~ Ry 2 , Rz 1 ~ Rz 4 Specifically, aromatic rings possessed by the aromatic hydrocarbon group in [the name] include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic complex rings in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms. Examples of heteroatoms in aromatic complex rings include oxygen atoms, sulfur atoms, nitrogen atoms, etc. Rx 1 ~ Rx 4 , Ry 1 ~ Ry 2 , Rz 1 ~ Rz 4 In the case of the aromatic hydrocarbon group, the aromatic ring is preferably not to contain heteroatoms in terms of compatibility with component (A), and aromatic rings such as benzene, fluorene, naphthalene, anthracene, phenanthrene, and biphenyl are more preferable.

[0738] Rx1 ~ Rx 4 , Ry 1 ~ Ry 2 , Rz 1 ~ Rz 4 Specifically, the aromatic hydrocarbon group in the above may be a group in which one hydrogen atom has been removed from the aromatic ring (aryl group: e.g., phenyl group, naphthyl group, etc.), a group in which one hydrogen atom of the aromatic ring is substituted with an alkylene group (e.g., benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc., arylalkyl group, etc.). The number of carbon atoms of the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0739] Rx 1 ~ Rx 4 , Ry 1 ~ Ry 2 , Rz 1 ~ Rz 4 Examples of cyclic aliphatic hydrocarbon groups include aliphatic hydrocarbon groups that contain a ring in their structure.

[0740] Examples of ring-containing aliphatic hydrocarbon groups in this structure include alicyclic hydrocarbon groups (groups from which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which alicyclic hydrocarbon groups are bonded to the ends of straight-chain or branched-chain aliphatic hydrocarbon groups, and groups in which alicyclic hydrocarbon groups are interposed in the middle of straight-chain or branched-chain aliphatic hydrocarbon groups.

[0741] The above-mentioned alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms.

[0742] The above alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. As for the monocyclic alicyclic hydrocarbon group, it is preferable to have one or more hydrogen atoms removed from a monocycloalkane. The monocycloalkane is preferably one having 3 to 6 carbon atoms, and specifically, examples include cyclopentane and cyclohexane. As for the polycyclic alicyclic hydrocarbon group, it is preferable to have one or more hydrogen atoms removed from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 30 carbon atoms.

[0743] The straight-chain aliphatic hydrocarbon group that may be bonded to the alicyclic hydrocarbon group is preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As for the straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferred, and specifically, examples include a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], a pentamethylene group [-(CH2)5-], etc.

[0744] The branched-chain aliphatic hydrocarbon group that 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. As for the branched-chain aliphatic hydrocarbon group, a branched-chain alkylene group is preferred, specifically, alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-; Examples include alkyltrimethylene groups such as -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-; alkylalkylene groups such as alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2CH2-. Among the alkyl groups, a straight-chain alkyl group having 1 to 5 carbon atoms is preferred.

[0745] Also, Rx 1 ~ Rx 4 , Ry 1 ~ Ry 2 , Rz 1 ~ Rz 4 With that ring-shaped mechanism, -COOR XYZ , -OC(=O)R XYZ Regarding, R XYZ Examples include lactone-containing cyclic groups, carbonate-containing cyclic groups, or -SO2- containing cyclic groups.

[0746] Rx 1 ~ Rx 4 , Ry 1 ~ Ry 2 , Rz 1 ~ Rz 4 As substituents in the cyclic group of, the Rd described above 0Examples of substituents that are identical to the polycyclic aromatic cyclic group that can have are those in the case.

[0747] Rx 1 ~ Rx 4 , Ry 1 ~ Ry 2 , Rz 1 ~ Rz 4 Among the above, as substituents for the cyclic group, alkyl groups, halogen atoms, and alkyl halides are preferred from the perspective of compatibility with component (A).

[0748] Chain-type alkyl groups that may have substituents:

[0749] Rx 1 ~ Rx 4 , Ry 1 ~ Ry 2 , Rz 1 ~ Rz 4 The chain-type alkyl group may be either a straight chain type or a branched chain type.

[0750] As for the straight-chain alkyl group, it is preferable that the number of carbon atoms be 1 to 20, more preferable that the number of carbon atoms be 1 to 15, and most preferable that the number of carbon atoms be 1 to 10. Specifically, examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decanyl group, undecyl group, dodecyl group, tridecyl group, isotridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, isohexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, henicosyl group, docosyl group, etc.

[0751] As for the branched chain type alkyl group, it is preferable that the number of carbon atoms is 3 to 20, more preferable that the number of carbon atoms is 3 to 15, and most preferable that the number of carbon atoms is 3 to 10. 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, 4-methylpentyl group, etc.

[0752] Chain-type alkenyl groups that may have substituents:

[0753] Rx 1 ~ Rx 4 , Ry 1 ~ Ry 2 , Rz 1 ~ Rz 4 The chain-type alkenyl group may be either a straight chain type or a branched chain type, and it is preferable that the number of carbon atoms be 2 to 10, more preferable that the number of carbon atoms be 2 to 5, even more preferable that the number of carbon atoms be 2 to 4, and particularly preferable that the number of carbon atoms be 3. Examples of straight-chain alkenyl groups include vinyl groups, propphenyl groups (allyl groups), butynyl groups, etc. Examples of branched-chain alkenyl groups include 1-propphenyl groups, 2-propphenyl groups (allyl groups), 1-methylpropphenyl groups, 2-methylpropphenyl groups, etc.

[0754] Rx 1 ~ Rx 4 , Ry 1 ~ Ry 2 , Rz 1 ~ Rz 4 As substituents in the chain-type alkyl or alkenyl group of, for example, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and the above Rx 1 ~ Rx 4 , Ry 1 ~ Ry 2 , Rz 1 ~ Rz4 Examples include ring-shaped structures in . Among them, Rx 1 ~ Rx 4 , Ry 1 ~ Ry 2 , Rz 1 ~ Rz 4 As substituents in the chain-type alkyl or alkenyl group of, with respect to compatibility with component (A), a halogen atom, an alkyl halide, and the above Rx 1 ~ Rx 4 , Ry 1 ~ Ry 2 , Rz 1 ~ Rz 4 The ring-shaped device exemplified in this case is desirable.

[0755] Among the above equation (d0-an0), Ry 1 ~ Ry 2 They may be combined with each other to form a ring structure.

[0756] This Ry 1 ~ Ry 2 The ring structure formed by is one side (Ry) of the six-membered ring in equation (d0-an0). 1 and Ry 2 They share bonds between the carbon atoms bonded to each other, and this ring structure may be a dicyclic hydrocarbon or an aromatic hydrocarbon. In addition, this ring structure may be a polycyclic structure consisting of ring structures other than this.

[0757] Ry 1 ~ Ry 2 The alicyclic hydrocarbon formed by may be polycyclic or monocyclic. Monocycloalkanes are preferred as monocyclic alicyclic hydrocarbons. The monocycloalkanes are preferably those having 3 to 6 carbon atoms, and specifically, examples include cyclopentane and cyclohexane. Polycycloalkanes are preferred as polycyclic alicyclic hydrocarbons. The polycycloalkanes are preferably those having 7 to 30 carbon atoms.

[0758] Ry1 ~ Ry 2 Examples of the aromatic hydrocarbon rings formed by include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic complex rings in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms. 1 ~ Ry 2 The aromatic hydrocarbon ring formed by (A) is preferably not to contain heteroatoms in terms of compatibility with component (A), and aromatic rings such as benzene, fluorene, naphthalene, anthracene, phenanthrene, and biphenyl are more preferable.

[0759] Ry 1 ~ Ry 2 The ring structure (alicyclic hydrocarbon, aromatic hydrocarbon) formed by may have a substituent. As for the substituent here, the Rx described above 1 ~ Rx 4 , Ry 1 ~ Ry 2 , Rz 1 ~ Rz 4 Examples include those identical to the substituents in the cyclic group (e.g., alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, nitro groups, carbonyl groups, etc.). Among these, Ry 1 ~ Ry 2 As substituents in the ring structure formed by (A), alkyl groups, halogen atoms, and alkyl halide groups are preferred in terms of compatibility with component (A).

[0760] Ry 1 ~ Ry 2 Among the ring structures formed, aromatic hydrocarbons that may have substituents are more preferable.

[0761] In the above equation (d0-an0), Rz 1 ~ Rz 4 Two or more may be combined to form a ring structure. For example, Rz 1 Silver, Rz 2 ~ Rz4 It may form a ring structure with any of the following. Specifically, one side (Rz) of the six-membered ring in equation (d0-an0) 1 and Rz 2 The carbon atom bonded to Rz 3 and Rz 4 A ring structure sharing the bonds of carbon atoms that are bonded, Rz 1 and Rz 2 A ring structure formed by combining, Rz 3 and Rz 4 Examples include ring structures formed by combining.

[0762] These Rz 1 ~ Rz 4 The ring structure formed by two or more of them may be an alicyclic hydrocarbon or an aromatic hydrocarbon, and it is preferable that it be an aromatic hydrocarbon. In addition, this ring structure may be a polycyclic structure consisting of ring structures other than this.

[0763] Rz 1 ~ Rz 4 The alicyclic hydrocarbons formed by two or more of the groups may be polycyclic or monocyclic. Monocycloalkanes are preferred as monocyclic alicyclic hydrocarbons. The monocycloalkanes are preferably those having 3 to 6 carbon atoms, and specifically, examples include cyclopentane and cyclohexane. Polycycloalkanes are preferred as polycyclic alicyclic hydrocarbons. The polycycloalkanes are preferably those having 7 to 30 carbon atoms, and specifically, polycycloalkanes having a polycyclic skeleton of a cross-linked ring system such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; or polycycloalkanes having a polycyclic skeleton of a condensed ring system such as a cyclic group having a steroid skeleton are more preferred.

[0764] It may be a complex ring structure in which some carbon atoms are substituted with heteroatoms, and a nitrogen-containing complex ring is particularly desirable, specifically examples include cyclic imides.

[0765] Rz 1 ~ Rz 4 Examples of aromatic hydrocarbon rings formed by two or more of these include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic complex rings in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms. Rz 1 ~ Rz 4 The aromatic hydrocarbon rings formed by two or more of the above are preferably not to contain heteroatoms in terms of compatibility with component (A), and aromatic rings such as benzene, fluorene, naphthalene, anthracene, phenanthrene, and biphenyl are more preferable.

[0766] Rz 1 ~ Rz 4 The ring structure (alicyclic hydrocarbon, aromatic hydrocarbon) formed by may have a substituent. As for the substituent here, the Rx described above 1 ~ Rx 4 , Ry 1 ~ Ry 2 , Rz 1 ~ Rz 4 Examples include those identical to the substituents in the cyclic group (e.g., alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, nitro groups, carbonyl groups, etc.). Among these, Rz 1 ~ Rz 4 As substituents in the ring structure formed by (A), alkyl groups, halogen atoms, and alkyl halide groups are preferred in terms of compatibility with component (A).

[0767] Rz 1 ~ Rz 4 The ring structure formed by two or more of them is, among them, one side (Rz) of the six-membered ring in formula (d0-an0). 1 and Rz2 The carbon atom bonded to Rz 3 and Rz 4 A ring structure that shares the bonds of carbon atoms bonded together is desirable, and an directional ring structure is more desirable.

[0768] In addition, in the above formula (d0-an0), "where the valence allows" is as follows.

[0769] That is, Rz 1 and Rz 2 The carbon atom bonded to Rz 3 and Rz 4 In the case where the bond between the carbon atoms is a single bond, Rz 1 , Rz 2 , Rz 3 and Rz 4 The entirety of exists. Rz 1 and Rz 2 The carbon atom bonded to Rz 3 and Rz 4 In the case where the bond between the carbon atoms is a double bond, Rz 1 or Rz 2 Only one side exists, and also Rz 3 and Rz 4 Only one of them exists. Also, for example, Rz 1 and Rz 3 In the case where this combines to form a directional ring structure, Rz 2 and Rz 4 does not exist.

[0770] In the above equation (d0-an0), Rx 1 ~ Rx 4 Two or more may be combined to form a ring structure. For example, Rx 1 silver, Rx 2 ~ Rx 4 It may form a ring structure with any of them.

[0771] These Rx 1 ~ Rx 4The ring structure formed by two or more of them may be an alicyclic hydrocarbon or an aromatic hydrocarbon. In addition, this ring structure may be a polycyclic structure composed of ring structures other than this.

[0772] Rx 1 ~ Rx 4 The alicyclic hydrocarbons formed by two or more of the groups may be polycyclic or monocyclic. Monocycloalkanes are preferred as monocyclic alicyclic hydrocarbons. The monocycloalkanes are preferably those having 3 to 6 carbon atoms, and specifically, examples include cyclopentane and cyclohexane. Polycycloalkanes are preferred as polycyclic alicyclic hydrocarbons. The polycycloalkanes are preferably those having 7 to 30 carbon atoms, and specifically, polycycloalkanes having a polycyclic skeleton of a cross-linked ring system such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; or polycycloalkanes having a polycyclic skeleton of a condensed ring system such as a cyclic group having a steroid skeleton are more preferred.

[0773] Rx 1 ~ Rx 4 Examples of aromatic hydrocarbon rings formed by two of them include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic complex rings in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms. Rx 1 ~ Rx 4 The aromatic hydrocarbon ring formed by two of the components is preferably not to contain heteroatoms in terms of compatibility with component (A), and aromatic rings such as benzene, fluorene, naphthalene, anthracene, phenanthrene, and biphenyl are more preferable.

[0774] Rx 1 ~ Rx 4 The ring structure (alicyclic hydrocarbon, aromatic hydrocarbon) formed by may have a substituent. As for the substituent here, the Rx described above 1 ~ Rx4 , Ry 1 ~ Ry 2 , Rz 1 ~ Rz 4 Examples include those identical to the substituents in the cyclic group (e.g., alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, nitro groups, carbonyl groups, etc.). Among these, Rx 1 ~ Rx 4 As substituents in the ring structure formed by (A), alkyl groups, halogen atoms, and alkyl halide groups are preferred in terms of compatibility with component (A).

[0775] Rx 1 ~ Rx 4 Among the ring structures formed by two or more of them, alicyclic hydrocarbons are preferred.

[0776] Also, Rx 1 ~ Rx 4 The ring structure formed by two or more of them, among them, the above Rx 1 ~ Rx 2 At least one of the above Rx 3 ~ Rx 4 It is preferable that at least one of them is bonded to one another to form a cross-linked ring structure, and it is more preferable that this ring structure is a cycloaliphatic hydrocarbon.

[0777] The above Rx 1 ~ Rx 2 At least one of the above Rx 3 ~ Rx 4 A 2-ring structure (Ry) in which at least one of them combines with another to form a ring structure. 1 , Ry 2 , Rz 1 and Rz 2 , Rz 3 and Rz 4 The number of carbon atoms constituting the ring structure (which also includes carbon atoms bonded to each other) is preferably 7 to 16.

[0778] In the above equation (d0-an0), Rx 1 ~ Rx 4 2 or more of, Ry 1 ~ Ry 2 , or Rz 1 ~ Rz 4 Two or more of these combine to form a directional ring. The directional ring is identical to the directional ring described in the above equation (d0).

[0779] In the above equation (d0-an0), Rx 1 ~ Rx 4 , Ry 1 ~ Ry 2 and Rz 1 ~ Rz 4 At least one of them has an anion represented by the above general formula (d0-r-an1), and the entire anion part becomes an anion of value n. n is an integer greater than or equal to 1. Rx 1 ~ Rx 4 , Ry 1 ~ Ry 2 , Rz 1 ~ Rz 4 Each of the above may contribute to the anion. Also, Rx 1 ~ Rx 4 In cases where two or more of them combine to form a ring structure, the carbon atom forming the ring structure or the hydrogen atom bonded to said carbon atom may be substituted with the above-mentioned anion group. 1 ~ Ry 2 In cases where two or more of them are bonded to each other to form a ring structure, the carbon atom forming the ring structure or the hydrogen atom bonded to said carbon atom may be substituted with the anion group. Rz 1 ~ Rz 4 In cases where two or more of them combine to form a ring structure, the carbon atom forming the ring structure or the hydrogen atom bonded to the carbon atom may be substituted with the anion group.

[0780] In the above equation (d0-r-an1), Yd0 The 2-fold connector in the above is Yd in the above equation (d0). 0 It is identical to the connector of 2 in .

[0781] (D0) The number of anionic groups in the components may be 1 or 2 or more.

[0782] (D0) The component is an anion of value n as a whole. n is an integer greater than or equal to 1, preferably 1 or 2, and more preferably 1.

[0783] In the above equation (d0-an0), Rx 1 ~ Rx 4 , Ry 1 ~ Ry 2 and Rz 1 ~ Rz 4 At least one of them has the acid-degrading group described above. A preferred embodiment of the acid-degrading group is the same as the acid-degrading group described in formula (d0) above.

[0784] (D0) As for the anion part in the component, an anion represented by the following general formula (d0-an1) is more preferable in terms of acid diffusion inhibition.

[0785] [Chemical Formula 69]

[0786]

[0787] [In the food, Rx 5 ~ Rx 6 Each represents, independently, a hydrocarbon group or hydrogen atom that may have a substituent. Rx 7 ~ Rx 8 Each may independently represent a hydrocarbon group or hydrogen atom that may have a substituent, 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. Ry 1 ~ Ry 2Each may independently represent a hydrocarbon group or a hydrogen atom that may have a substituent, or may be bonded to each other to form a ring structure.

[0788] [Chemical Formula 70]

[0789]

[0790] is a double bond or a single bond. Rz 1 ~ Rz 4 Each may independently represent a hydrocarbon group or a hydrogen atom that may have a substituent, provided that the valence allows, or two or more may be bonded together to form a ring structure. However, Rx 5 ~ Rx 6 , Rx 7 ~ Rx 8 , Ry 1 ~ Ry 2 , or Rz 1 ~ Rz 4 Two or more of combine with each other to form a directional ring. Also, Rx 5 ~ Rx 8 , Ry 1 ~ Ry 2 and Rz 1 ~ Rz 4 At least one of them has an anion group represented by the following general formula (d0-r-an1), and the entire anion part becomes an anion of value n. Also, Rx 5 ~ Rx 8 , Ry 1 ~ Ry 2 and Rz 1 ~ Rz 4 At least one of them has an acid-degrading group. n is an integer greater than or equal to 1.

[0791] [Chemical Formula 71]

[0792]

[0793] [In the middle of the meal, Yd 0 is a 2-gauge connector or single bond. * indicates a bond loss.]

[0794] In the above equation (d0-an1), Rx 5 ~ Rx 6 Each represents, independently, a hydrocarbon group or hydrogen atom that may have a substituent. Rx 5 ~ Rx 6 The hydrocarbon group that may have a substituent in is Rx in the formula (d0-an0) described above. 1 ~ Rx 4 It is the same as the explanation for hydrocarbon groups that may have substituents in.

[0795] In the above equation (d0-an1), Rx 7 ~ Rx 8 Each of these may independently represent a hydrocarbon group or hydrogen atom that may have a substituent, or they may be bonded to each other to form a ring structure. Such Rx 7 ~ Rx 8 is Rx in the equation (d0-an0) described above. 1 ~ Rx 4 It is identical to the explanation for.

[0796] In the above equation (d0-an1), p is 1 or 2, and when p = 2, multiple Rx 7 ~ Rx 8 The values ​​may differ from each other. For an anion represented by the general formula (d0-an1), when p = 1, it has a bicycloheptane ring structure, and when p = 2, it has a bicyclooctane ring structure.

[0797] Among the above equation (d0-an1), Ry 1 ~ Ry 2 Each may independently represent a hydrocarbon group or hydrogen atom that may have a substituent, or they may be bonded to each other to form a ring structure. Such Ry 1 ~ Ry 2 is Ry in the above-described equation (d0-an0). 1 ~ Ry 2 It is the same as.

[0798] Rz 1 ~ Rz 4 Each may independently represent a hydrocarbon group or a hydrogen atom that may have a substituent, provided the valence allows, or two or more may be bonded together to form a ring structure. Such Rz 1 ~ Rz 4 is Rz in the equation (d0-an0) described above. 1 ~ Rz 4 It is the same as.

[0799] In the above equation (d0-an1), Rx 5 ~ Rx 6 , Rx 7 ~ Rx 8 , Ry 1 ~ Ry 2 , or Rz 1 ~ Rz 4 Two or more of these combine to form a directional ring. The directional ring is the same as that described in the above equation (d0).

[0800] In the above equation (d0-an1), Rx 5 ~ Rx 8 , Ry 1 ~ Ry 2 and Rz 1 ~ Rz 4 At least one of them has an anion group represented by the above formula (d0-r-an1), and the entire anion part becomes an anion of value n. n is an integer greater than or equal to 1, preferably 1 or 2, and more preferably 1.

[0801] In the above equation (d0-an1), Rx 5 ~ Rx 8 , Ry 1 ~ Ry 2 and Rz 1 ~ Rz 4 At least one of them has an acid-degrading group. A preferred embodiment of the acid-degrading group is the same as the acid-degrading group described in the above formula (d0).

[0802] Among the above, as for the anion part of the (D0) component, an anion represented by p = 2 in the above formula (d0-an1), that is, an anion represented by the following general formula (d0-an2), is more preferable.

[0803] [Chemical Formula 72]

[0804]

[0805] [In the food, Rx 5 ~ Rx 6 Each represents, independently, a hydrocarbon group or hydrogen atom that may have a substituent. Multiple Rx 7 ~ Rx 8 Each may independently represent a hydrocarbon group or hydrogen atom that may have a substituent, or two or more may be bonded together to form a ring structure. 1 ~ Ry 2 Each may independently represent a hydrocarbon group or a hydrogen atom that may have a substituent, or may be bonded to each other to form a ring structure.

[0806] [Chemical Formula 73]

[0807]

[0808] is a double bond or a single bond. Rz 1 ~ Rz 4 Each may independently represent a hydrocarbon group or a hydrogen atom that may have a substituent, provided that the valence allows, or two or more may be bonded together to form a ring structure. However, Rx 5 ~ Rx 6 , Rx 7 ~ Rx 8 2 or more of, Ry 1 ~ Ry 2 , or Rz 1 ~ Rz 4 Two or more of combine with each other to form a directional ring. Also, Rx 5 ~ Rx 8 , Ry1 ~ Ry 2 and Rz 1 ~ Rz 4 At least one of them has an anion group represented by the following general formula (d0-r-an1), and the entire anion part becomes an anion of value n. Also, Rx 5 ~ Rx 8 , Ry 1 ~ Ry 2 and Rz 1 ~ Rz 4 At least one of them has an acid-degrading group. n is an integer greater than or equal to 1.

[0809] [Chemical Formula 74]

[0810]

[0811] [In the middle of the meal, Yd 0 is a 2-gauge connector or single bond. * indicates a bond loss.]

[0812] In the above equation (d0-an2), Rx 5 ~ Rx 6 , Rx 7 ~ Rx 8 , Ry 1 ~ Ry 2 , Rz 1 ~ Rz 4 is Rx in the equation (d0-an1) described above. 5 ~ Rx 6 , Rx 7 ~ Rx 8 , Ry 1 ~ Ry 2 , Rz 1 ~ Rz 4 and are identical to each.

[0813] In the above equation (d0-an2), Rx 5 ~ Rx 6 , Rx 7 ~ Rx 8 2 or more of, Ry 1 ~ Ry 2 , or Rz 1 ~ Rz 4Two or more of these combine to form a directional ring. The directional ring is the same as that described in the above equation (d0).

[0814] In the above equation (d0-an2), Rx 5 ~ Rx 8 , Ry 1 ~ Ry 2 and Rz 1 ~ Rz 4 At least one of them has an anion group represented by the above formula (d0-r-an1), and the entire anion part becomes an anion of value n. n is an integer greater than or equal to 1, preferably 1 or 2, and more preferably 1.

[0815] In the above equation (d0-an2), Rx 5 ~ Rx 8 , Ry 1 ~ Ry 2 and Rz 1 ~ Rz 4 At least one of them has the acid-degrading group described above. A preferred embodiment of the acid-degrading group is the same as the acid-degrading group described in formula (d0) above.

[0816] Among the above equations (d0-an0), (d0-an1), and (d0-an2), Ry 1 ~ Ry 2 It is preferable that they combine to form a ring structure, and the ring structure formed is more preferably an aromatic hydrocarbon (aromatic ring, aromatic complex ring) that may have substituents.

[0817] Among the above equations (d0-an0), (d0-an1), and (d0-an2), Rz 1 ~ Rz 4 It is preferable that they combine with 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 bonded to Rz 3 and Rz 4A ring structure that shares a bond of carbon atoms is preferred, and an aromatic hydrocarbon (aromatic ring, aromatic complex ring) that may have substituents is more preferred.

[0818] Among the above equations (d0-an1) and (d0-an2), Rx 7 ~ Rx 8 It is preferable that they combine to form a ring structure, and the ring structure formed is more preferably an aromatic hydrocarbon (aromatic ring, aromatic complex ring) that may have substituents.

[0819] In the above equation (d0-an2), Rx 7 ~ Rx 8 The ring structure formed in is one side (Rx) of the six-membered ring in the formula 7 and Rx 8 A ring structure that shares a bond between the same carbon atoms is preferred, and an aromatic hydrocarbon (aromatic ring, aromatic complex ring) that may have substituents is more preferred.

[0820] For all anions represented by the above equation (d0-an2), such Rx 7 ~ Rx 8 , Ry 1 ~ Ry 2 , Rz 1 ~ Rz 4 In each of the above, the number of ring structures formed by combining with each other may be one or two or more, and two or three are preferred.

[0821] In this embodiment, the anion portion of component (D0) is particularly preferred to be an anion represented by the following general formula (d0-an3) in terms of CDU and resolution improvement.

[0822] [Chemical Formula 75]

[0823]

[0824] [In the food, Rx 5 ~ Rx6 Each represents, independently, a hydrocarbon group or hydrogen atom that may have a substituent.

[0825] [Chemical Formula 76]

[0826]

[0827] is a double bond or a single bond. Rz 1 ~ Rz 4 Each may independently represent a hydrocarbon group or a hydrogen atom that may have a substituent, provided that the valence allows, or two or more may be bonded together to form a ring structure. However, Rx 5 ~ Rx 6 and Rz 1 ~ Rz 4 At least one of them has an anion represented by the following general formula (d0-r-an1), and the entire anion part becomes an anion of value n. n is an integer greater than or equal to 1. Also, Rx 5 ~ Rx 6 and Rz 1 ~ Rz 4 At least one of them has an acid-degrading group. R 021 It is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, a carbonyl group, or a nitro group. n1 is an integer from 1 to 3. n11 is an integer from 0 to 8. R 022 is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, a carbonyl group, or a nitro group. n2 is an integer from 1 to 3. n21 is an integer from 0 to 8.

[0828] [Chemical Formula 77]

[0829]

[0830] [In the middle of the meal, Yd 0 is a 2-gauge connector or single bond. * indicates a bond loss.]

[0831] In the above equation (d0-an3), Rx 5 ~ Rx 6, Rz 1 ~ Rz 4 is Rx in the above equation (d0-an1). 5 ~ Rx 6 , Rz 1 ~ Rz 4 and are identical to each.

[0832] In the above equation (d0-an3), R 021 It is silver, an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, a carbonyl group, or a nitro group.

[0833] R 021 As for the alkyl group, an alkyl group having 1 to 5 carbon atoms is preferred, and a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group is more preferred.

[0834] R 021 As for the alkoxy group, an alkoxy group having 1 to 5 carbon atoms is preferred, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group are more preferred, and a methoxy group and an ethoxy group are even more preferred.

[0835] R 021 As for the halogen atom, a fluorine atom is preferred.

[0836] R 021 Examples of alkyl halide groups 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.

[0837] Among them, R 021 In terms of compatibility with component (A), alkyl groups, halogen atoms, and alkyl halides are preferred.

[0838] In the above formula (d0-an3), n1 is an integer from 1 to 3, preferably 1 or 2, and more preferably 1.

[0839] In the above formula (d0-an3), n11 is an integer from 0 to 8, preferably an integer from 0 to 4, more preferably 0, 1 or 2, and even more preferably 0 or 1.

[0840] In the above equation (d0-an3), R 022 is an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, a carbonyl group, or a nitro group, and each of the above R 021 One can cite the same as. Among them, R 022 In terms of compatibility with component (A), alkyl groups, halogen atoms, and alkyl halides are preferred.

[0841] In the above formula (d0-an3), n2 is an integer from 1 to 3, preferably 1 or 2, and particularly preferably 1.

[0842] In the above formula (d0-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.

[0843] However, among the above equation (d0-an3), Rx 5 ~ Rx 6 and Rz 1 ~ Rz 4 At least one of them has an anion group represented by the above formula (d0-r-an1), and the entire anion part becomes an anion of value n. n is an integer greater than or equal to 1, preferably 1 or 2, and more preferably 1.

[0844] In the above equation (d0-an3), Rx 5 ~ Rx 6 and Rz 1 ~ Rz 4 At least one of them has the acid-degrading group described above. A preferred embodiment of the acid-degrading group is the same as the acid-degrading group described in formula (d0) above.

[0845] Among the above equations (d0-an0), (d0-an1), (d0-an2), and (d0-an3), in that the effect of the present invention is excellent, the above Rz 1 ~ Rz 4 It is preferable that at least one of them has an anion group. The above Rz 1 ~ Rz 4 In cases where two or more of them combine to form a ring structure, the carbon atom forming the ring structure or the hydrogen atom bonded to the carbon atom may be substituted with the anion group.

[0846] Among the above equations (d0-an0), (d0-an1), (d0-an2), and (d0-an3), in that the effect of the present invention is excellent, the above Rz 1 ~ Rz 4 It is preferable that at least one of them has an acid-degrading group. The above Rz 1 ~ Rz 4 In cases where two or more of them combine to form a ring structure, the hydrogen atom bonded to the carbon atom forming the ring structure may be substituted with the acid-degrading group.

[0847] Specific examples of the anion portion of component (D0) are shown below.

[0848] [Chemical Formula 78]

[0849]

[0850] [Chemical Formula 79]

[0851]

[0852] [Chemical Formula 80]

[0853]

[0854] (D0) Among the above, an anion represented by any one of the chemical formulas (d0-an-1) to (d0-an-21) is preferred, an anion represented by any one of the chemical formulas (d0-an-1) to (d0-an-15) is more preferred, and an anion represented by any one of the chemical formulas (d0-an-1) to (d0-an-3), (d0-an-8), (d0-an-9), (d0-an-12), (d0-an-14), and (d0-an-15) is even more preferred.

[0855] {(D0) component cationic part}

[0856] Among the above general formula (d0), M m＋ represents an organic cation of m. Among these, sulfonium cations and iodonium cations are preferred.

[0857] m is an integer greater than or equal to 1.

[0858] M m＋ As for the organic cations, the same as the cations represented by the general formulas (ca-1) to (ca-5) can be preferably cited, and the cation represented by the general formula (ca-1) is more preferable.

[0859] In the resist composition of the present embodiment, the (D0) component is preferably a compound represented by the following general formula (d0-1).

[0860] [Chemical Formula 81]

[0861]

[0862] [In the food, Rx 1 ~ Rx 4 Each may independently represent a hydrocarbon group or hydrogen atom that may have a substituent, or two or more may be bonded together to form a ring structure. Ry 1 ~ Ry 2Each may independently represent a hydrocarbon group or a hydrogen atom that may have a substituent, or may be bonded to each other to form a ring structure.

[0863] [Chemical Formula 82]

[0864]

[0865] is a double bond or a single bond. Rz 1 ~ Rz 4 Each may independently represent a hydrocarbon group or a hydrogen atom that may have a substituent, provided that the valence allows, or two or more may be bonded together to form a ring structure. However, Rx 1 ~ Rx 4 2 or more of, Ry 1 ~ Ry 2 , or Rz 1 ~ Rz 4 At least one of the two or more of combines with each other to form a directional ring. Also, Rx 1 ~ Rx 4 , Ry 1 ~ Ry 2 and Rz 1 ~ Rz 4 At least one of them has an anion group represented by the following general formula (d0-r-an1), and the entire anion part becomes an anion of value n. Also, Rx 1 ~ Rx 4 , Ry 1 ~ Ry 2 and Rz 1 ~ Rz 4 At least one of them has the above acid-degrading group. n is an integer greater than or equal to 1. m is an integer greater than or equal to 1, wherein M m＋ represents an organic cation of m.

[0866] [Chemical Formula 83]

[0867]

[0868] [In the middle of the meal, Yd 0is a 2-gauge connector or single bond. * indicates a bond loss.]

[0869] The anion part of the compound represented by the above general formula (d0-1) is identical to the anion represented by the above general formula (d0-an0).

[0870] The acid-degradable group having the anion portion of the compound represented by the general formula (d0-1) is preferably the acid-degradable group represented by the general formula (pg-1). In the acid-degradable group represented by the general formula (pg-1), Rpg is preferably a cyclic acid-dissociable group, an acid-dissociable group represented by any one of the general formulas (pg-r-1) to (pg-r-3) is more preferable, and an acid-dissociable group represented by the general formula (pg-r-1) is even more preferable.

[0871] More specifically, it is preferable that Rpg is an acid-dissociable group represented by the general formula (a1-r2-1).

[0872] Yd in the above general formula (d0-r-an1) 0 As for the linker, a divalent linker including an ester link or a divalent linker including an ether link is preferred, and a linker represented by the general formula (y-d0-1) or (y-d0-2) is more preferred.

[0873] The cation part of the compound represented by the above general formula (d0-1) is identical to the cation part of the compound represented by the above general formula (d0).

[0874] (D0) Specific examples of components are given below, but are not limited to these.

[0875] [Chemical Formula 84]

[0876]

[0877] [Chemical Formula 85]

[0878]

[0879] In the resist composition of the present embodiment, the (D0) component may be used alone or in combination with two or more types.

[0880] In the resist composition of the present embodiment, the content of component (D0) is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of component (A), more preferably 1 to 15 parts by mass, and even more preferably 3 to 10 parts by mass.

[0881] (D0) If the content of the component is greater than or equal to the lower limit of the above-mentioned preferred range, the CDU and resolution are further improved in resist pattern formation. On the other hand, if it is less than or equal to the upper limit of the preferred range, the sensitivity can be maintained more effectively.

[0882] In the resist composition of the present embodiment, component (D) may contain a basic component other than the component (D0) described above.

[0883] Examples of basic components other than (D0) include a photodegradable base (D1) that decomposes upon exposure to light and loses its acid diffusion control ability (hereinafter referred to as "(D1) component"), a nitrogen-containing organic compound (D2) that does not correspond to the (D1) component (hereinafter referred to as "(D2) component"), etc.

[0884] · (D1) Regarding the component

[0885] As for the (D1) component, it is not particularly limited as long as it decomposes upon exposure to light and loses acid diffusion controllability, and one or more compounds selected from the group consisting of the compound represented by the following general formula (d1-1) (hereinafter referred to as the “(d1-1) component”), the compound represented by the following general formula (d1-2) (hereinafter referred to as the “(d1-2) component”), and the compound represented by the following general formula (d1-3) (hereinafter referred to as the “(d1-3) component”) are preferred.

[0886] Components (d1-1) to (d1-3) do not act as quenchers because they decompose in the exposed portion of the resist film and lose their acid diffusion control properties (basicity), but act as quenchers in the unexposed portion of the resist film.

[0887] [Chemical Formula 86]

[0888]

[0889] [In the middle of the meal, Rd 1 ~ Rd 4 is a cyclic group that may have substituents, a chain-type alkyl group that may have substituents, or a chain-type alkenyl group that may have substituents. provided that Rd in formula (d1-2) 2 In this case, it is assumed that no fluorine atoms are bonded to the carbon atoms adjacent to the S atoms. Yd 1 is a single coupling or a 2-valent connector. m is an integer greater than or equal to 1, where M m＋ Each is independently an organic cation of m.

[0890] {(d1-1) component}

[0891] ·· Anionbu

[0892] In Equation (d1-1), Rd 1 is a cyclic group that may have substituents, a chain-type alkyl group that may have substituents, or a chain-type alkenyl group that may have substituents, and each of the above R' 201 One can cite the same thing as.

[0893] Among these, Rd 1As for the group, an aromatic hydrocarbon group that may have a substituent, an aliphatic cyclic group that may have a substituent, or a chain-type alkyl group that may have a substituent is preferred. Substituents that may be present in these groups include hydroxyl groups, oxo groups, alkyl groups, aryl groups, fluorine atoms, fluorinated alkyl groups, lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-7), respectively, ether bonds, ester bonds, or combinations thereof. When ether bonds or ester bonds are included as substituents, an alkylene group may be interposed, and in this case, linking groups represented by the formulas (y-al-1) to (y-al-5), respectively, are preferred as substituents. Additionally, Rd 1 In the case where the aromatic hydrocarbon group, the aliphatic cyclic group, or the chain-type alkyl group has a linking group represented by the general formulas (y-al-1) to (y-al-7) respectively as a substituent, in the general formulas (y-al-1) to (y-al-7), Rd in formula (d3-1) 1 In the above, what is bonded to the carbon atom constituting the aromatic hydrocarbon group, the aliphatic cyclic group, or the chain-type alkyl group is V' in the general formulas (y-al-1) to (y-al-7). 101 am.

[0894] The above aromatic hydrocarbon group preferably includes a polycyclic structure comprising a phenyl group, a naphthyl group, and a bicyclooctane backbone (a polycyclic structure consisting of a bicyclooctane backbone and ring structures other than this).

[0895] The above-mentioned aliphatic cyclic group is more preferably a group obtained by removing one or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0896] The above chain-type alkyl group preferably has 1 to 10 carbon atoms, and specifically, examples include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups; and branched-chain alkyl groups such as 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, and 4-methylpentyl groups.

[0897] When the above chain-type alkyl group is a fluorinated alkyl group having a fluorine atom or 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 atoms. Examples of atoms other than fluorine atoms include oxygen atoms, sulfur atoms, nitrogen atoms, etc.

[0898] A preferred specific example of the anion portion of component (d1-1) is shown below.

[0899] [Chemical Formula 87]

[0900]

[0901] ·· Kationbu

[0902] In equation (d1-1), M m＋ is an organic cation of m.

[0903] M m＋ As for the organic cations, the same as the cations represented by the general formulas (ca-1) to (ca-5) above may be preferably cited, the cation represented by the general formula (ca-1) above is more preferable, and the cations represented by the formulas (ca-1-1) to (ca-1-72) above are even more preferable.

[0904] (d1-1) The ingredients may be used as a single type or in combination of two or more types.

[0905] {(d1-2) components}

[0906] ·· Anionbu

[0907] In equation (d1-2), Rd 2 is a cyclic group that may have substituents, a chain-type alkyl group that may have substituents, or a chain-type alkenyl group that may have substituents, and the above R' 201 One can cite the same thing as.

[0908] However, Rd 2 In this case, the carbon atom adjacent to the S atom is assumed not to have a fluorine atom bonded to it (not fluorine substituted). By doing so, the anion of component (d1-2) becomes a suitable weak acid anion, and the quenching ability as component (D) is improved.

[0909] Rd 2 It is preferable that the group be a chain-type alkyl group that may have substituents or an aliphatic cyclic group that may have substituents, and it is more preferable that the group be an aliphatic cyclic group that may have substituents.

[0910] The chain-type alkyl group preferably has 1 to 10 carbon atoms, and more preferably has 3 to 10 carbon atoms.

[0911] The aliphatic cyclic group is a group obtained by removing one or more hydrogen atoms from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. (it may have a substituent); it is more preferable that it is a group obtained by removing one or more hydrogen atoms from camphor.

[0912] Rd 2 The hydrocarbon group may have a substituent, and the substituent may be Rd of the above formula (d1-1). 1 Examples of substituents that may be present in the hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, chain-type alkyl group) include those that are identical to the hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, chain-type alkyl group).

[0913] (d1-2) Among the above, the anion part of the component is preferably a camphor sulfonic acid anion.

[0914] A preferred specific example of the anion portion of component (d1-2) is shown below.

[0915] [Chemical Formula 88]

[0916]

[0917] ·· Kationbu

[0918] In equation (d1-2), M m＋ is an organic cation of m, and M in the above formula (d1-1). m＋ It is the same as.

[0919] (d1-2) The ingredients may be used as a single type or in combination of two or more types.

[0920] {(d1-3) components}

[0921] ·· Anionbu

[0922] In equation (d1-3), Rd 3 is a cyclic group that may have substituents, a chain-type alkyl group that may have substituents, or a chain-type alkenyl group that may have substituents, and the above R' 201 Examples identical to the above may be given, and it is preferable that the cyclic group containing a fluorine atom, a chain-type alkyl group, or a chain-type alkenyl group. Among these, a fluorinated alkyl group is preferred, and the above Rd 1 It is more preferable that it be identical to the fluorinated alkyl group.

[0923] In equation (d1-3), Rd 4 is a cyclic group that may have substituents, a chain-type alkyl group that may have substituents, or a chain-type alkenyl group that may have substituents, and the above R' 201 One can cite the same thing as.

[0924] Among these, it is preferable that the alkyl group, alkoxy group, alkenyl group, or cyclic group be one that may have a substituent.

[0925] Rd 4 The alkyl group in the above is preferably a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms, and specifically, examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, etc. Rd 4 Some of the hydrogen atoms of the alkyl group may be substituted with hydroxyl groups, cyano groups, etc.

[0926] Rd 4 The alkoxy group in the above is preferably an alkoxy group having 1 to 5 carbon atoms, and specifically, examples of alkoxy groups having 1 to 5 carbon atoms include methoxy groups, ethoxy groups, n-propoxy groups, iso-propoxy groups, n-butoxy groups, and tert-butoxy groups. Among these, methoxy groups and ethoxy groups are preferred.

[0927] Rd 4 The alkenyl group in [the above] is the above R' 201 Examples of alkenyl groups include vinyl groups, propenyl groups (allyl groups), 1-methylpropenyl groups, and 2-methylpropenyl groups. These groups may additionally have alkyl groups having 1 to 5 carbon atoms or alkyl halide groups having 1 to 5 carbon atoms as substituents.

[0928] Rd 4 The ring-shaped device in the above R' 201 Examples include the same as the cyclic group in [the example], and an alicyclic group obtained by removing one or more hydrogen atoms from cycloalkanes such as cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, or an aromatic group such as a phenyl group or a naphthyl group is preferred. Rd 4 When A is a cycloaliphatic group, the resist composition dissolves well in organic solvents, thereby improving lithography characteristics. In addition, Rd 4In the case where the group is an aromatic group, in lithography using EUV or the like as an exposure light source, the resist composition has excellent light absorption efficiency and good sensitivity and lithography characteristics.

[0929] In equation (d1-3), Yd 1 It is a single bond or a two-linked connector.

[0930] Yd 1 Examples of divalent linkers in [formula] include, but are not particularly limited, divalent hydrocarbon groups that may have substituents (aliphatic hydrocarbon groups, aromatic hydrocarbon groups), divalent linkers containing heteroatoms, etc. These are each Ya in the above formula (a2-1). 21 Examples include divalent hydrocarbon groups that may have substituents, and divalent linkers containing heteroatoms, as exemplified in the description of divalent linkers in [the text].

[0931] Yd 1 The alkylene group is preferably a carbonyl group, an ester bond, an amide bond, an alkylene group, or a combination thereof. The alkylene group is more preferably a straight-chain or branched-chain alkylene group, and even more preferably a methylene group or an ethylene group.

[0932] A preferred specific example of the anion portion of component (d1-3) is shown below.

[0933] [Chemical Formula 89]

[0934]

[0935] [Chemical Formula 90]

[0936]

[0937] ·· Kationbu

[0938] In equation (d1-3), M m＋ is an organic cation of m, and M in the above formula (d1-1). m＋ It is the same as.

[0939] (d1-3) The ingredients may be used as a single type or in combination of two or more types.

[0940] (D1) For the component, any one of the above components (d1-1) to (d1-3) may be used, or two or more may be used in combination.

[0941] When the resist composition contains component (D1), the content of component (D1) in the resist composition is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of component (A1), and more preferably 0.5 to 5 parts by mass.

[0942] (D1) If the content of the component is above a desirable lower limit, particularly good lithography characteristics and resist pattern shape are easily obtained. On the other hand, if it is below an upper limit, good sensitivity can be maintained and throughput is excellent.

[0943] (D1) Method of manufacturing the component:

[0944] The method of manufacturing the above components (d1-1) and (d1-2) is not particularly limited and can be manufactured by known methods.

[0945] In addition, the method of preparing component (d1-3) is not particularly limited and, for example, is prepared in the same manner as the method described in US2012-0149916.

[0946] · (D2) Regarding the component

[0947] (D) As a component, it may contain a nitrogen-containing organic compound component that does not correspond to the above (D1) component (hereinafter referred to as “(D2) component”).

[0948] As for the (D2) component, it is not particularly limited as long as it acts as an acid diffusion control agent and does not correspond to the (D1) component, and any known one may be used. Among these, an aliphatic amine is preferred, and among these, a secondary aliphatic amine or a tertiary aliphatic amine is more preferred.

[0949] 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.

[0950] Examples of aliphatic amines include amines (alkylamines or alkyl alcoholamines) in which at least one hydrogen atom of ammonia NH3 is substituted with an alkyl group or hydroxyalkyl group having 12 or fewer carbon atoms, or cyclic amines.

[0951] 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 5 to 10 carbon atoms are more preferred, and tri-n-pentylamine or tri-n-octylamine is particularly preferred.

[0952] Examples of cyclic amines include, for instance, heterocyclic compounds containing a nitrogen atom as a heteroatom. The heterocyclic compound may be a monocyclic type (aliphatic monocyclic amine) or a polycyclic type (aliphatic polycyclic amine).

[0953] Examples of aliphatic monocyclic amines include piperidine and piperazine.

[0954] As for aliphatic polycyclic amines, it is preferable that the number of carbon atoms is 6 to 10, and specifically, examples include 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, hexamethylenetetramine, 1,4-diazabicyclo[2.2.2]octane.

[0955] 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., and triethanolamine triacetate is preferred.

[0956] Also, as the (D2) component, an aromatic amine may be used.

[0957] Examples of aromatic amines include 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or derivatives thereof, tribenzylamine, 2,6-diisopropylaniline, N-tert-butoxycarbonylpyrrolidine, etc.

[0958] Among the above, the component (D2) is preferably an alkylamine, and a trialkylamine having 5 to 10 carbon atoms is more preferably.

[0959] (D2) One type of ingredient may be used alone, or two or more types may be used in combination.

[0960] When the resist composition contains component (D2), the content of component (D2) in the resist composition is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of component (A1), more preferably 0.1 to 5 parts by mass, and even more preferably 0.5 to 5 parts by mass.

[0961] (D2) If the content of the component is above a desirable lower limit, particularly good lithography characteristics and resist pattern shape are easily obtained. On the other hand, if it is below an upper limit, good sensitivity can be maintained and throughput is excellent.

[0962] Among the total amount of component (D) contained in the resist composition of the present embodiment, the content of component (D0) is preferably 50 mass% or more, more preferably 70 mass% or more, and even more preferably 90 mass% or more, and component (D) may consist only of component (D0).

[0963] <Other ingredients>

[0964] The resist composition of the present embodiment may additionally contain other components in addition to the components (A), (B), and (D) described above. Examples of other components include the components (E), (F), and (S) shown below.

[0965] ≪At least one compound (E) selected from the group consisting of organic carboxylic acids, phosphoric oxo acids, and derivatives thereof≫

[0966] The resist composition of the present embodiment may contain, as an optional component, at least one compound (E) selected from the group consisting of organic carboxylic acids, phosphoric oxo acids, and derivatives thereof, for the purpose of preventing sensitivity degradation or improving the shape of the resist pattern and stability over time after exposure (hereinafter referred to as “component (E)”).

[0967] As organic carboxylic acids, specifically, acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, etc., and among them, salicylic acid is preferred.

[0968] Phosphoric oxo acids include phosphoric acid, phosphonic acid, phosphinic acid, etc., and among these, phosphonic acid is particularly preferred.

[0969] Derivatives of phosphorus oxoacid include, for example, esters in which a hydrogen atom of the oxoacid is substituted with a hydrocarbon group, and the hydrocarbon group may include an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 15 carbon atoms, etc.

[0970] Examples of phosphoric acid derivatives include phosphate esters such as di-n-butyl phosphate and diphenyl phosphate.

[0971] Derivatives of phosphonic acid include phosphonic acid esters such as phosphonic acid dimethyl ester, phosphonic acid di-n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, and phosphonic acid dibenzyl ester.

[0972] Examples of derivatives of phosphinic acid include phosphinic acid esters and phenylphosphinic acid.

[0973] In the resist composition of the present embodiment, component (E) may be used alone or two or more types may be used in combination.

[0974] 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 (A). By keeping it within the above range, the lithography characteristics are further improved.

[0975] ≪Fluorine Additive Ingredients (F)≫

[0976] The resist composition of the present embodiment may contain a fluorine additive component (hereinafter referred to as “(F) component”) to impart water repellency to the resist film or to improve lithography properties.

[0977] (F) As a component, 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 may be used.

[0978] (F) More specifically as a component, a polymer having a constituent unit (f1) represented by the following general formula (f1-1) may be cited. The polymer is preferably a polymer (homopolymer) consisting only of the constituent unit (f1) represented by the following formula (f1-1); a copolymer of the constituent unit (f1) and the constituent unit (a1); and a copolymer of the constituent unit (f1), a constituent unit derived from acrylic acid or methacrylic acid, and the constituent unit (a1), and more preferably a copolymer of the constituent unit (f1) 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 or 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.

[0979] [Chemical Formula 91]

[0980]

[0981] [In the formula, R is the same as above, and Rf 102 and Rf 103Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms, and Rf 102 and Rf 103 It may be the same or different. nf 1 is an integer from 0 to 5, and Rf 101 It is an organic group containing a fluorine atom.

[0982] In formula (f1-1), R bonded to the carbon atom at the α position is the same as above. As R, a hydrogen atom or a methyl group is preferred.

[0983] In Equation (f1-1), Rf 102 and Rf 103 As the halogen atom, a fluorine atom is preferred. Rf 102 and Rf 103 As for the alkyl group having 1 to 5 carbon atoms, examples include the same as the alkyl group having 1 to 5 carbon atoms of R, and a methyl group or an ethyl group is preferred. Rf 102 and Rf 103 As an alkyl halide group having 1 to 5 carbon atoms, specifically, a group in which some or all of the hydrogen atoms of an alkyl group having 1 to 5 carbon atoms are substituted with a halogen atom may be used. As the halogen atom, a fluorine atom is preferred. Among these, Rf 102 and Rf 103 As for the group, a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms is preferred, a hydrogen atom, a fluorine atom, a methyl group, or an ethyl group is more preferred, and a hydrogen atom is even more preferred.

[0984] In equation (f1-1), nf 1 is an integer from 0 to 5, preferably an integer from 0 to 3, and more preferably 1 or 2.

[0985] In Equation (f1-1), Rf 101It is preferable that it be an organic group containing fluorine atoms, or a hydrocarbon group containing fluorine atoms.

[0986] The hydrocarbon group containing fluorine atoms may be of any straight chain type, branched chain type, or ring type, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 15, and particularly preferably 1 to 10.

[0987] In addition, regarding the hydrocarbon group containing fluorine atoms, it is preferable that 25% or more of the hydrogen atoms in the hydrocarbon group are fluorinated, more preferable that 50% or more are fluorinated, and particularly preferable that 60% or more are fluorinated, in that the hydrophobicity of the resist film during immersion exposure is increased.

[0988] Among them, Rf 101 For the group, a fluorinated hydrocarbon group having 1 to 6 carbon atoms is more preferable, and a trifluoromethyl group, -CH2-CF3, -CH2-CF2-CF3, -CH(CF3)2, -CH2-CH2-CF3, -CH2-CH2-CF2-CF2-CF2-CF3 is particularly preferred.

[0989] (F) The weight average molecular weight (Mw) of the component (based on polystyrene equivalent 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 the value is below the upper limit of this range, there is sufficient solubility in a solvent for resist to use as a resist, and if the value is above the lower limit of this range, the water repellency of the resist film is good.

[0990] (F) The dispersion (Mw / Mn) of the component is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.0 to 2.5.

[0991] In the resist composition of the present embodiment, component (F) may be used alone or two or more types may be used in combination.

[0992] When the resist composition contains component (F), the content of component (F) is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of component (A), and more preferably 1 to 10 parts by mass.

[0993] ≪Organic Solvent Components (S)≫

[0994] The resist composition of the present embodiment can be prepared by dissolving a resist material in an organic solvent component (hereinafter referred to as "(S) component").

[0995] (S) As for the component, it is sufficient to dissolve each component used to form a homogeneous solution, and any one of those known as solvents for chemically amplified resist compositions can be appropriately selected and used.

[0996] (S) As components, for example, lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol; compounds having ester bonds such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; derivatives of polyhydric alcohols such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, or compounds having ether bonds such as monophenyl ether [among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred]; Examples include cyclic ethers such as dioxane, esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate; aromatic organic solvents such as anisole, ethylbenzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetol, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, mesitylene, and dimethyl sulfoxide (DMSO).

[0997] In the resist composition of the present embodiment, component (S) may be used as a single type or as a mixture of two or more solvents. Among these, PGMEA, PGME, γ-butyrolactone, EL, and cyclohexanone are preferred.

[0998] In addition, as for the (S) component, a mixed solvent comprising PGMEA and a polar solvent is also preferred. The mixing ratio (mass ratio) can be appropriately determined by considering the compatibility between PGMEA and the polar solvent, but preferably, it is within the range of 1:9 to 9:1, and more preferably 2:8 to 8:2.

[0999] More specifically, when EL or cyclohexanone is incorporated as a polar solvent, the mass ratio of PGMEA to EL or cyclohexanone is preferably 1:9 to 9:1, more preferably 2:8 to 8:2. Also, when PGME is incorporated as a polar solvent, the mass ratio of PGMEA to PGME is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, and even more preferably 3:7 to 7:3. Additionally, a mixed solvent of PGMEA, PGME, and cyclohexanone is also preferred.

[1000] In addition, as a (S) component, a mixed solvent of at least one selected from PGMEA and EL and γ-butyrolactone is also preferred. In this case, the mass ratio of the former to the latter is preferably 70:30 to 95:5.

[1001] The amount of component (S) used is not particularly limited and is appropriately set according to the thickness of the coating film 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 within the range of 0.1 to 20 mass%, preferably 0.2 to 15 mass%.

[1002] The resist composition of the present embodiment may additionally contain, as desired, miscible additives, such as additional resins for improving the performance of the resist film, dissolution inhibitors, plasticizers, stabilizers, colorants, anti-halation agents, dyes, etc.

[1003] The resist composition of the present embodiment may be purified by dissolving the resist material in component (S) and then removing impurities, etc., using a polyimide porous membrane, a polyamideimide porous membrane, etc. For example, the resist composition may be purified by using a filter made of a polyimide porous membrane, a filter made of a polyamideimide porous membrane, a filter made of a polyimide porous membrane and a polyamideimide porous membrane, etc. Examples of the polyimide porous membrane and the polyamideimide porous membrane include, for instance, those described in Japanese Patent Publication No. 2016-155121.

[1004] The resist composition of the present embodiment described above contains a compound (D0) represented by the general formula (d0) ((D0) component).

[1005] (D0) component has a specific bulky structure in the anion portion (a condensation ring type group including a condensation ring containing one or more directional rings). As a result, the uniformity of (D0) component within the resist film is increased, and acid generated from component (B) at the boundary between the exposed and unexposed portions of the resist film is trapped by component (D0) without bias.

[1006] Additionally, the acid-degradable group of the anion portion of component (D0) is detached from the acid-dissociable group constituting the acid-degradable group in the exposure portion of the resist film, thereby generating a polar group. As a result, the hydrophobicity of component (D0) is reduced, and the affinity between component (D0) and the developer (alkali developer) is improved.

[1007] Therefore, it is presumed that the resist composition of the present embodiment containing component (D0) can form a resist pattern with good CDU and resolution.

[1008] (Resist pattern formation method)

[1009] A method for forming a resist pattern related to a second aspect of the present invention comprises a process of forming a resist film on a support using a resist composition related to a first aspect of the present invention described above, a process of exposing the resist film to light, and a process of developing the resist film after exposure to form a resist pattern.

[1010] One embodiment of such a resist pattern formation method is a resist pattern formation method carried out as follows.

[1011] First, the resist composition of the above-described embodiment is applied onto a support using a spinner or the like, and a bake (post-applied 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.

[1012] Next, regarding the resist film, selective exposure is performed using an exposure device such as an electron beam lithography device or an ArF exposure device, for example, by exposure with a mask (mask pattern) having a predetermined pattern formed therein or by lithography by direct irradiation of 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 condition of, for example, 80 to 150 ℃.

[1013] Next, the above resist film is developed. In the case of an alkaline development process, an alkaline developer is used for the development process, and in the case of a solvent development process, a developer containing an organic solvent (organic developer) is used.

[1014] After the development process, a rinsing treatment is preferably performed. For the rinsing treatment, 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.

[1015] In the case of a solvent development process, after the above development or rinsing treatment, the developer or rinsing solution attached to the pattern may be removed using a supercritical fluid.

[1016] Drying is performed after developing or rinsing. In addition, in some cases, baking (post-baking) may be performed after the above developing process.

[1017] In this way, a resist pattern can be formed.

[1018] The support material is not particularly limited and may use conventionally known materials; examples include substrates for electronic components or substrates having a predetermined wiring pattern formed thereon. More specifically, examples include silicon wafers, metal substrates such as copper, chrome, iron, and aluminum, or glass substrates. For the material of the wiring pattern, examples include copper, aluminum, nickel, and gold.

[1019] In addition, as a support, an inorganic and / or organic film may be formed on a substrate as described above. Examples of inorganic films include inorganic anti-reflective films (inorganic BARC). Examples of organic films include organic anti-reflective films (organic BARC) or organic films such as the lower organic film in a multilayer resist method.

[1020] Here, the multilayer resist method is a method of forming at least one organic film (lower organic film) and at least one resist film (upper resist film) on a substrate, and performing patterning of the lower organic film using the resist pattern formed on the upper resist film as a mask, and it is said that a pattern with a high aspect ratio can be formed. That is, according to the multilayer resist method, since the required thickness can be secured by the lower organic film, the resist film can be made thin, and it becomes possible to form a fine pattern with a high aspect ratio.

[1021] The multilayer resist method is basically divided into a method having a two-layer structure of an upper resist film and a lower organic film (two-layer resist method) and a method having a multilayer structure of three or more layers with one or more intermediate layers (such as metal thin films) formed between the upper resist film and the lower organic film (three-layer resist method).

[1022] The wavelength used for exposure is not particularly limited and can be carried out using radiation such as an ArF excimer laser, a KrF excimer laser, an F2 excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray, or soft X-ray. The above resist composition is highly useful for a KrF excimer laser, an ArF excimer laser, EB, or EUV, is even more useful for an ArF excimer laser, EB, or EUV, and is particularly useful for EB or EUV. That is, the resist pattern forming method of the present embodiment is a particularly useful method when the process of exposing the resist film includes an operation of exposing the resist film to EUV (extreme ultraviolet) or EB (electron beam).

[1023] The method of exposing the resist film may be a conventional exposure (dry exposure) performed in an inert gas such as air or nitrogen, or a liquid immersion lithography, but liquid immersion lithography is preferred.

[1024] Immersion exposure is an exposure method in which the space between the resist film and the lens at the lowest position of the exposure device is filled with a solvent (immersion medium) having a refractive index greater than that of air, and exposure (immersion exposure) is performed in that state.

[1025] As for the immersion medium, a solvent having a refractive index greater than that of air and smaller than that of the resist film being exposed is preferred. The refractive index of such a solvent is not particularly limited as long as it falls within the above range.

[1026] Examples of solvents having a refractive index greater than that of air and smaller than that of the resist film include water, fluorine-based inert liquids, silicon-based solvents, hydrocarbon-based solvents, etc.

[1027] Specific examples of fluorine-based inert liquids include liquids having fluorine-based compounds such as C3HCl2F5, C4F9OCH3, C4F9OC2H5, and C5H3F7 as the main component, and preferably have a boiling point of 70 to 180°C, and more preferably 80 to 160°C. If the fluorine-based inert liquid has a boiling point within the above range, it is desirable in that the medium used for immersion can be removed in a simple manner after the exposure is finished.

[1028] As for fluorine-based inert liquids, perfluoroalkyl compounds in which all hydrogen atoms of an alkyl group are replaced by fluorine atoms are particularly preferred. Specific examples of perfluoroalkyl compounds include perfluoroalkyl ether compounds and perfluoroalkylamine compounds.

[1029] In addition, specifically, the perfluoroalkyl ether compound may be perfluoro(2-butyl-tetrahydrofuran) (boiling point 102 °C), and the perfluoroalkylamine compound may be perfluorotributylamine (boiling point 174 °C).

[1030] Water is preferably used as an immersion medium from the perspectives of cost, safety, environmental issues, and versatility.

[1031] Examples of alkaline developers used for development in the alkaline development process include, for instance, an aqueous solution of 0.1 to 10 mass% tetramethylammonium hydroxide (TMAH).

[1032] The organic solvent contained in the organic developer used for development treatment in the solvent development process may be one capable of dissolving component (A) (component (A) prior to exposure) and may be appropriately selected from known organic solvents. Specifically, examples include polar solvents such as ketone-based solvents, ester-based solvents, alcohol-based solvents, nitrile-based solvents, amide-based solvents, and ether-based solvents, as well as hydrocarbon-based solvents.

[1033] Ketone solvents are organic solvents containing CC(=O)-C in their structure. Ester solvents are organic solvents containing CC(=O)-OC in their structure. Alcohol solvents are organic solvents containing alcoholic hydroxyl groups in their structure. "Alcoholic hydroxyl group" refers to a hydroxyl group bonded to a carbon atom of an aliphatic hydrocarbon group. Nitrile solvents are organic solvents containing nitrile groups in their structure. Amid solvents are organic solvents containing amide groups in their structure. Ether solvents are organic solvents containing COC in their structure.

[1034] Among organic solvents, there are also organic solvents that contain multiple types of functional groups in their structure that characterize each of the above solvents; in such cases, they shall be considered to correspond to any solvent type containing the functional groups possessed by the said organic solvent. For example, diethylene glycol monomethyl ether shall be considered to correspond to either the alcohol-based solvent or the ether-based solvent among the above classifications.

[1035] Hydrocarbon solvents are hydrocarbon solvents composed of hydrocarbons that may be halogenated and do not have substituents other than halogen atoms. As for the halogen atom, fluorine atoms are preferred.

[1036] Among the organic solvents contained in the organic developer, polar solvents are preferred, and ketone-based solvents, ester-based solvents, nitrile-based solvents, etc. are preferred.

[1037] Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutylketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonyl acetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthyl ketone, isophorone, propylene carbonate, γ-butyrolactone, methylamyl ketone (2-heptanone), etc. Among these, methylamyl ketone (2-heptanone) is preferred as a ketone solvent.

[1038] Ester-based solvents include, for example, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate. Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, Examples include propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, etc. Among these, butyl acetate is preferred as an ester-based solvent.

[1039] Examples of nitrile-based solvents include acetonitrile, propionitrile, valeronitrile, butyronitrile, etc.

[1040] In organic developer solutions, known additives may be incorporated as needed. Examples of such additives include surfactants. Surfactants are not particularly limited, but examples include ionic or nonionic fluorine-based and / or silicone-based surfactants. As for the surfactant, nonionic surfactants are preferred, and nonionic fluorine-based surfactants or nonionic silicone-based surfactants are more preferred.

[1041] When a surfactant is incorporated, the amount incorporated is typically 0.001 to 5 mass% with respect to the total amount of the organic developer, preferably 0.005 to 2 mass%, and more preferably 0.01 to 0.5 mass%.

[1042] Development processing can be carried out by known development methods, such as a method of immersing a support in a developer solution for a certain period of time (dip method), a method of paving the developer solution onto the surface of the support by surface tension and stopping it for a certain period of time (paddle method), a method of spraying the developer solution onto the surface of the support (spray method), and a method of continuously dispensing the developer solution while scanning a developer solution dispensing nozzle at a certain speed onto a support rotating at a certain speed (dynamic dispensing method).

[1043] As for the organic solvent contained in the rinse solution used for the rinsing treatment after the development treatment in the solvent development process, for example, among the organic solvents exemplified as organic solvents used in the organic developer solution, one that is difficult to dissolve the resist pattern may be appropriately selected and used. Typically, at least one type of solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is used. Among these, at least one type selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, and amide solvents is preferred, at least one type selected from alcohol solvents and ester solvents is more preferred, and alcohol solvents are particularly preferred.

[1044] The alcohol-based solvent used in the rinse solution is preferably a monohydric alcohol having 6 to 8 carbon atoms, and the monohydric alcohol may be of any straight-chain, branched, or cyclic form. Specifically, examples include 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, benzyl alcohol, etc. Among these, 1-hexanol, 2-heptanol, and 2-hexanol are preferred, and 1-hexanol and 2-hexanol are more preferred.

[1045] These organic solvents may be used individually or in combination of two or more types. In addition, they may be used in combination with other organic solvents or water. However, considering the development characteristics, the amount of water in the rinsing solution is preferably 30 mass% or less, more preferably 10 mass% or less, even more preferably 5 mass% or less, and particularly preferably 3 mass% or less with respect to the total amount of the rinsing solution.

[1046] In the rinse solution, known additives may be incorporated as needed. Examples of such additives include surfactants. The surfactants may be the same as those mentioned above, and nonionic surfactants are preferred, and nonionic fluorine-based surfactants or nonionic silicone-based surfactants are more preferred.

[1047] When a surfactant is incorporated, the amount incorporated is typically 0.001 to 5 mass% with respect to the total amount of the rinse liquid, preferably 0.005 to 2 mass%, and more preferably 0.01 to 0.5 mass%.

[1048] Rinsing treatment (cleaning treatment) using a rinsing solution can be carried out by known rinsing methods. Examples of such rinsing treatment methods include a method of continuously applying a rinsing solution onto a support rotating at a constant speed (rotary application method), a method of immersing the support in a rinsing solution for a certain period of time (dip method), and a method of spraying a rinsing solution onto the surface of the support (spray method).

[1049] According to the resist pattern forming method of the present embodiment described above, since the resist composition described above is used, a resist pattern with good CDU and resolution can be formed.

[1050] (compound)

[1051] The compound related to the third aspect of the present invention is a compound represented by the following general formula (d0).

[1052] [Chemical Formula 92]

[1053]

[1054] [In the middle of the meal, Rd 0 Yd is a condensed cyclic group comprising a condensed ring containing one or more aromatic rings. The condensed cyclic group has, as a substituent, an acid-degrading group that decomposes upon the action of an acid to generate a polar group. 0It is a 2-valent connector or single bond. M m＋ represents an organic cation of valence m. m is an integer greater than or equal to 1.

[1055] The compound represented by the above general formula (d0) is identical to the component (D0) in the resist composition related to the first aspect of the present invention described above.

[1056] [Method for preparing a compound represented by general formula (d0)]

[1057] (D0) The component can be manufactured using a known method.

[1058] As a specific method for manufacturing component (D0), a method for manufacturing a compound represented by the general formula (d'0), which is an example of component (D0), is shown below.

[1059] First, a compound X1 represented by the following general formula (X-1) is reacted with a compound (Alc-1) represented by the following general formula (Alc-1) having a desired acid dissociable group (Rpg) to obtain a compound (D0pre) represented by the following general formula (D0pre) (Process 1).

[1060] Next, by performing a salt exchange reaction between compound (D0pre) and compound (S-1) represented by the following general formula (S-1) in the presence of a base, a compound represented by general formula (d'0), which is an example of component (D0), can be obtained (second process).

[1061] In addition, in the following reaction scheme, for convenience, "RpgO-C=O-Rd 00 Although it is expressed as 」, 「RpgO-C=O-Rd 00 」 is "Rd in general formula (d0) 0 This is an example of 」.

[1062] [Chemical Formula 93]

[1063]

[1064] [In the middle of the meal, Rd 00... is a condensed ring type group comprising a condensed ring containing one or more aromatic rings. Rpg is an acid-dissociable group represented by the general formula (pg-r-1) described above, an acid-dissociable group represented by the general formula (pg-r-2), an acid-dissociable group represented by the general formula (pg-r-3), or an acid-dissociable group represented by the general formula (pg-r-4). Z - is a halogen ion. (M m＋ ) 1 / m represents an organic cation of valence m. m is an integer greater than or equal to 1.

[1065] Process 1:

[1066] The first process is, for example, a process of dissolving compound (X-1) and compound (Alc-1) in an organic solvent (THF, etc.) and carrying out a reaction in the presence of a base to obtain compound (D0pre).

[1067] Specifically, examples of such bases include sodium hydride, K2CO3, Cs2CO3, lithium diisopropylamide (LDA), triethylamine, 4-dimethylaminopyridine, etc.

[1068] The reaction temperature is, for example, 0 to 50 ℃, and the reaction time is, for example, 10 minutes or more and 24 hours or less.

[1069] Among the above formulas, Rd 00 It is a condensation ring type including a condensation ring comprising one or more directional rings, and Rd in the general formula (d0). 0 It is identical to a condensation ring type that includes one or more directional rings.

[1070] Process 2:

[1071] The second process is, for example, a process of reacting a compound (D0pre) and a salt exchange compound (S-1) in the presence of a solvent such as water, dichloromethane, acetonitrile, or chloroform, and a base to obtain a compound represented by the general formula (d'0), which is an example of a component (D0).

[1072] Specifically, examples of such bases include sodium hydride, K2CO3, Cs2CO3, lithium diisopropylamide (LDA), triethylamine, 4-dimethylaminopyridine, etc.

[1073] Among the above formulas, Z - Specifically, examples include bromide ions, chloride ions, etc.

[1074] The reaction temperature is, for example, 0 to 100°C, and the reaction time is, for example, 10 minutes or more and 24 hours or less.

[1075] Among the above formulas, (M m＋ ) 1 / m is (M in the above general formula (d0). m＋ ) 1 / m It is identical to.

[1076] After the salt exchange reaction is completed, the compound in the reaction solution may be isolated and purified. Conventionally known methods may be used for isolation and purification, and, for example, a combination of concentration, solvent extraction, distillation, crystallization, recrystallization, chromatography, etc. may be used.

[1077] The structure of the compound obtained as described above is, 1 H-nuclear magnetic resonance (NMR) spectroscopy, 13 C-NMR spectral method, 19 It can be identified by general organic analysis methods such as F-NMR spectroscopy, infrared absorption (IR) spectroscopy, mass spectrometry (MS), elemental analysis, and X-ray crystal diffraction.

[1078] (D0) In the method for manufacturing a component, between the first and second processes, a process may be included in which a compound (D0pre) is reacted with a hydroxy acid to obtain a compound represented by the general formula (D0pre) which is different from the compound (D0pre).

[1079] Specifically, examples of such hydroxy acids include compounds represented by the following chemical formula (K-1) and compounds represented by the following chemical formula (K-2).

[1080] [Chemical Formula 94]

[1081]

[1082] In addition, the method for manufacturing component (D0) may include a process of reacting the compound (D0pre) obtained by the first process above with a diol such as ethylene glycol to obtain an intermediate, and reacting the obtained intermediate with a dicarboxylic acid such as oxalic acid to obtain a compound represented by the general formula (D0pre) which is different from the compound (D0pre).

[1083] The raw materials used in each process may be commercially available or synthesized.

[1084] For example, when synthesizing compound (X-1), compound (X-1) can be obtained by carrying out a Diels-Alder reaction with an aromatic compound (e.g., anthracene) and an alkene (e.g., maleic anhydride).

[1085] The compound related to the third aspect of the present invention described above is a compound useful as an acid diffusion control agent in the resist composition related to the first aspect of the present invention described above.

[1086] (Acid diffusion control agent)

[1087] The acid diffusion control agent related to the fourth aspect of the present invention comprises the compound related to the third aspect described above.

[1088] Such acid diffusion control agents are useful as acid diffusion control agents for chemically amplified resist compositions.

[1089] The compound related to the third embodiment described above has a carboxylate anion in the anion portion, and therefore generates a relatively weak acid upon exposure compared to the fluorinated alkylsulfonate anion, etc., in the anion portion of the acid generating agent generally used in chemically amplified resist compositions.

[1090] By using such acid diffusion control agents in chemically amplified resist compositions, CDU and resolution performance are further improved in resist pattern formation. By using such acid generating agent components, CDU and resolution performance are further improved, particularly in resist pattern formation using EB or EUV light sources.

[1091] Examples

[1092] The present invention will be explained in more detail below by way of examples, but the present invention is not limited by these examples.

[1093] In this embodiment, the compound represented by the chemical formula (X-1-1) is denoted as "compound (X-1-1)", and compounds represented by other chemical formulas are denoted in the same way.

[1094] <Preparation of Compound (X-1)>

[1095] (Preparation Example 1-1)

[1096] Anthracene (20.0 g, 112.2 mmol), maleic anhydride (16.6 g, 168.3 mmol), aluminum chloride (1.50 g, 11.2 mmol), and toluene (200 g) were added to a 300 mL three-necked flask and reacted at 80 °C for 4 hours under stirring. After cooling, ultrapure water (155 g) was added and stirred for 30 minutes, after which the precipitated solid was filtered. The filtrate was dissolved again in a mixed solvent of THF (93 g) and methylene chloride (680 g), washed three times with ultrapure water (155 g), and the organic layer was concentrated using a rotary evaporator. The concentrate was recrystallized with ethyl acetate to obtain compound (X-1-1).

[1097] [Chemical Formula 95]

[1098]

[1099] (Preparation Example 1-2)

[1100] Compound (X-1-2) was obtained in the same manner as the preparation example of compound (X-1-1), except that anthracene (20.0 g, 112.2 mmol) was changed to 2,3,6,7-tetramethylanthracene (26.3 g, 108.6 mmol).

[1101] [Chemical Formula 96]

[1102]

[1103] <Preparation of Compound (DOpre)>

[1104] (Preparation Example 2-1)

[1105] In a 500 mL three-necked flask, a THF / hexane solution of 1.06 M lithium diisopropylamide (LDA) (87 mL, 92.3 mmol) was added and cooled to 5 °C. Then, a solution of 1-methylcyclopentanol (10.9 g, 108.6 mmol) dissolved in THF (30 g) was added and reacted for 2 hours at 5 °C or below. After that, a solution of compound (X1-1) (15.0 g, 54.3 mmol) dissolved in THF (225 g) was added and reacted for 2 hours at 5 °C or below. The reaction mixture was added to ultrapure water (205 g) over 30 minutes, then diheptane (205 g) was added, stirred for 30 minutes, and the organic layer was removed. After washing the aqueous layer three times with heptane (100 g), tert-butylmethyl ether (MTBE) (150 g) and a 10% aqueous citric acid solution (205 g, 106.1 mmol) were added and stirred for 30 minutes, after which the aqueous layer was removed. The recovered organic layer was washed three times with ultrapure water (150 g) and the organic layer was concentrated using a rotary evaporator. The concentrate was recrystallized with ethyl acetate to obtain compound (D0pre-01).

[1106] [Chemical Formula 97]

[1107]

[1108] (Preparation Example 2-2)

[1109] Compound (D0pre-08) was obtained in the same manner as the preparation example of compound (D0pre-01), except that compound (X-1-1) (15.0 g, 54.3 mmol) was changed to compound (X-1-2) (18.1 g, 54.3 mmol).

[1110] [Chemical Formula 98]

[1111]

[1112] (Preparation Example 2-3)

[1113] Compound (D0pre-06) was obtained in the same manner as the preparation example of compound (D0pre-01), except that 1-methylcyclopentanol (10.9 g, 108.6 mmol) was changed to t-butyl alcohol (8.0 g, 108.6 mmol).

[1114] [Chemical Formula 99]

[1115]

[1116] (Preparation Example 2-4)

[1117] Compound (D0pre-07) was obtained in the same manner as the preparation example of compound (D0pre-01), except that 1-methylcyclopentanol (10.9 g, 108.6 mmol) was changed to 2-methyl-2-adamantanol (18.1 g, 108.6 mmol).

[1118] [Chemical Formula 100]

[1119]

[1120] (Preparation Example 2-5)

[1121] Compound (D0pre-01) (11.0 g, 29.2 mmol), compound (K-1) (3.2 g, 32.1 mmol), and dichloromethane (170 g) were added to a 300 mL three-necked flask and dissolved by stirring at room temperature. Next, diisopropylcarbodiimide (4.1 g, 32.1 mmol) and dimethylaminopyridine (0.045 g, 0.4 mmol) were added and reacted at room temperature for 5 hours. The reaction mixture was filtered, and the filtrate was concentrated using a rotary evaporator. The concentrate was dissolved in acetonitrile (30 g), added dropwise to MTBE (180 g), and the precipitated solid was filtered. The filtrate was dissolved again in acetonitrile (30 g), added dropwise to MTBE (180 g), and the precipitated solid was filtered. After repeating this operation twice, the compound (D0pre-02) was obtained by drying the filtrate under reduced pressure.

[1122] [Chemical Formula 101]

[1123]

[1124] (Preparation Example 2-6)

[1125] Compound (D0pre-03) was obtained in the same manner as the preparation example of compound (D0pre-02), except that compound (K-1) (3.2 g, 32.1 mmol) was changed to compound (K-2) (5.6 g, 32.1 mmol).

[1126] [Chemical Formula 102]

[1127]

[1128] (Preparation Example 2-7)

[1129] Compound (D0pre-04) was obtained in the same manner as the preparation example of compound (D0pre-02), except that compound (K-1) (3.2 g, 32.1 mmol) was changed to compound (K-3) (2.4 g, 32.1 mmol).

[1130] [Chemical Formula 103]

[1131]

[1132] (Preparation Example 2-8)

[1133] Compound (D0pre-05pre) was obtained in the same manner as the preparation example of compound (D0pre-02), except that compound (K-1) (3.2 g, 32.1 mmol) was changed to ethylene glycol (2.0 g, 32.1 mmol).

[1134] [Chemical Formula 104]

[1135]

[1136] Next, compound (D0pre-05pre) (9.0 g, 21.4 mmol), oxalic acid (2.1 g, 23.5 mmol), and dichloromethane (95 g) were added to a 300 mL three-necked flask and dissolved by stirring at room temperature. Next, diisopropylcarbodiimide (3.0 g, 23.5 mmol) and dimethylaminopyridine (0.033 g, 0.3 mmol) were added and reacted at room temperature for 5 hours. The reaction mixture was filtered, and the filtrate was concentrated using a rotary evaporator. The concentrate was dissolved in acetonitrile (15 g), added dropwise to MTBE (80 g), and the precipitated solid was filtered. The filtrate was again dissolved in acetonitrile (15 g), added dropwise to MTBE (80 g), and the precipitated solid was filtered. After repeating this operation twice, the compound (D0pre-05) was obtained by drying the filtrate under reduced pressure.

[1137] [Chemical Formula 105]

[1138]

[1139] <Preparation of Compound (D0)>

[1140] (Preparation Example 3-1)

[1141] Compound (D0pre-01) (3.0 g, 8.0 mmol) and compound (S-1-1) (2.86 g, 8.4 mmol) were dissolved in dichloromethane (50 g), a 5% aqueous solution of tetramethylammonium hydroxide (TMAH) (14.5 g) was added, and the mixture was reacted at room temperature for 30 minutes. After the reaction was finished, the aqueous phase was removed, and the organic phase was washed 5 times with ultrapure water (15.0 g). The organic phase was concentrated and dried using a rotary evaporator to obtain compound (D0-01).

[1142] [Chemical Formula 106]

[1143]

[1144] (Preparation Examples 3-2 to 3-11)

[1145] Compounds (D0-02) to (D0-11) shown below were obtained by making the same as the above "Example of Preparation of Compound (D0-01)", except that the combination of compound (D0pre-01) and salt exchange compound (S-1-1) in the above "Example of Preparation of Compound (D0-01)" was changed to the compounds (D0pre-01) to (D0pre-08) described above and the salt exchange compounds (S-1-1) to (S-1-4) below.

[1146] The structures of compounds (D0-01) to (D0-11) are shown below.

[1147] [Chemical Formula 107]

[1148]

[1149] [Chemical Formula 108]

[1150]

[1151] [Chemical Formula 109]

[1152]

[1153] In addition, the structures of the compounds (D0-01) to (D0-11) described above are shown below. 1 It was identified from the analysis results of H-NMR measurements.

[1154] Compound (D0-01): Combination of compound (D0pre-01) and salt exchange compound (S-1-1)

[1155]

[1156] Compound (D0-02): Combination of compound (D0pre-02) and salt exchange compound (S-1-1)

[1157]

[1158] Compound (D0-03): Combination of compound (D0pre-03) and salt exchange compound (S-1-1)

[1159]

[1160] Compound (D0-04): Combination of compound (D0pre-04) and salt exchange compound (S-1-1)

[1161]

[1162] Compound (D0-05): Combination of compound (D0pre-05) and salt exchange compound (S-1-1)

[1163]

[1164] Compound (D0-06): Combination of compound (D0pre-06) and salt exchange compound (S-1-1)

[1165]

[1166] Compound (D0-07): Combination of compound (D0pre-07) and salt exchange compound (S-1-1)

[1167]

[1168] Compound (D0-08): Combination of compound (D0pre-08) and salt exchange compound (S-1-1)

[1169]

[1170] Compound (D0-09): Combination of Compound (D0pre-05) and Salt Exchange Compound (S-1-2)

[1171]

[1172] Compound (D0-10): Combination of compound (D0pre-04) and salt exchange compound (S-1-4)

[1173]

[1174] Compound (D0-11): Combination of compound (D0pre-01) and salt exchange compound (S-1-3)

[1175]

[1176] <Preparation of Resist Composition>

[1177] (Examples 1 to 13, Comparative Examples 1 to 4)

[1178] Each component shown in Tables 1 and 2 was mixed and dissolved to prepare the resist composition for each example.

[1179]

[1180]

[1181] In Tables 1 and 2, each abbreviation has the following meaning. The numbers in [ ] are the mixing amount (parts by mass).

[1182] (A)-1: A polymer compound represented by the following chemical formula (A1)-1. For this polymer compound (A1)-1, the weight-average molecular weight (Mw) equivalent to standard polystyrene obtained by GPC measurement is 7100, and the molecular weight dispersion (Mw / Mn) is 1.69. 13 The copolymer composition ratio (ratio of each constituent unit in the structural formula (molar ratio)) obtained by C-NMR is l / m = 50 / 50.

[1183] (A)-2: A polymer compound represented by the following chemical formula (A1)-2. For this polymer compound (A1)-2, the weight-average molecular weight (Mw) equivalent to standard polystyrene obtained by GPC measurement is 7000, and the molecular weight dispersion (Mw / Mn) is 1.72. 13 The copolymer composition ratio (ratio of each constituent unit in the structural formula (molar ratio)) obtained by C-NMR is l / m = 50 / 50.

[1184] [Chemical Formula 110]

[1185]

[1186] (B)-1: An acid-generating agent composed of the following compound (B1-1).

[1187] (B)-2: An acid-generating agent composed of the following compound (B1-2).

[1188] [Chemical Formula 111]

[1189]

[1190] (D0)-1 ~ (D0)-11: Each acid diffusion control agent composed of the above compounds (D0-01) ~ (D0-11).

[1191] (D1)-1 ~ (D1)-4: Each acid diffusion control agent composed of the following compounds (D1-1) ~ (D1-4).

[1192] (S)-1 : A mixed solvent of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 60 / 40 (mass ratio).

[1193] [Chemical Formula 112]

[1194]

[1195] <Formation of Resist Pattern>

[1196] A resist composition of each example was applied to an 8-inch silicon substrate treated with hexamethyldisilazane (HMDS) using a spinner, and a pre-bake (PAB) treatment was performed on a hot plate at a temperature of 110°C for 60 seconds, and then dried to form a resist film with a thickness of 50 nm.

[1197] Next, regarding the above resist film, an electron beam lithography device JEOL-JBX-9300FS (manufactured by Nippon Electronics Co., Ltd.) was used to perform lithography (exposure) at an acceleration voltage of 100 kV to form a contact hole pattern (hereinafter referred to as the "CH pattern") in which holes with a diameter of 32 nm were arranged at equal intervals (pitch 64 nm). After that, a heating (PEB) treatment was performed after exposure at 110°C for 60 seconds.

[1198] Next, at 23°C, an alkaline reaction was performed for 60 seconds using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) “NMD-3” (product name, manufactured by Tokyo Ohka Industrial Co., Ltd.).

[1199] After that, a water rinse was performed for 15 seconds using pure water.

[1200] As a result, a CH pattern was formed with holes of diameter 32 nm spaced at equal intervals (pitch 64 nm).

[1201] [Evaluation of In-plane Uniformity of Pattern Dimensions (CDU)]

[1202] With respect to the CH pattern formed by the above <Formation of Resist Pattern>, the hole diameter (nm) of each hole was measured by observing the CH pattern from above using a measuring SEM (scanning electron microscope, acceleration voltage 500 V, product name: CG5000, manufactured by Hitachi High-Tech Corporation). Then, a value (3σ) of three times the standard deviation (σ) calculated from the measurement results was obtained. The result is shown in Table 3 as "CDU (nm)".

[1203] The 3σ obtained in this way means that the smaller the value, the higher the uniformity of the dimensions (CD) of the multiple holes formed in the resist film.

[1204] [Assessment of Limit Resolution]

[1205] The limiting resolution at the optimal exposure amount (Eop) at which the above CH pattern is formed, specifically the hole diameter (nm) of the pattern that is resolved when the exposure amount is gradually reduced from the optimal exposure amount (Eop) to form the CH pattern, was determined using a scanning electron microscope S-9380 (manufactured by Hitachi High-Tech Corporation). The results are shown in Table 3 as "limiting resolution (nm)".

[1206]

[1207] As shown in Table 3, it was confirmed that the resist composition of the example could form a resist pattern with good CDU and limiting resolution compared to the resist composition of the comparative example.

[1208] As a result of confirming the effect according to the difference in the anion portion of the (D0) component by comparing Examples 1 to 8, the resist compositions containing the (D0) component of Examples 2, 4, and 5, in particular, had superior CDU and limit resolution.

[1209] In comparison of the (D0) components contained in the resist compositions of Examples 1 and 6, in which only the acid dissociation group of the (D0) component is different, the acid dissociation group of the anionic portion of the (D0) component of Example 1, which is a monocyclic alicyclic group, has a higher dissociation ability of the acid dissociation group compared to the chain-type acid dissociation group of the anionic portion of the (D0) component of Example 6, it is presumed that the (D0) component of Example 1 was able to improve affinity with the developer more.

[1210] In comparison of the (D0) components contained in the resist compositions of Examples 1 and 7, in which only the acid dissociation group of the (D0) component is different, the acid dissociation group of the anionic portion of the (D0) component of Example 1, which is a monocyclic alicyclic group, is moderately less hydrophobic compared to the acid dissociation group of the anionic portion of the (D0) component of Example 7, so it is presumed that the (D0) component of Example 1 was able to improve affinity with the developer while maintaining uniformity within the resist film.

[1211] In comparison of the (D0) component contained in the resist compositions of Examples 1 and 8, which differ only in the acid dissociation properties of the (D0) component, the non-cyclooctane backbone of the anionic part of the (D0) component of Example 1 has a moderately lower hydrophobicity compared to the non-cyclooctane backbone of the anionic part of the (D0) component of Example 8 having four methyl groups, so it is presumed that the (D0) component of Example 1 was able to improve affinity with the developer while maintaining uniformity within the resist film.

Claims

Claim 1 A resist composition that generates acid upon exposure and changes solubility in a developer solution upon the action of the acid, comprising a substrate component (A) whose solubility in a developer solution changes upon the action of the acid, an acid generating agent component (B) that generates acid upon exposure, and an acid diffusion controlling agent component (D) that controls the diffusion of acid generated from the acid generating agent component (B) upon exposure, wherein the acid diffusion controlling agent component (D) comprises a compound (D0) represented by the following general formula (d0). [In the middle of the meal, Rd 0 The polycyclic aromatic ring is a polycyclic aromatic ring formed by the multiple condensation of aromatic hydrocarbon rings, or an aromatic hydrocarbon ring-aliphatic hydrocarbon ring condensed ring formed by the condensation of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring. The polycyclic aromatic ring and the aromatic hydrocarbon ring-aliphatic hydrocarbon ring condensed ring may have, as a substituent, an acid-degradable group represented by the following general formula (pg-1), and may have an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, a nitro group, or a carbonyl group. Yd 0 It is a 2-valent connector or single bond. M m＋ represents an organic cation of valence m. m is an integer greater than or equal to 1. [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 bonding hand.] [In equation (pg-r-1), Rd 1 ~ Rd 3 Rd, each independently, as a hydrocarbon group 1 and Rd 2 They may combine with each other to form a ring. In Equation (pg-r-2), Rd 001 Yd is a straight-chain or branched-chain aliphatic hydrocarbon group. 002 is a single coupling or a two-way connector. Rd 002 is a hydrogen atom or a substituent. 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), Xd is a secondary carbon atom. X is an alicyclic hydrocarbon ring that may have substituents. Ar is a benzene ring or a naphthalene ring. Rm 02 is a substituent. n02 is an integer from 1 to 4. In equation (pg-r-4), Rd' 1 , Rd' 2 is a hydrogen atom or an alkyl group. Rd' 3 As a hydrocarbon group, Rd' 3 Eun, Rd' 1 , Rd' 2 It may form a ring by combining with any of the following.* indicates the bond loss with the oxygen atom (-O-) in the above general formula (pg-1). Claim 2 A resist composition according to claim 1, wherein the acid diffusion control agent component (D) comprises a compound represented by the following general formula (d0-1). [In the food, Rx 1 ~ Rx 4 Each may independently represent an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, a nitro group, or a hydrocarbon group or hydrogen atom that may have a carbonyl group, or two or more may be bonded together to form a ring structure. 1 ~ Ry 2 Each may independently represent an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, a nitro group, or a hydrocarbon group or hydrogen atom having a carbonyl group, or may be bonded to each other to form a ring structure. is a double bond or a single bond. Rz 1 ~ Rz 4 Each may independently represent, where valence permits, an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, a nitro group, or a hydrocarbon group or hydrogen atom that may have a carbonyl group, or two or more may be bonded together to form a ring structure. However, Rx 1 ~ Rx 4 2 or more of, Ry 1 ~ Ry 2 , or Rz 1 ~ Rz 4 At least one of the two or more of combines with each other to form a directional ring. Also, Rx 1 ~ Rx 4 , Ry 1 ~ Ry 2 and Rz 1 ~ Rz 4 At least one of them has an anion group represented by the following general formula (d0-r-an1), and the entire anion part becomes an anion of value n. Also, Rx 1 ~ Rx 4 , Ry 1 ~ Ry 2 and Rz 1 ~ Rz 4 At least one of them has an acid-degrading group represented by the above general formula (pg-1). n is an integer greater than or equal to 1. m is an integer greater than or equal to 1, wherein M m＋ represents an organic cation of m. [In the middle of the meal, Yd 0 is a 2-gauge connector or single bond. * indicates a bond loss.] Claim 3 delete Claim 4 A method for forming a resist pattern, comprising: a process of forming a resist film on a support using a resist composition described in claim 1; a process of exposing the resist film to light; and a process of developing the resist film after exposure to form a resist pattern. Claim 5 A compound represented by the following general formula (d0). [In the middle of the meal, Rd 0 The polycyclic aromatic ring is a polycyclic aromatic ring formed by the multiple condensation of aromatic hydrocarbon rings, or an aromatic hydrocarbon ring-aliphatic hydrocarbon ring condensed ring formed by the condensation of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring. The polycyclic aromatic ring and the aromatic hydrocarbon ring-aliphatic hydrocarbon ring condensed ring may have, as a substituent, an acid-degradable group represented by the following general formula (pg-1), and may have an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, a nitro group, or a carbonyl group. Yd 0 It is a 2-valent connector or single bond. M m＋ represents an organic cation of valence m. m is an integer greater than or equal to 1. [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 bonding hand.] [In equation (pg-r-1), Rd 1 ~ Rd 3 Rd, each independently, as a hydrocarbon group 1 and Rd 2 They may combine with each other to form a ring. In Equation (pg-r-2), Rd 001 Yd is a straight-chain or branched-chain aliphatic hydrocarbon group. 002 is a single coupling or a two-way connector. Rd 002 is a hydrogen atom or a substituent. 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), Xd is a secondary carbon atom. X is an alicyclic hydrocarbon ring that may have substituents. Ar is a benzene ring or a naphthalene ring. Rm 02 is a substituent. n02 is an integer from 1 to 4. In equation (pg-r-4), Rd' 1 , Rd' 2 is a hydrogen atom or an alkyl group. Rd' 3 As a hydrocarbon group, Rd' 3 Eun, Rd' 1 , Rd' 2 It may form a ring by combining with any of the following.* indicates the bond loss with the oxygen atom (-O-) in the above general formula (pg-1). Claim 6 An acid diffusion control agent comprising the compound described in claim 5.

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