Resist composition, resist pattern forming method, and compound

Abstract

To provide a resist composition good in all of sensitivity, CDU and resolution, a resist pattern forming method using the resist composition, and a compound used in the resist composition.SOLUTION: The resist composition contains a compound containing a cation (C0) represented by formula (c0) (where Z+ represents S+ or I+; Ar1, Ar2 and Ar3 represent aromatic rings; I represents an iodine atom; Rz11, Rz21 and Rz31 represent C1-5 alkyl groups; and lz1, lz2, lz3, mz1, mz2, mz3, nz1, nz2 and nz3 represent integers of 0 or more, provided that at least one of lz1, mz1 and nz1 represents an integer of 1 or more and at least one of lz2, mz2 and nz2 represents an integer of 1 or more).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resist composition, a method for forming a resist pattern, and a compound.

Background Art

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

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

[0004] In the formation of a resist pattern, the behavior of the acid generated from the acid generator component upon exposure is also regarded as a factor that greatly affects lithography characteristics. On the other hand, it has been proposed to use an acid diffusion controller that controls the diffusion of the acid generated from the acid generator component upon exposure together with the acid generator component.

[0005] For example, Patent Document 1 discloses a resist composition that employs a compound composed of a sulfonate anion containing an aromatic ring having an iodine atom or a bromine atom and a triphenylsulfonium cation having two or more fluorine atoms or a perfluoroalkyl group as an acid generator component.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] As the miniaturization of resist patterns progresses, for example, in lithography using EUV or EB, the formation of fine patterns with a size of several tens of nm is targeted. Along with such miniaturization of resist patterns, improvements in lithography-specific properties such as sensitivity, roughness, and resolution have become issues. However, these lithography properties are usually in a trade-off relationship, and when any one of the properties is improved, the other properties tend to deteriorate. In a resist composition, it is required to improve sensitivity, roughness, and resolution without sacrificing any of them.

[0008] The present invention has been made in view of the above circumstances, and an object thereof is to provide a resist composition having good sensitivity, CDU, and resolution, a resist pattern forming method using the resist composition, and a compound used in the resist composition.

Means for Solving the Problems

[0009] In order to solve the above problems, the present invention employs the following configuration. That is, a first aspect of the present invention is a resist composition that generates an acid upon exposure and whose solubility in a developer changes by the action of the acid, and contains a compound containing a cation (C0) represented by the following general formula (c0).

[0010]

Chemical Formula

[0011] A second aspect of the present invention is a resist pattern forming method including a step of forming a resist film on a support using the resist composition according to the first aspect, a step of exposing the resist film, and a step of developing the exposed resist film to form a resist pattern.

[0012] A third aspect of the present invention is a compound containing a cation (C0) represented by the general formula (c0).

Effects of the Invention

[0013] According to the present invention, it is possible to provide a resist composition having good sensitivity, CDU, and resolution, a resist pattern forming method using the resist composition, and a compound used in the resist composition.

Modes for Carrying Out the Invention

[0014] In this specification and the claims of this patent, "aliphatic" is a relative concept with respect to aromatic, and is defined to mean a group, compound, etc. that does not have aromaticity. Unless otherwise specified, the "alkyl group" shall include linear, branched, and cyclic monovalent saturated hydrocarbon groups. The same applies to the alkyl group in the alkoxy group. Unless otherwise specified, the "alkylene group" shall include linear, branched, and cyclic divalent saturated hydrocarbon groups. Examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The "structural unit" means a monomer unit (monomeric unit) that constitutes a high molecular compound (resin, polymer, copolymer). When it is described as "may have a substituent", it includes both the case of substituting a hydrogen atom (-H) with a monovalent group and the case of substituting a methylene group (-CH 2 -) with a divalent group. "Exposure" is a concept that includes the entire irradiation of radiation.

[0015] The "acid-decomposable group" is a group having acid-decomposability such that at least a part of the bonds in the structure of the acid-decomposable group can be cleaved by the action of an acid. Examples of the acid-decomposable group whose polarity increases by the action of an acid include a group that decomposes by the action of an acid to generate a polar group. Examples of the polar group include a carboxy group, a hydroxy group, an amino group, a sulfo group (-SO 3 H), etc. More specifically, examples of the acid-decomposable group include a group in which the polar group is protected by an acid-dissociable group (for example, a group in which a hydrogen atom of an OH-containing polar group is protected by an acid-dissociable group).

[0016] The "acid-dissociable group" means both (i) a group having acid-dissociability such that the bond between the acid-dissociable group and the atom adjacent to the acid-dissociable group can be cleaved by the action of an acid, or (ii) a group in which, after a part of the bonds are cleaved by the action of an acid, a decarboxylation reaction further occurs, whereby the bond between the acid-dissociable group and the atom adjacent to the acid-dissociable group can be cleaved. The acid-dissociable group constituting the acid-decomposable group needs to be a group with a lower polarity than the polar group generated by the dissociation of the acid-dissociable group. Thus, when the acid-dissociable group dissociates by the action of an acid, a polar group with a higher polarity than the acid-dissociable group is generated and the polarity increases. As a result, the polarity of the entire component (A1) increases. By increasing the polarity, relatively, the solubility in the developer changes. When the developer is an alkaline developer, the solubility increases, and when the developer is an organic developer, the solubility decreases.

[0017] The "base material component" is an organic compound having a film-forming ability. The organic compounds used as the base material component are roughly classified into non-polymers and polymers. As the non-polymer, those having a molecular weight of 500 or more and less than 4000 are usually used. Hereinafter, in the case of "low molecular compound", it means a non-polymer having a molecular weight of 500 or more and less than 4000. As the polymer, those having a molecular weight of 1000 or more are usually used. Hereinafter, in the case of "resin", "high molecular compound" or "polymer", it means a polymer having a molecular weight of 1000 or more. As the molecular weight of the polymer, the weight average molecular weight in terms of polystyrene by GPC (gel permeation chromatography) shall be used.

[0018] The "derived structural unit" means a structural unit formed by the cleavage of a multiple bond between carbon atoms, for example, an ethylenic double bond. In the "acrylic acid ester", the hydrogen atom bonded to the α-position carbon atom may be substituted with a substituent. The substituent (R αx ) is an atom or group other than a hydrogen atom. Also, it shall include itaconic acid diesters in which the substituent (R αx ) is substituted with a substituent containing an ester bond, and α-hydroxyacrylic esters in which the substituent (R αx ) is substituted with a hydroxyalkyl group or a group obtained by modifying its hydroxyl group. In addition, the α-position carbon atom of the acrylic acid ester means the carbon atom to which the carbonyl group of acrylic acid is bonded, unless otherwise specified. Hereinafter, an acrylate in which a hydrogen atom bonded to a carbon atom at the α-position is substituted with a substituent may be referred to as an α-substituted acrylate.

[0019] The term "derivative" refers to a concept that includes those in which a hydrogen atom at the α-position of the target compound is substituted with another substituent such as an alkyl group or a halogenated alkyl group, and derivatives thereof. Examples of such derivatives include those in which a hydrogen atom of the hydroxyl group of the target compound, which may have a hydrogen atom at the α-position substituted with a substituent, is substituted with an organic group; those in which a substituent other than a hydroxyl group is bonded to the target compound, which may have a hydrogen atom at the α-position substituted with a substituent, and the like. Here, the α-position refers to the first carbon atom adjacent to the functional group, unless otherwise specified. Examples of the substituent that substitutes the hydrogen atom at the α-position of hydroxystyrene include the same ones as R αx and the like.

[0020] In this specification and the claims of the present patent, depending on the structure represented by a chemical formula, there may be an asymmetric carbon, and enantiomers or diastereomers may exist. In that case, those isomers are represented by one chemical formula. Those isomers may be used alone or as a mixture.

[0021] (Resist composition) The resist composition according to the first aspect of the present invention generates an acid upon exposure, and the solubility in a developer changes by the action of the acid. Such a resist composition contains a compound containing a cation (C0) represented by the general formula (c0) (hereinafter, also referred to as "compound (C)"). Compound (C) may be a base material component (A) (hereinafter, also referred to as "(A) component") whose solubility in a developer changes by the action of an acid. Compound (C) may be an acid generator component (B) (hereinafter, also referred to as "(B) component") that generates an acid upon exposure. Compound (C) may be an acid diffusion control agent component (D) (hereinafter, also referred to as "(D) component") that traps the acid generated upon exposure (that is, controls the diffusion of the acid).

[0022] The resist composition of this embodiment has an acid generating ability to generate an acid upon exposure, and the component (A) may generate an acid upon exposure, and the component (B) may generate an acid upon exposure. Specifically, the resist composition of this embodiment may contain (1) the component (B) as a component that generates an acid upon exposure; (2) the component (A) may be a component that generates an acid upon exposure; (3) the component (A) may be a component that generates an acid upon exposure and may contain the component (B). That is, in the cases of (2) and (3) above, the component (A) becomes a "base material component that generates an acid upon exposure and whose solubility in a developer changes due to the action of the acid". When the component (A) is a base material component that generates an acid upon exposure and whose solubility in a developer changes due to the action of the acid, it is preferable that the component (A1) described later is a polymer compound that generates an acid upon exposure and whose solubility in a developer changes due to the action of the acid. As such a polymer compound, a resin having a structural unit that generates an acid upon exposure can be used. As the structural unit that generates an acid upon exposure, known ones can be used.

[0023] When a resist film is formed using the resist composition of this embodiment and selective exposure is performed on the resist film, an acid is generated from the component (A) or the component (B) in the exposed portion of the resist film, and due to the action of the acid, the solubility of the component (A) in the developer changes, while in the unexposed portion of the resist film, the solubility of the component (A) in the developer does not change. Therefore, a difference in solubility in the developer occurs between the exposed portion and the unexposed portion. Therefore, when the resist film is developed, when the resist composition is positive, the exposed portion of the resist film is dissolved and removed to form a positive resist pattern, and when the resist composition is negative, the unexposed portion of the resist film is dissolved and removed to form a negative resist pattern.

[0024] In this specification, a resist composition in which the exposed portion of the resist film is dissolved and removed to form a positive resist pattern is referred to as a positive resist composition, and a resist composition in which the unexposed portion of the resist film is dissolved and removed to form a negative resist pattern is referred to as a negative resist composition. The resist composition of this embodiment may be a positive resist composition or a negative resist composition. Further, the resist composition of this embodiment may be for an alkali development process using an alkali developer for the development process during resist pattern formation, or may be for a solvent development process using a developer containing an organic solvent (organic-based developer) for the development process.

[0025] <Compound (C) containing cation (C0)> The resist composition of this embodiment contains a compound (C) containing a cation (C0) represented by the following general formula (c0).

[0026] [Chemical formula] [In the formula, Z + represents S + or I + . Ar 1 , Ar 2 and Ar 3 each independently represent an aromatic ring. I is an iodine atom. Rz 11 , Rz 21 and Rz 31 each independently represent an alkyl group having 1 to 5 carbon atoms. Rz 12 , Rz 22 and Rz 32 each independently represent a substituent. Rz 12 , Rz 22 and Rz 32 are bonded to each other to form Z in the formula + , Ar 1 , Ar 2 and Ar 3It may form a condensed ring together. lz1, lz2, lz3, mz1, mz2, mz3, nz1, nz2 and nz3 are each independently an integer of 0 or more as long as the valence permits. However, at least one of lz1, mz1 and nz1 is an integer of 1 or more, and at least one of lz2, mz2 and nz2 is an integer of 1 or more. Z + is S + in the case of, nz31 is 1, and Z + is I + in the case of, nz31 is 0. ]

[0027] In the formula (c0), Z + is preferably S + .

[0028] In the formula (c0), Ar 1 , Ar 2 and Ar 3 The aromatic rings in include unsubstituted aryl groups having 6 to 20 carbon atoms, preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.

[0029] In the formula (c0), the alkyl group having 1 to 5 carbon atoms in Rz 11 , Rz 21 and Rz 31 is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably a linear or branched alkyl group having 1 to 3 carbon atoms, and still more preferably a methyl group, an ethyl group or an isopropyl group.

[0030] Rz 12 , Rz 22 and Rz 32 The substituents in are not particularly limited as long as they are groups that substitute the hydrogen atoms of the aromatic rings in Ar 1 , Ar 2 and Ar 3 in the formula (c0). Examples of the substituent include a hydroxy group, a hydroxyalkyl group, an alkoxy group, a carbonyl group, a carboxy group, an acyl group, an ester group, an alkyl group, a fluorine atom, a bromine atom, a halogenated alkyl group, a cyano group, an amino group, a nitro group and the like. As the hydroxyalkyl group, those having 1 to 6 carbon atoms are preferable, those having 1 to 5 carbon atoms are more preferable, those having 1 to 3 carbon atoms are still more preferable, and those having 1 or 2 carbon atoms are particularly preferable. The alkyl group in the hydroxyalkyl group may be linear or branched. The number of hydroxy groups in the hydroxyalkyl group is preferably 1 to 3, more preferably 1 or 2, and still more preferably 1. Specific examples of the hydroxyalkyl group include a methylol group and an ethyrol group. As the alkoxy group, those having 1 to 6 carbon atoms are preferable, those having 1 to 5 carbon atoms are more preferable, those having 1 to 3 carbon atoms are still more preferable, and those having 1 or 2 carbon atoms are particularly preferable. The alkyl group in the alkoxy group may be linear or branched. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group. As the acyl group, those having 1 to 6 carbon atoms are preferable, those having 1 to 5 carbon atoms are more preferable, those having 1 to 3 carbon atoms are still more preferable, and those having 1 or 2 carbon atoms are particularly preferable. The alkyl group in the acyl group may be linear or branched. A specific example of the acyl group includes an acetyl group. As the ester group, a group represented by -COOR y (R y being an alkyl group) is preferable. The ester group preferably has 1 to 6 carbon atoms, more preferably 1 to 5 carbon atoms, still more preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms. The alkyl group in the above R y may be linear or branched. A specific example of the ester group includes a methyl ester group. The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 5 carbon atoms, still more preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms. The alkyl group may be linear or branched. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and the like.

[0031] Among them, Rz 12 、Rz 22 and Rz32 As the substituent in

[0032] Rz 12 Rz 22 and Rz 32 are mutually bonded to form Z in the formula + Ar 1 Ar 2 and Ar 3 to form a condensed ring together, as the group formed by the linkage of any two of Rz 12 Rz 22 and Rz 32 there may be mentioned a single bond, an alkylene group having 1 to 3 carbon atoms, a carbonyl group (-C(=O)-), an ether bond (-O-), an ester bond (-O-C(=O)-, -C(=O)-O-), etc.

[0033] In the formula (c0), lz1, mz1 and nz1 are preferably integers from 0 to 3, more preferably integers from 0 to 2, and still more preferably 0 or 1.

[0034] In the formula (c0), lz2, mz2 and nz2 are preferably integers from 0 to 3, more preferably integers from 0 to 2, and still more preferably 0 or 1.

[0035] In the formula (c0), lz3, mz3 and nz3 are preferably integers from 0 to 2, more preferably 0 or 1, and still more preferably 0.

[0036] In the formula (c0), when an iodine atom (I) is bonded to the aromatic ring in Ar 1 Ar 2 or Ar 3 the aromatic ring may or may not be bonded to an acyl group -C(=O)-Rz 11 -C(=O)-Rz 12 or -C(=O)-Rz 13 but it is preferably not bonded. That is, the aromatic ring in Ar 1 Ar 2 or Ar 3 is the aromatic ring with an iodine atom (I) and an acyl group -C(=O)-Rz 11, -C(=O)-Rz 12 or -C(=O)-Rz 13 is preferably bonded to different aromatic rings. For example, when lz1 is an integer of 1 or more, lz2 is 0, and it is preferable that mz2 or nz2 is an integer of 1 or more.

[0037] Specific examples of the cation (C0) are shown below, but are not limited thereto.

[0038]

Chemical formula

[0039] <Substrate component (A)> In the resist composition of the present embodiment, as the component (A), it is preferable to use a resin component (A1) (hereinafter also referred to as the "(A1) component") whose solubility in a developer changes by the action of an acid. By using the (A1) component, since the polarity of the substrate component changes before and after exposure, good development contrast can be obtained not only in the alkali development process but also in the solvent development process. As the component (A), other high molecular compounds and / or low molecular compounds may be used in combination with the (A1) component.

[0040] In the resist composition of the present embodiment, the component (A) may be used alone or in combination of two or more.

[0041] ·Regarding the (A1) component The (A1) component is a resin component whose solubility in a developer changes by the action of an acid. As the (A1) component, those having a structural unit (a1) containing an acid-decomposable group whose polarity increases by the action of an acid are preferable. The (A1) component may have other structural units as necessary in addition to the structural unit (a1).

[0042] ≪Structural unit (a1)≫ The constitutional unit (a1) is a constitutional unit containing an acid-decomposable group whose polarity increases by the action of an acid.

[0043] Examples of the acid-dissociable group include those proposed as the acid-dissociable group of the base resin for chemically amplified resist compositions. Specific examples of those proposed as the acid-dissociable group of the base resin for chemically amplified resist compositions include the "acetal-type acid-dissociable group", "tertiary alkyl ester-type acid-dissociable group", "tertiary alkyloxycarbonyl acid-dissociable group", and "secondary alkyloxycarbonyl acid-dissociable group" described below.

[0044] Acetal-type acid-dissociable group: Examples of the acid-dissociable group that protects the carboxy group or hydroxyl group among the polar groups include, for example, an acid-dissociable group represented by the following general formula (a1-r-1) (hereinafter sometimes referred to as an "acetal-type acid-dissociable group").

[0045] [Chemical formula] [In the formula, Ra’ 1 , Ra’ 2 is a hydrogen atom or an alkyl group. Ra’ 3 is a hydrocarbon group, and Ra’ 3 may be bonded to either Ra’ 1 , Ra’ 2 to form a ring.]

[0046] In formula (a1-r-1), it is preferable that at least one of Ra’ 1 and Ra’ 2 is a hydrogen atom, and more preferably both are hydrogen atoms. Ra’ 1 or Ra’ 2When it is an alkyl group, examples of the alkyl group include the same ones as the alkyl groups listed as substituents that may be bonded to the carbon atom at the α-position in the description of the above α-substituted acrylic acid ester, and an alkyl group having 1 to 5 carbon atoms is preferred. Specifically, a linear or branched alkyl group is preferably mentioned. 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. are mentioned, a methyl group or an ethyl group is more preferred, and a methyl group is particularly preferred.

[0047] In formula (a1-r-1), Ra’ 3 Examples of the hydrocarbon group of include a linear or branched alkyl group, or a cyclic hydrocarbon group. The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms. Specifically, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, etc. are mentioned. Among these, a methyl group, an ethyl group or an n-butyl group is preferred, and a methyl group or an ethyl group is more preferred.

[0048] The branched alkyl group preferably has 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms. Specifically, an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, a 2,2-dimethylbutyl group, etc. are mentioned, and an isopropyl group is preferred.

[0049] Ra’ 3 When Ra’ is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group. As the aliphatic hydrocarbon group which is a monocyclic group, a group obtained by removing one hydrogen atom from monocycloalkane is preferred. As the monocycloalkane, those having 3 to 6 carbon atoms are preferred, and specifically, cyclopentane, cyclohexane, etc. are mentioned. As the aliphatic hydrocarbon group which is a polycyclic group, a group obtained by removing one hydrogen atom from a polycycloalkane is preferable. As the polycycloalkane, those having 7 to 12 carbon atoms are preferable. Specifically, adamantane, norbornane, isobornane, tricyclo 2,6 decane, tetracyclododecane and the like can be mentioned.

[0050] Ra’ 3 When the cyclic hydrocarbon group of Ra’ becomes an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. This aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and may be monocyclic or polycyclic. The number of carbon atoms of the aromatic ring is preferably 5 to 30, more preferably 5 to 20, still more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocyclic rings in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom, and the like. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocyclic ring include a pyridine ring and a thiophene ring. Ra’ 3 Specific examples of the aromatic hydrocarbon group in Ra’ include a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocyclic ring (aryl group or heteroaryl group); a group obtained by removing one hydrogen atom from an aromatic compound containing two or more aromatic rings (for example, biphenyl, fluorene, etc.); a group in which one of the hydrogen atoms of the aromatic hydrocarbon ring or aromatic heterocyclic ring is substituted with an alkylene group (for example, arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms of the alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocyclic ring is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0051] Ra’3 The cyclic hydrocarbon group in 3 may have a substituent. Examples of such a substituent include -RP1, -RP2 - O - RP1, -RP2 - CO - RP1, -RP2 - CO - ORP1, -RP2 - O - CO - RP1, -RP2 - OH, -RP2 - CN, or -RP2 - COOH (hereinafter these substituents are also collectively referred to as "Rax5"). Here, R P1 is a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms, a monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms. Also, R P2 is a single bond, a divalent linear saturated hydrocarbon group having 1 to 10 carbon atoms, a divalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms. However, some or all of the hydrogen atoms of the linear saturated hydrocarbon group, aliphatic cyclic saturated hydrocarbon group, and aromatic hydrocarbon group of R P1 and R P2 may be substituted with fluorine atoms. The above aliphatic cyclic hydrocarbon group may have one or more of the above substituents alone, or may have one or more of a plurality of types of the above substituents. Examples of the monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, etc. Examples of the monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms include monocyclic aliphatic saturated hydrocarbon groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a cyclododecyl group, etc.; polycyclic aliphatic saturated hydrocarbon groups such as a bicyclo[2.2.2]octanyl group, a tricyclo[5.2.1.02,6]decanyl group, a tricyclo[3.3.1.13,7]decanyl group, a tetracyclo[6.2.1.13,6.02,7]dodecanyl group, an adamantyl group, etc. Examples of the monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms include groups obtained by removing one hydrogen atom from aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene.

[0052] Ra’ 3 is Ra’ 1 , Ra’ 2 When any of them binds to form a ring, the cyclic group is preferably a 4- to 7-membered ring, more preferably a 4- to 6-membered ring. Specific examples of the cyclic group include a tetrahydropyranyl group and a tetrahydrofuranyl group.

[0053] Tertiary alkyl ester type acid dissociable group: Among the above polar groups, examples of the acid dissociable group that protects the carboxy group include acid dissociable groups represented by the following general formula (a1-r-2). Among the acid dissociable groups represented by the following formula (a1-r-2), those composed of an alkyl group may be hereinafter referred to as "tertiary alkyl ester type acid dissociable groups" for convenience.

[0054]

Chemical formula

[0055] Ra’ 4 Examples of the hydrocarbon group of Ra’ Ra’ 4 include a linear or branched alkyl group, a linear or cyclic alkenyl group, or a cyclic hydrocarbon group. Examples of the linear or branched alkyl group and cyclic hydrocarbon group (aliphatic hydrocarbon group which is a monocyclic group, aliphatic hydrocarbon group which is a polycyclic group, aromatic hydrocarbon group) in Ra’ Ra’ 4The chain or cyclic alkenyl group in [the compound] preferably has 2 to 10 carbon atoms. Ra’ 5 , Ra’ 6 As the hydrocarbon group of [the compound], those similar to the above Ra’ 3 can be mentioned.

[0056] Ra’ 5 and Ra’ 6 are bonded to each other to form a ring, preferably 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 mentioned. On the other hand, when Ra’ 4 ~Ra’ 6 are not bonded to each other and are independent hydrocarbon groups, preferably a group represented by the following general formula (a1-r2-4) can be mentioned.

[0057] [Chemical formula] [In formula (a1-r2-1), Ra’ 10 represents a linear or branched alkyl group having 1 to 12 carbon atoms, which may be partially substituted with a halogen atom or a heteroatom-containing group. Ra’ 11 represents a group that forms an aliphatic cyclic group together with the carbon atom to which Ra’ 10 is bonded. 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 of this cyclic hydrocarbon group may be substituted. Ra 101 ~Ra 103 are each independently a hydrogen atom, a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms, or a monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms. Some or all of the hydrogen atoms of this linear saturated hydrocarbon group and aliphatic cyclic saturated hydrocarbon group may be substituted. Ra 101 ~Ra 103 Two or more of them may be bonded to each other to form a cyclic structure. In formula (a1-r2-3), Yaa is a carbon atom. Xaa is a group that forms an aliphatic cyclic group together with Yaa. Ra104 is an aromatic hydrocarbon group which may have a substituent. In formula (a1-r2-4), Ra’ 12 and Ra’ 13 are each independently a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms. Some or all of the hydrogen atoms of this linear saturated hydrocarbon group may be substituted. Ra’ 14 is a hydrocarbon group which may have a substituent. * represents a bond (the same applies hereinafter).]

[0058] In the above formula (a1-r2-1), Ra’ 10 is a linear or branched alkyl group having 1 to 12 carbon atoms, some of which may be substituted with a halogen atom or a heteroatom-containing group.

[0059] Ra’ 10 As the linear alkyl group in Ra’, it has 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, and particularly preferably 1 to 5 carbon atoms. Ra’ 10 As the branched alkyl group in Ra’, those similar to the above Ra’ 3 can be mentioned.

[0060] Ra’ 10 The alkyl group in Ra’ may be partially substituted with a halogen atom or a heteroatom-containing group. For example, some of the hydrogen atoms constituting the alkyl group may be substituted with a halogen atom or a heteroatom-containing group. Also, some of the carbon atoms (such as methylene groups) constituting the alkyl group may be substituted with a heteroatom-containing group. Examples of the heteroatom mentioned here include an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the heteroatom-containing group include (-O-), -C(=O)-O-, -O-C(=O)-, -C(=O)-, -O-C(=O)-O-, -C(=O)-NH-, -NH-, -S-, -S(=O) 2 -, -S(=O) 2 -O- and the like.

[0061] In formula (a1-r2-1), Ra’ 11 (Ra’10 An aliphatic cyclic group formed together with a carbon atom to which it is bonded) is Ra' in formula (a1-r-1) 3 The group exemplified as an aliphatic hydrocarbon group (alicyclic hydrocarbon group) which is a monocyclic group or a polycyclic group of is preferable. Among them, a monocyclic alicyclic hydrocarbon group is preferable, and specifically, a cyclopentyl group and a cyclohexyl group are more preferable.

[0062] In formula (a1-r2-2), examples of the cyclic hydrocarbon group formed by Xa together with Ya include a group obtained by further removing one or more hydrogen atoms from the cyclic monovalent hydrocarbon group (aliphatic hydrocarbon group) of Ra' in the above formula (a1-r-1). 3 The cyclic hydrocarbon group formed by Xa together with Ya may have a substituent. Examples of this substituent include the same substituents as those that the cyclic hydrocarbon group of Ra' 3 may have. In formula (a1-r2-2), Ra 101 ~Ra 103 Examples of the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms in include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, and the like. Ra 101 ~Ra 103 Examples of the monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms in include monocyclic aliphatic saturated hydrocarbon groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a cyclododecyl group; bicyclo[2.2.2]octanyl group, tricyclo[5.2.1.0 2,6 decanyl group, tricyclo[3.3.1.1 3,7 decanyl group, tetracyclo[6.2.1.1 3,6 .0 2,7 dodecanyl group, adamantyl group, and other polycyclic aliphatic saturated hydrocarbon groups and the like. Ra 101 ~Ra 103 ​Among them, from the viewpoint of ease of synthesis, a hydrogen atom or a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms is preferable, and among them, a hydrogen atom, a methyl group, or an ethyl group is more preferable, and a hydrogen atom is particularly preferable.

[0063] The above Ra 101 ~Ra 103 Examples of the substituent of the linear saturated hydrocarbon group or the aliphatic cyclic saturated hydrocarbon group represented by include, for example, the same groups as the above Ra x5 can be mentioned.

[0064] Ra 101 ~Ra 103 Examples of the group containing a carbon-carbon double bond formed by two or more of Ra

[0065] 3 combining with each other to form a cyclic structure include, for example, a cyclopentenyl group, a cyclohexenyl group, a methylcyclopentenyl group, a methylcyclohexenyl group, a cyclopentylideneethenyl group, a cyclohexylideneethenyl group, and the like. Among these, from the viewpoint of ease of synthesis, a cyclopentenyl group, a cyclohexenyl group, or a cyclopentylideneethenyl group is preferable. In formula (a1-r2-3), the aliphatic cyclic group formed by Xaa and Yaa is preferably the group mentioned as the aliphatic hydrocarbon group which is a monocyclic group or a polycyclic group of Ra' 104 in formula (a1-r-1). 104 Examples of the aromatic hydrocarbon group for Ra in formula (a1-r2-3) include groups obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring having 5 to 30 carbon atoms. Among them, Ra

[0066] Ra in formula (a1-r2-3)104 Examples of the substituent that may be possessed include, for example, a methyl group, an ethyl group, a propyl group, a hydroxy group, a carboxy group, a halogen atom, an alkoxy group (such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc.), an alkyloxycarbonyl group, and the like.

[0067] In formula (a1-r2-4), Ra’ 12 and Ra’ 13 are each independently a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms. Examples of the monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms in Ra’ 12 and Ra’ 13 include the same ones as the monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms in the above Ra 101 ~Ra 103 Some or all of the hydrogen atoms of this linear saturated hydrocarbon group may be substituted. Ra’ 12 and Ra’ 13 Among them, an alkyl group having 1 to 5 carbon atoms is preferable, an alkyl group having 1 to 5 carbon atoms is more preferable, a methyl group and an ethyl group are even more preferable, and a methyl group is particularly preferable. When the linear saturated hydrocarbon group represented by the above Ra’ 12 and Ra’ 13 is substituted, examples of the substituent include the same groups as the above Ra x5 for example.

[0068] In formula (a1-r2-4), Ra’ 14 is a hydrocarbon group that may have a substituent. Examples of the hydrocarbon group in Ra’ 14 include a linear or branched alkyl group or a cyclic hydrocarbon group.

[0069] Ra’ 14The linear alkyl group in

[0070] Ra’ 14 is preferably an alkyl group having 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms. Specifically, isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 1,1-diethylpropyl group, 2,2-dimethylbutyl group, etc. may be mentioned, and an isopropyl group is preferable.

[0071] Ra’ 14 When becomes a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group. As the aliphatic hydrocarbon group which is a monocyclic group, a group obtained by removing one hydrogen atom from monocycloalkane is preferable. As the monocycloalkane, those having 3 to 6 carbon atoms are preferable, and specifically, cyclopentane, cyclohexane, etc. may be mentioned. As the aliphatic hydrocarbon group which is a polycyclic group, a group obtained by removing one hydrogen atom from polycycloalkane is preferable. As the polycycloalkane, those having 7 to 12 carbon atoms are preferable, and specifically, adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 decane, tetracyclododecane, etc. may be mentioned.

[0072] Ra’ 14 Examples of the aromatic hydrocarbon group in include the same ones as the aromatic hydrocarbon group in Ra 104 Among them, Ra’ 14is preferably a group obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring having 6 to 15 carbon atoms, more preferably a group obtained by removing one or more hydrogen atoms from benzene, naphthalene, anthracene or phenanthrene, still more preferably a group obtained by removing one or more hydrogen atoms from benzene, naphthalene or anthracene, particularly preferably a group obtained by removing one or more hydrogen atoms from naphthalene or anthracene, and most preferably a group obtained by removing one or more hydrogen atoms from naphthalene. Ra’ 14 Examples of the substituent that Ra 104 may have include the same ones as those of the substituent that

[0073] Ra’ in the formula (a1-r2-4) 14 When Ra’ is a naphthyl group, the position bonding to the tertiary carbon atom in the formula (a1-r2-4) may be either the 1-position or the 2-position of the naphthyl group. Ra’ in the formula (a1-r2-4) 14 When Ra’ is an anthryl group, the position bonding to the tertiary carbon atom in the formula (a1-r2-4) may be any of the 1-position, 2-position or 9-position of the anthryl group.

[0074] Specific examples of the group represented by the formula (a1-r2-1) are given below.

[0075]

Chemical formula

[0076]

Chemical formula

[0077]

Chemical formula

[0078] Specific examples of the group represented by the formula (a1-r2-2) are given below.

[0079] [Chemistry]

[0080] [Chemistry]

[0081] [Chemistry]

[0082] Specific examples of the group represented by the formula (a1-r2-3) are given below.

[0083] [Chemistry]

[0084] Specific examples of the group represented by the formula (a1-r2-4) are given below.

[0085] [Chemistry]

[0086] Tertiary alkyloxycarbonyl acid dissociable group: As the acid dissociable group for protecting the hydroxyl group among the polar groups, for example, an acid dissociable group represented by the following general formula (a1-r-3) (hereinafter sometimes referred to as "tertiary alkyloxycarbonyl acid dissociable group" for convenience) can be mentioned.

[0087] [Chemistry] [In the formula, Ra’ 7 ~Ra’ 9 are each an alkyl group.]

[0088] In formula (a1-r-3), Ra’ 7 ~Ra’ 9Each alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms. Also, 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.

[0089] Secondary alkyl ester type acid dissociable group: Among the above polar groups, examples of the acid dissociable group for protecting the carboxy group include acid dissociable groups represented by the following general formula (a1-r-4).

[0090] [Chemical formula] [In the formula, Ra’ 10 is a hydrocarbon group. Ra’ 11a and Ra’ 11b are each independently a hydrogen atom, a halogen atom or an alkyl group. Ra’ 12 is a hydrogen atom or a hydrocarbon group. Ra’ 10 and Ra’ 11a or Ra’ 11b and may be bonded to each other to form a ring. Ra’ 11a or Ra’ 11b and Ra’ 12 and may be bonded to each other to form a ring.]

[0091] In the formula, Ra’ 10 and Ra’ 12 Examples of the hydrocarbon group in are the same as those of the above Ra’ 3 . In the formula, Ra’ 11a and Ra’ 11b Examples of the alkyl group in are the same as those of the alkyl group in the above Ra’ 1 . In the formula, Ra’ 10 and Ra’ 12 The hydrocarbon groups in, and Ra’ 11a and Ra’ 11bThe alkyl group in may have a substituent. Examples of this substituent include Ra as described above. x5 and the like.

[0092] Ra’ 10 and Ra’ 11a or Ra’ 11b may combine with each other to form a ring. The ring may be a polycyclic ring or a monocyclic ring, and may be an alicyclic ring or an aromatic ring. The alicyclic ring and the aromatic ring may contain heteroatoms.

[0093] Ra’ 10 and Ra’ 11a or Ra’ 11b Among the rings formed by combining with each other, monocycloalkene, a ring in which some of the carbon atoms of monocycloalkene are substituted with heteroatoms (such as oxygen atoms, sulfur atoms), and monocycloalkadiene are preferred, cycloalkene having 3 to 6 carbon atoms is preferred, and cyclopentene or cyclohexene is preferred.

[0094] Ra’ 10 and Ra’ 11a or Ra’ 11b The ring formed by combining with each other may be a fused ring. Specific examples of the fused ring include indane and the like.

[0095] Ra’ 10 and Ra’ 11a or Ra’ 11b The ring formed by combining with each other may have a substituent. Examples of this substituent include Ra as described above. x5 and the like.

[0096] Ra’ 11a or Ra’ 11b and Ra’ 12 may combine with each other to form a ring. Examples of the ring include the same rings as those formed by Ra’ 10 and Ra’ 11a or Ra’ 11b combining with each other.

[0097] Specific examples of the group represented by the formula (a1-r-4) are given below.

[0098]

Chemical formula

[0099] Examples of the structural unit (a1) include a structural unit derived from an acrylate ester in which a hydrogen atom bonded to a carbon atom at the α-position may be substituted with a substituent, a structural unit derived from acrylamide, and a structural unit in which at least a part of the hydrogen atom in the hydroxyl group of a structural unit derived from hydroxystyrene or a hydroxystyrene derivative is protected with a substituent containing the acid-decomposable group, and a structural unit in which at least a part of the hydrogen atom in -C(=O)-OH of a structural unit derived from vinylbenzoic acid or a vinylbenzoic acid derivative is protected with a substituent containing the acid-decomposable group.

[0100] Among them, as the structural unit (a1), a structural unit derived from an acrylate ester in which a hydrogen atom bonded to a carbon atom at the α-position may be substituted with a substituent is preferable. Preferable specific examples of such a structural unit (a1) include structural units represented by the following general formulas (a1-1), (a1-2), or (a1-3).

[0101]

Chemical formula

[0102] In the above formulas (a1-1) to (a1-3), the alkyl group of R having 1 to 5 carbon atoms is preferably a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, 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. can be mentioned. The halogenated alkyl group having 1 to 5 carbon atoms is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. As the halogen atom, a fluorine atom is particularly preferable. As 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 preferable, and from the viewpoint of easy availability in industry, a hydrogen atom or a methyl group is most preferable.

[0103] In the above formula (a1-1), Va 1 The divalent hydrocarbon group in may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0104] Va 1 The aliphatic hydrocarbon group as the divalent hydrocarbon group in may be saturated or unsaturated, and usually preferably saturated. More specifically, examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, or an aliphatic hydrocarbon group containing a ring in its structure.

[0105] The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferred. Specifically, a methylene group [-CH 2 -], an ethylene group [-(CH 2 ) 2 -], a trimethylene group [-(CH 2 ) 3 -], a tetramethylene group [-(CH 2 ) 4 -], a pentamethylene group [-(CH 2 ) 5 -], etc. may be mentioned. The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, still more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferred. Specifically, -CH(CH 3 )-, -CH(CH 2 CH 3 )-, -C(CH 3 ) 2 -, -C(CH 3 )(CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 2 CH 3 )-, -C(CH 2 CH 3 ) 2 -, etc. alkylmethylene groups; -CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )-, -C(CH 3 ) 2 CH 2 -, -CH(CH 2 CH 3 )CH 2 -, -C(CH 2 CH 3 ) 2-CH 2 - alkyl ethylene groups such as -CH(CH 3 )CH 2 CH 2 -,-CH 2 CH(CH 3 )CH 2 - alkyl trimethylene groups such as -CH(CH 3 )CH 2 CH 2 CH 2 -,-CH 2 CH(CH 3 )CH 2 CH 2 - alkyl alkylene groups such as alkyl tetramethylene groups and the like can be mentioned. As the alkyl group in the alkyl alkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

[0106] Examples of the aliphatic hydrocarbon group containing a ring in the above structure include an alicyclic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), a group in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include the same ones as the linear aliphatic hydrocarbon group or the branched aliphatic hydrocarbon group described above. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be polycyclic or monocyclic. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specifically includes cyclopentane, cyclohexane, and the like. As the polycyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a polycycloalkane is preferable, and the polycycloalkane preferably has 7 to 12 carbon atoms, and specifically includes adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 decane, tetracyclododecane, and the like.

[0107] Va 1 In the formula, the aromatic hydrocarbon group as the divalent hydrocarbon group is a hydrocarbon group having an aromatic ring. Such an aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30 carbon atoms, still more preferably 5 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, and most preferably 6 to 12 carbon atoms. However, the number of carbon atoms does not include the number of carbon atoms in the substituent. Specific examples of the aromatic ring of the aromatic hydrocarbon group include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene; and aromatic heterocyclic rings in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Examples of the heteroatom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic hydrocarbon group include a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring (arylene group); a group in which one hydrogen atom of a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring (aryl group) is substituted with an alkylene group (for example, a group obtained by further removing one hydrogen atom from the 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, or a 2-naphthylethyl group). 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.

[0108] In the formula (a1-1), Ra 1 is preferably an acid dissociable group represented by the above general formula (a1-r-2) or (a1-r-4). Among these, a group represented by the general formula (a1-r2-1) or an acid dissociable group represented by the general formula (a1-r-4) is more preferable.

[0109] In the formula (a1-2), Wa 1 n in a2The monovalent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity, and may be saturated or unsaturated, and is usually preferably saturated. Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, or a group combining a linear or branched aliphatic hydrocarbon group and an aliphatic hydrocarbon group containing a ring in the structure. Said n a2 The monovalent to tetravalent is preferably divalent to tetravalent, more preferably divalent or trivalent. In the formula (a1-2), Ra 2 is preferably an acid dissociable group represented by the above general formula (a1-r-1).

[0110] In the formula (a1-3), Ya 001 The divalent linking group in is not particularly limited, and examples of suitable ones include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom. Ya 001 is preferably an ester bond [-C(=O)-O-, -O-C(=O)-], an ether bond (-O-), a linear or branched alkylene group, an aromatic hydrocarbon group or a combination thereof, or a single bond. The number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4, and particularly preferably 1 to 3. Among these, Ya 001 is more preferably a combination of an ester bond [-C(=O)-O-, -O-C(=O)-] and a linear alkylene group, or a single bond, and even more preferably a single bond.

[0111] In the formula (a1-3), Ya 01 The divalent linking group in is not particularly limited, and examples of suitable ones include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom. Ya 01Among these, an ester bond [-C(=O)-O-, -O-C(=O)-], an ether bond (-O-), a linear or branched alkylene group, an aromatic hydrocarbon group, or a combination thereof, or a single bond is preferable. Among these, Ya 01 is more preferably a combination of an ester bond [-C(=O)-O-, -O-C(=O)-] and a linear alkylene group, or a single bond, and even more preferably a single bond.

[0112] In the formula (a1-3), Rax 01 is preferably an acid dissociable group represented by the above general formula (a1-r-2) or (a1-r-4). Among these, an acid dissociable group represented by the general formula (a1-r-2) is more preferable, and a group represented by the general formula (a1-r2-1) is even more preferable.

[0113] In the formula (a1-3), Rz 01 The alkyl group, halogenated alkyl group, and alkoxy group in are preferably those having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, even more preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms. The alkyl group, halogenated alkyl group, and alkoxy group may be linear or branched. Rz 01 The halogen atom in is preferably a fluorine atom, iodine atom, or bromine atom. Rz 01 The halogen atom of the halogenated alkyl group in is preferably a fluorine atom, iodine atom, or bromine atom, and more preferably a fluorine atom. Rz 01 is preferably a hydroxy group.

[0114] In the formula (a1-3), q is an integer of 0 to 3. When q is 0, it is a benzene structure, when q is 1, it is a naphthalene structure, when q is 2, it is an anthracene structure, and when q is 3, it is a tetracene structure. In the formula (a1-3), n is an integer of 0 or more, preferably 0 to 5, more preferably 0 to 3, and even more preferably 1 or 2. In the formula (a1-3), n ≦ q × 2 + 4. For example, when q is 1 and it has a naphthalene structure, all six hydrogen atoms of the naphthalene may be substituted with hydroxy groups. Further, in the naphthalene, Ya 001 , -Ya 01 -C(=O)-O-Ra 01 groups, and the substitution positions of the hydroxy groups are not particularly limited.

[0115] Specific examples of the structural unit (a1) are shown below. In the following formulas, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0116]

Chemical formula

[0117]

Chemical formula

[0118]

Chemical formula

[0119]

Chemical formula

[0120]

Chemical formula

[0121]

Chemical formula

[0122]

Chemical formula

[0123]

Chemical formula

[0124]

Chem.

[0125] In the following formulas, R α represents a hydrogen atom, a methyl group or a trifluoromethyl group. Each Rz independently represents a hydrogen atom, an alkyl group, a halogen atom, a halogenated alkyl group, a hydroxy group, or an alkoxy group.

[0126]

Chem.

[0127]

Chem.

[0128]

Chem.

[0129]

Chem.

[0130]

Chem.

[0131] (A1) component's constituent unit (a1) may be one kind or two or more kinds. As the constituent unit (a1), the constituent unit represented by the above formula (a1-1) or the constituent unit represented by the above formula (a1-3) is more preferable because the characteristics (sensitivity, shape, etc.) in lithography using an electron beam or EUV can be more easily enhanced. Among them, since it is suitable for enhancing reactivity in EB or EUV applications, the acid dissociable group (Ra1 , Rax 01 ) is preferably an acid dissociable group represented by the above general formula (a1-r2-1), (a1-r2-3), (a1-r2-4) or (a1-r-4), and among them, it is particularly preferable to select a cyclic group.

[0132] Alternatively, the constitutional unit (a1) may include a constitutional unit represented by the following general formula (a1-1-1).

[0133]

Chemical formula

[0134] In the formula (a1-1-1), R, Va 1 and n a1 are the same as R, Va 1 and n a1 in the formula (a1-1).

[0135] The description of the acid dissociable group represented by the general formula (a1-r2-1), (a1-r2-3), (a1-r2-4) or (a1-r-4) is as described above. Among them, since it is suitable for enhancing reactivity in EB or EUV, it is preferable to select an acid dissociable group that is a cyclic group.

[0136] The proportion of the constitutional unit (a1) in the component (A1) is preferably 5 to 80 mol%, more preferably 10 to 75 mol%, still more preferably 30 to 70 mol%, and particularly preferably 40 to 70 mol% with respect to the total (100 mol%) of all the constitutional units constituting the component (A1). By setting the ratio of the structural unit (a1) to be equal to or higher than the lower limit of the above-mentioned preferred range, lithography characteristics such as sensitivity, resolution, and CDU improvement are enhanced. On the other hand, when it is equal to or lower than the upper limit of the above-mentioned preferred range, a balance with other structural units can be achieved, and various lithography characteristics become favorable.

[0137] ≪Other Structural Units≫ (Component A1) may, in addition to the above-described structural unit (a1), have other structural units as necessary. Examples of other structural units include, for example, a structural unit (a10) represented by the general formula (a10-1) described later; a structural unit (a2) containing a lactone-containing cyclic group; a structural unit (a5) that generates an acid upon exposure; a structural unit (a6) having acid diffusion control properties; a structural unit (a0) containing a cation (C0); a structural unit (a8) derived from a compound represented by the general formula (a8-1) described later, and the like.

[0138] Structural unit (a10): The structural unit (a10) is a structural unit represented by the following general formula (a10-1).

[0139] [Chemical formula] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. Ya x1 is a single bond or a divalent linking group. Wa x1 is an aromatic hydrocarbon group which may have a substituent. n ax1 is an integer of 1 or more. ]

[0140] In the formula (a10-1), R is the same as R in the general formula (a1-1). As 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 preferable, and from the viewpoint of easy availability in industry, a hydrogen atom or a methyl group is particularly preferable.

[0141] In the formula (a10-1), Ya x1is a single bond or a divalent linking group. In the above chemical formula, Ya x1 The divalent linking group in is not particularly limited, but examples of suitable ones include a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a heteroatom, and the like.

[0142] · A divalent hydrocarbon group which may have a substituent: The divalent hydrocarbon group which may have a substituent may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0143] ·· Aliphatic hydrocarbon group The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated. Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, or an aliphatic hydrocarbon group containing a ring in its structure, and the like.

[0144] ··· Linear or branched aliphatic hydrocarbon group The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. The linear aliphatic hydrocarbon group is preferably a linear alkylene group. Specifically, it includes a methylene group [-CH 2 -], an ethylene group [-(CH 2 ) 2 -], a trimethylene group [-(CH 2 ) 3 -], a tetramethylene group [-(CH 2 ) 4 -], a pentamethylene group [-(CH 2 ) 5 -], and the like. The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, still more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. As the branched-chain aliphatic hydrocarbon group, a branched-chain alkylene group is preferred. Specifically, -CH(CH 3 )-, -CH(CH 2 CH 3 )-, -C(CH 3 ) 2 -, -C(CH 3 )(CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 2 CH 3 )-, -C(CH 2 CH 3 ) 2 - and other alkylmethylene groups; -CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )-, -C(CH 3 ) 2 CH 2 -, -CH(CH 2 CH 3 )CH 2 -, -C(CH 2 CH 3 ) 2 -CH 2 - and other alkylethylene groups; -CH(CH 3 )CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 - and other alkyltrimethylene groups; -CH(CH 3 )CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 CH 2 - and other alkyltetramethylene groups and other alkylalkylene groups. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0145] The linear or branched aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, a carbonyl group, and the like.

[0146] ··· an aliphatic hydrocarbon group containing a ring in the structure Examples of the aliphatic hydrocarbon group containing a ring in the structure include a cyclic aliphatic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring) which may contain a substituent containing a heteroatom in the ring structure, a group in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, a group in which the cyclic aliphatic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group, and the like. Examples of the linear or branched aliphatic hydrocarbon group are the same as those described above. The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms. The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferred. The monocycloalkane preferably has 3 to 6 carbon atoms, and specifically includes cyclopentane, cyclohexane, and the like. As the polycyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a polycycloalkane is preferred, and the polycycloalkane preferably has 7 to 12 carbon atoms, and specifically includes adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 decane, tetracyclododecane, and the like.

[0147] The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and the like. As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferred, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. As the alkoxy group as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferable, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, a tert-butoxy group are more preferable, and a methoxy group and an ethoxy group are even more preferable. As the halogen atom as the substituent, a fluorine atom is preferable. Examples of the halogenated alkyl group as the substituent include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with the halogen atom. In the cyclic aliphatic hydrocarbon group, some of the carbon atoms constituting the ring structure may be substituted with a substituent containing a hetero atom. Examples of the substituent containing a hetero atom include -O-, -C(=O)-O-, -S-, -S(=O) 2 -, -S(=O) 2 -O- is preferable.

[0148] ·· aromatic hydrocarbon group The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. This aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. However, the number of carbon atoms does not include the number of carbon atoms in the substituent. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocyclic rings in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with hetero atoms, and the like. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocyclic ring include a pyridine ring and a thiophene ring. Specific examples of the aromatic hydrocarbon group include a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocyclic ring (arylene group or heteroarylene group); a group obtained by removing two hydrogen atoms from an aromatic compound containing two or more aromatic rings (such as biphenyl, fluorene, etc.); a group in which one hydrogen atom of a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocyclic ring (aryl group or heteroaryl group) is substituted with an alkylene group (for example, a group obtained by further removing one hydrogen atom from the aryl group in an arylalkyl group such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms 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.

[0149] The hydrogen atom of the aromatic hydrocarbon group may be substituted with a substituent. For example, the hydrogen atom bonded to the aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, etc. As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group is more preferable. Examples of the alkoxy group, halogen atom, and halogenated alkyl group as the substituent include those exemplified as the substituent for substituting the hydrogen atom of the cyclic aliphatic hydrocarbon group.

[0150] ·Divalent linking group containing a heteroatom: Examples of the divalent linking group containing a heteroatom include -O-, -C(=O)-O-, -O-C(=O)-, -C(=O)-, -O-C(=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)- (H may be substituted with a substituent such as an alkyl group, an acyl group, etc.), -S-, -S(=O) 2 -, -S(=O) 2-O-, general formula -Y 21 -O-Y 22 -,-Y 21 -O-,-Y 21 -C(=O)-O-,-C(=O)-O-Y 21 -,-[Y 21 -C(=O)-O] m” -Y 22 -,-Y 21 -O-C(=O)-Y 22 - or -Y 21 -S(=O) 2 -O-Y 22 - represented groups [wherein, Y 21 and Y 22 are each independently a divalent hydrocarbon group which may have a substituent, O is an oxygen atom, and m” is an integer of 0 to 3.] etc. may be mentioned. When the divalent linking group containing the hetero atom is -C(=O)-NH-,-C(=O)-NH-C(=O)-,-NH-,-NH-C(=NH)-, the H thereof 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 carbon atoms, and particularly preferably 1 to 5 carbon atoms. General formula -Y 21 -O-Y 22 -,-Y 21 -O-,-Y 21 -C(=O)-O-,-C(=O)-O-Y 21 -,-[Y 21 -C(=O)-O] m” -Y 22 -,-Y 21 -O-C(=O)-Y 22 - or -Y 21 -S(=O) 2 -O-Y 22 - in, Y 21 and Y 22 are each independently a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include the same ones as described above. Y 21As for this, a linear aliphatic hydrocarbon group is preferable, a linear alkylene group is more preferable, a linear alkylene group having 1 to 5 carbon atoms is still more preferable, and a methylene group or an ethylene group is particularly preferable. Y 22 As for this, a linear or branched aliphatic hydrocarbon group is preferable, and a methylene group, an ethylene group or an alkylmethylene group is more preferable. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group. In the group represented by the formula -[Y 21 -C(=O)-O] m” -Y 22 -, m” is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 1. That is, in the formula -[Y 21 -C(=O)-O] m” -Y 22 -, as the group represented by the formula, a group represented by the formula -Y 21 -C(=O)-O-Y 22 - is particularly preferable. Among them, the group represented by the formula -(CH 2 ) a’ -C(=O)-O-(CH 2 ) b’ - is preferable. In the formula, a’ is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, still more preferably 1 or 2, and most preferably 1. b’ is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, still more preferably 1 or 2, and most preferably 1.

[0151] Ya x1 As for this, a single bond, an ester bond [-C(=O)-O-, -O-C(=O)-], an ether bond (-O-), a linear or branched alkylene group, or a combination thereof is preferable, and a single bond, an ester bond [-C(=O)-O-, -O-C(=O)-] is more preferable.

[0152] In the formula (a10-1), Wa x1is an aromatic hydrocarbon group which may have a substituent. Wa x1 Examples of the aromatic hydrocarbon group in ax1 include a group obtained by removing (n + 1) hydrogen atoms from an aromatic ring which may have a substituent. The aromatic ring here is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons. The number of carbon atoms of the aromatic ring is preferably 5 to 30, more preferably 5 to 20, still more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocyclic rings in which a part of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Examples of the heteroatom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocyclic ring include a pyridine ring and a thiophene ring. x1 Examples of the aromatic hydrocarbon group in ax1 also include a group obtained by removing (n + 1) hydrogen atoms from an aromatic compound (such as biphenyl and fluorene) containing an aromatic ring which may have two or more substituents. x1 Among the above, as ax1 Wa, a group obtained by removing (n ax1 + 1) hydrogen atoms from benzene, naphthalene, anthracene or biphenyl is preferable, a group obtained by removing (n ax1 + 1) hydrogen atoms from benzene or naphthalene is more preferable, and a group obtained by removing (n

[0153] Wa x1 The aromatic hydrocarbon group in may have a substituent or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, and a halogenated alkyl group. Examples of the alkyl group, alkoxy group, halogen atom, and halogenated alkyl group as the substituent include Ya x1Those similar to those listed as substituents of the cyclic aliphatic hydrocarbon group in [are listed]. The substituent is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably a linear or branched alkyl group having 1 to 3 carbon atoms, still more preferably an ethyl group or a methyl group, and particularly preferably a methyl group. Wa x1 The aromatic hydrocarbon group in [is preferably unsubstituted].

[0154] In the above formula (a10-1), n ax1 is an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 5, still more preferably 1, 2 or 3, and particularly preferably 1 or 2.

[0155] Specific examples of the structural unit (a10) represented by the above formula (a10-1) are shown below. In the following formulas, R α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

[0156]

Chemical formula

[0157]

Chemical formula

[0158]

Chemical formula

[0159] (A1) component may have one or more than two structural units (a10). The (A1) component may or may not have the structural unit (a10), but preferably has the structural unit (a10). When the (A1) component has the structural unit (a10), the proportion of the structural unit (a10) in the (A1) component is preferably 20 to 80 mol%, more preferably 25 to 70 mol%, still more preferably 30 to 60 mol%, and particularly preferably 30 to 50 mol% with respect to the total (100 mol%) of all the structural units constituting the (A1) component. By setting the proportion of the structural unit (a10) to be not less than the lower limit value, the sensitivity is more likely to be enhanced. On the other hand, by setting it to be not more than the upper limit value, it becomes easier to balance with other structural units.

[0160] Structural unit (a2): The (A1) component may or may not have a structural unit (a2) containing a lactone-containing cyclic group (excluding those corresponding to the structural unit (a1)). The lactone-containing cyclic group of the structural unit (a2) is effective in enhancing the adhesion of the resist film to the substrate when the (A1) component is used for forming the resist film. Further, by having the structural unit (a2), for example, effects such as appropriately adjusting the acid diffusion length, enhancing the adhesion of the resist film to the substrate, and appropriately adjusting the solubility during development, etc., the lithography characteristics and the like become good.

[0161] The "lactone-containing cyclic group" refers to a cyclic group containing a ring (lactone ring) containing -O-C(=O)- in its ring skeleton. Counting the lactone ring as the first ring, in the case of only the lactone ring, it is a monocyclic group, and when it further has other ring structures, regardless of the structure, it is called a polycyclic group. The lactone-containing cyclic group may be a monocyclic group or a polycyclic group. The lactone-containing cyclic group in the structural 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) can be mentioned.

[0162]

Chemical formula

[0163] In the general formulas (a2-r-1) to (a2-r-7), Ra’ 21 As the alkyl group in, an alkyl group having 1 to 6 carbon atoms is preferable. The alkyl group is preferably linear or branched. 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, a hexyl group and the like can be mentioned. Among these, a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable. Ra’ 21 As the alkoxy group in, an alkoxy group having 1 to 6 carbon atoms is preferable. The alkoxy group is preferably linear or branched. Specifically, a group in which the alkyl group mentioned as the alkyl group in the above Ra’ 21 is linked to an oxygen atom (-O-) can be mentioned. Ra’ 21 As the halogen atom in, a fluorine atom is preferable. Ra’ 21 As the halogenated alkyl group in, a group in which a part or all of the hydrogen atoms of the alkyl group in the above Ra’ 21 are substituted with the halogen atom can be mentioned. As the halogenated alkyl group, a fluorinated alkyl group is preferable, and a perfluoroalkyl group is particularly preferable.

[0164] Ra’ 21 In -COOR” and -OC(=O)R” in, each of R” is a hydrogen atom, an alkyl group, or a lactone-containing cyclic group. The alkyl group in “R” may be linear, branched or cyclic, and preferably has 1 to 15 carbon atoms. When “R” is a linear or branched alkyl group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably a methyl group or an ethyl group. When “R” is a cyclic alkyl group, it preferably has 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, a group obtained by removing one or more hydrogen atoms from a monocycloalkane which may or may not be substituted with a fluorine atom or a fluorinated alkyl group; a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as bicycloalkane, tricycloalkane, tetracycloalkane, etc. can be exemplified. More specifically, a group obtained by removing one or more hydrogen atoms from a monocycloalkane such as cyclopentane, cyclohexane, etc.; adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 decane, a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as tetracyclododecane, etc. can be mentioned. Examples of the lactone-containing cyclic group in “R” include the same groups as those represented by the general formulas (a2-r-1) to (a2-r-7) respectively. Ra’ 21 The hydroxyalkyl group in is preferably one having 1 to 6 carbon atoms, and specifically, a group in which at least one of the hydrogen atoms of the alkyl group in the above Ra’ 21 is substituted with a hydroxyl group can be mentioned.

[0165] Ra’ 21 Among the above, as Ra’, each is preferably independently a hydrogen atom or a cyano group.

[0166] In the general formulas (a2-r-2), (a2-r-3), and (a2-r-5), the alkylene group having 1 to 5 carbon atoms in A” is preferably a linear or branched alkylene group, and examples thereof include a methylene group, an ethylene group, an n-propylene group, and an isopropyl group. When the alkylene group contains an oxygen atom or a sulfur atom, specific examples thereof include groups in which -O- or -S- is interposed at the terminal or between carbon atoms of the alkylene group. For example, -O-CH 2 -, -CH 2 -O-CH 2 -, -S-CH 2 -, -CH 2 -S-CH 2 - and the like. As A”, an alkylene group having 1 to 5 carbon atoms or -O- is preferable, an alkylene group having 1 to 5 carbon atoms is more preferable, and a methylene group is most preferable.

[0167] Specific examples of the groups represented by the general formulas (a2-r-1) to (a2-r-7) are given below.

[0168]

Chemical formula

[0169]

Chemical formula

[0170] As the constitutional unit (a2), among others, a constitutional unit derived from an acrylate in which a hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent is preferable. Such a constitutional unit (a2) is preferably a constitutional unit represented by the following general formula (a2-1).

[0171]

Chemical formula

[0172] In the formula (a2-1), R is the same as described above. As 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 preferable, and from the viewpoint of easy availability in industry, a hydrogen atom or a methyl group is particularly preferable.

[0173] In the formula (a2-1), Ya 21 The divalent linking group in is not particularly limited, but a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a heteroatom, etc. are preferably exemplified. Ya 21 The divalent linking group in Ya is the same as the divalent linking group in Ya in the general formula (a10-1) above. x1 is exemplified.

[0174] Ya 21 is preferably a single bond, an ester bond [-C(=O)-O-], an ether bond (-O-), a linear or branched alkylene group, or a combination thereof.

[0175] In the formula (a2-1), Ya 21 is a single bond, and La 21 is preferably -COO- or -OCO-.

[0176] In the formula (a2-1), Ra 21 is a lactone-containing cyclic group. Ra 21 The lactone-containing cyclic groups in are preferably the groups represented by the general formulas (a2-r-1) to (a2-r-7) described above, respectively.

[0177] (A1) component may have one or more than two kinds of constitutional units (a2). (A1) component may or may not have constitutional unit (a2). When (A1) component has constitutional unit (a2), the proportion of constitutional unit (a2) is preferably 1 to 20 mol%, more preferably 1 to 15 mol%, still more preferably 1 to 10 mol% with respect to the total of all constitutional units (100 mol%) constituting the (A1) component. When the proportion of constitutional unit (a2) is equal to or higher than the preferable lower limit value, the effect of containing constitutional unit (a2) can be sufficiently obtained due to the above-described effect, and when it is equal to or lower than the upper limit value, the balance with other constitutional units can be achieved, and various lithography characteristics become good.

[0178] Constitutional unit (a5): (A1) component may or may not have constitutional unit (a5) that generates an acid upon exposure. Known constitutional units can be used for constitutional unit (a5). By having constitutional unit (a5), the acid generated upon exposure is likely to be uniformly distributed in the resist film. Examples of constitutional unit (a5) include constitutional units containing the structure described in component (B) below. For example, constitutional units containing the structure represented by any of general formulas (b-1) to (b-3) described below can be mentioned. Examples of constitutional unit (a5) preferably include constitutional units represented by the following general formula (a5-1).

[0179] [Chemical formula] [In the formula, R m is an alkyl group having 1 to 5 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogen atom or a hydrogen atom. La 50 is a divalent linking group or a single bond. Ra 50 is a divalent hydrocarbon group which may have a substituent. n a5 is an integer of 0 to 2. La 51 is a divalent linking group. Ya 5is a divalent linking group which may have a heteroatom, or a single bond. Ra 51 and Ra 52 are each independently a hydrogen atom, a fluorine atom or a fluorinated alkyl group. n5 is an integer of 1 to 4. m is an integer of 1 or more, and M’ m+ is an m-valent onium cation. ]

[0180] {Anion part} In the formula (a5-1), R m is an alkyl group having 1 to 5 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogen atom or a hydrogen atom. R m The alkyl group having 1 to 5 carbon atoms is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and 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. can be mentioned. The halogenated alkyl group having 1 to 5 carbon atoms is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. Among the halogen atoms in the halogenated alkyl group, a fluorine atom is particularly preferable. R m is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms, and from the viewpoint of easy availability in industry, a hydrogen atom or a methyl group is most preferable.

[0181] In the formula (a5-1), La 50 is a divalent linking group or a single bond. La 50 The divalent linking group in La is not particularly limited, but a divalent hydrocarbon group which may have a substituent and a divalent linking group containing a heteroatom are preferably mentioned, and each is the same as the divalent hydrocarbon group which may have a substituent and the divalent linking group containing a heteroatom exemplified as the divalent linking group in the above Ya x1 respectively. Among these, La 50 is preferably an ester bond [-C(=O)-O-, -O-C(=O)-], an ether bond (-O-), a linear or branched alkylene group, an aromatic hydrocarbon group, a combination thereof, or a single bond. Among these, La 5 is more preferably an ester bond [-C(=O)-O-, -O-C(=O)-] or a single bond, and even more preferably an ester bond [-C(=O)-O-, -O-C(=O)-].

[0182] In the formula (a5-1), Ra 50 is a divalent hydrocarbon group which may have a substituent. Ra 50 The divalent hydrocarbon group in may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0183] ··Ra 50 The aliphatic hydrocarbon group in The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated. Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, or an aliphatic hydrocarbon group containing a ring in the structure, etc.

[0184] ···linear or branched aliphatic hydrocarbon group The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. The linear aliphatic hydrocarbon group is preferably a linear alkylene group. Specifically, a methylene group [-CH 2 -], an ethylene group [-(CH 2 ) 2 -], a trimethylene group [-(CH 2 ) 3 -], a tetramethylene group [-(CH 2 ) 4-), pentamethylene group [-(CH 2 ) 5 -), etc. The branched-chain aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, still more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. As the branched-chain aliphatic hydrocarbon group, a branched-chain alkylene group is preferred. Specifically, -CH(CH 3 )-, -CH(CH 2 CH 3 )-, -C(CH 3 ) 2 -, -C(CH 3 )(CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 2 CH 3 )-, -C(CH 2 CH 3 ) 2 -, etc. of alkylmethylene groups; -CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )-, -C(CH 3 ) 2 CH 2 -, -CH(CH 2 CH 3 )CH 2 -, -C(CH 2 CH 3 ) 2 -CH 2 -, etc. of alkylethylene groups; -CH(CH 3 )CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 -, etc. of alkyltrimethylene groups; -CH(CH 3 )CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 CH 2- Examples thereof include alkylalkylene groups such as alkyltetramethylene groups. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

[0185] The above linear or branched aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, a carbonyl group, and the like.

[0186] ··· an aliphatic hydrocarbon group containing a ring in the structure Examples of the aliphatic hydrocarbon group containing a ring in the structure include a cyclic aliphatic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring) which may contain a substituent containing a hetero atom in the ring structure, a group in which the cyclic aliphatic hydrocarbon group is bonded to the terminal of a linear or branched aliphatic hydrocarbon group, and a group in which the cyclic aliphatic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the above linear or branched aliphatic hydrocarbon group are the same as those described above. The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms. The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specifically includes cyclopentane, cyclohexane, and the like. As the polycyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a polycycloalkane is preferable. The polycycloalkane preferably has 7 to 12 carbon atoms, and specifically includes adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 decane, tetracyclododecane, and the like.

[0187] The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and the like. As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group is most preferable. As the alkoxy group as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferable, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group is more preferable, and a methoxy group or an ethoxy group is most preferable. Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable. Examples of the halogenated alkyl group as the substituent include a group in which some or all of the hydrogen atoms of the alkyl group are substituted with the halogen atoms. In the cyclic aliphatic hydrocarbon group, some of the carbon atoms constituting the ring structure may be substituted with a substituent containing a hetero atom. Examples of the substituent containing a hetero atom include -O-, -C(=O)-O-, -S-, -S(=O) 2 -, -S(=O) 2 -O- is preferable.

[0188] ··Ra 50 The aromatic hydrocarbon group in The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. This aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and it may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, still more preferably 6 to 15, and particularly preferably 6 to 12. However, the number of carbon atoms does not include the carbon atoms in the substituent. Specifically, as the aromatic ring, aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocyclic rings in which a part of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms, and the like can be mentioned. Examples of the heteroatom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specifically, as the aromatic heterocyclic ring, a pyridine ring, a thiophene ring, and the like can be mentioned. Specifically, as the aromatic hydrocarbon group, a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocyclic ring (arylene group or heteroarylene group); a group obtained by removing two hydrogen atoms from an aromatic compound containing two or more aromatic rings (for example, biphenyl, fluorene, etc.); a group in which one of the hydrogen atoms of a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocyclic ring (aryl group or heteroaryl group) is substituted with an alkylene group (for example, a group obtained by further removing one hydrogen atom from the 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, or a 2-naphthylethyl group), and the like can be mentioned. The number of carbon atoms in the alkylene group bonded to the aryl group or heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0189] The hydrogen atoms of the aromatic hydrocarbon group may be substituted with substituents. For example, the hydrogen atoms bonded to the aromatic ring in the aromatic hydrocarbon group may be substituted with substituents. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and the like. As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group is most preferable. As the alkoxy group, halogen atom, and halogenated alkyl group as the substituent, those exemplified as the substituent that substitutes the hydrogen atom of the cyclic aliphatic hydrocarbon group can be mentioned.

[0190] In the formula (a5-1), n a5 is an integer of 0 to 2. Among the above, Ra 50 is preferably an aliphatic hydrocarbon group containing a ring in the structure, more preferably a cyclic aliphatic hydrocarbon group that may contain a substituent containing a hetero atom in the ring structure, and still more preferably an alicyclic hydrocarbon group that may have a substituent and is a polycyclic group or a monocyclic group. Alternatively, among the above, Ra 50 is preferably an aromatic hydrocarbon group.

[0191] n a5 When it is 2, the two Ra 50 may both be alicyclic hydrocarbon groups that may have a substituent, may both be aromatic hydrocarbon groups, or may be a combination of an alicyclic hydrocarbon group that may have a substituent and an aromatic hydrocarbon group.

[0192] In the formula (a5-1), La 51 is a divalent linking group. La 51 Examples of the divalent linking group in La include non-hydrocarbon-based oxygen atom-containing linking groups such as an oxygen atom (ether bond: -O-), an ester bond (-C(=O)-O-), an oxycarbonyl group (-O-C(=O)-), an amide bond (-C(=O)-NH-), a carbonyl group (-C(=O)-), and a carbonate bond (-O-C(=O)-O-); combinations of the non-hydrocarbon-based oxygen atom-containing linking group and an alkylene group, etc. A sulfonyl group (-SO 2 -) may be further linked to this combination. Examples of such divalent linking groups include linking groups represented by the following general formulas (L-al-1) to (L-al-8). In the following general formulas (L-al-1) to (L-al-8), Ra in the above formula (a5-1) 50 is bonded to V' in the following general formulas (L-al-1) to (L-al-8). 101 That is.

[0193] [Chemical formula] [In the formula, 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 having 1 to 30 carbon atoms.]

[0194] The divalent saturated hydrocarbon group in V' 102 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.

[0195] The alkylene group in V' 101 and V' 102 may be a linear alkylene group or a branched alkylene group, and a linear alkylene group is preferred. The alkylene group in V' 101 and V' 102 Specifically, as the alkylene group, a methylene group [-CH 2 -]; -CH(CH 3 )-, -CH(CH 2 CH 3 )-, -C(CH 3 ) 2 -, -C(CH 3 )(CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 2 CH 3 )-, -C(CH 2 CH 3 ) 2-alkylmethylene groups such as; ethylene group [-CH 2 CH 2 -]; -CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )-, -C(CH 3 ) 2 CH 2 -, -CH(CH 2 CH 3 )CH 2 -alkyl ethylene groups such as; trimethylene group (n-propylene group) [-CH 2 CH 2 CH 2 -]; -CH(CH 3 )CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 -alkyl trimethylene groups such as; tetramethylene group [-CH 2 CH 2 CH 2 CH 2 -]; -CH(CH 3 )CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 CH 2 -alkyl tetramethylene groups such as; pentamethylene group [-CH 2 CH 2 CH 2 CH 2 CH 2 -] and the like. In addition, some of the methylene groups in the alkylene group in V' 101 or V' 102 may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms. The aliphatic cyclic group is preferably a divalent group obtained by further removing one hydrogen atom from the cyclic aliphatic hydrocarbon group (monocyclic aliphatic hydrocarbon group, polycyclic aliphatic hydrocarbon group) of Ra' 3 in the formula (a1-r-1), and more preferably a cyclohexylene group, a 1,5-adamantylene group or a 2,6-adamantylene group.

[0196] La 51 is preferably a divalent linking group containing an ester bond or a divalent linking group containing an ether bond, more preferably the linking groups represented by the above formulas (L-al-1) to (L-al-5), (L-al-8), and even more preferably the linking group represented by (L-al-3) or (L-al-8).

[0197] In the formula (a5-1), Ya 5 is a divalent linking group which may have a hetero atom or a single bond. Ya 5 The divalent linking group in Ya Ya 5 is not particularly limited, but preferably includes a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a hetero atom, and the like. x1 The divalent hydrocarbon group which may have a substituent and the divalent linking group containing a hetero atom in Ya Among the above, Ya 5 is preferably a linear or branched alkylene group or a single bond, and more preferably a single bond.

[0198] In the formula (a5-1), Ra 51 and Ra 52 are each independently a hydrogen atom, a fluorine atom or a fluorinated alkyl group. Ra 51 and Ra 52 The fluorinated alkyl group in each of them is preferably a linear or branched fluorinated alkyl group having 1 to 5 carbon atoms, and more preferably a trifluoromethyl group. In the formula (a5-1), at least one of Ra 3 - bonded to the carbon atom adjacent to SO 51 and Ra 52 is preferably a fluorine atom from the viewpoint of acid strength.

[0199] In the formula (a5-1), n5 is an integer of 1 to 4, and 1, 2 or 3 is preferable.

[0200] {Cation part} In the formula (a5-1), M’ m+ represents an m-valent onium cation. Among these, M’ m+ is preferably a sulfonium cation or an iodonium cation. m is an integer of 1 or more.

[0201] Preferable cation parts ((M’ m+ )) 1 / m include organic cations represented by the following general formulas (ca-1) to (ca-3), respectively.

[0202]

Chemical formula

[0203] In the above general formulas (ca-1) to (ca-3), examples of the aryl group in R 201 ~R 207 include unsubstituted aryl groups having 6 to 20 carbon atoms, and a phenyl group and a naphthyl group are preferable. R 201 ~R207 The alkyl group in 207 is preferably a linear or cyclic alkyl group having 1 to 30 carbon atoms. R 201 ~R 207 The alkenyl group in 207 preferably has 2 to 10 carbon atoms. R 201 ~R 207 and the substituent that R 210 may have includes, for example, an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, a group represented by the following general formulas (ca-r-1) to (ca-r-7), and the like.

[0204]

Chemical formula

[0205] Cyclic group which may have a substituent: 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. The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. Also, the aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

[0206] R’ 201 The aromatic hydrocarbon group in 201 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, still 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 substituent. R’ 201Specific examples of the aromatic ring in the aromatic hydrocarbon group include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or an aromatic heterocyclic ring in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms. Examples of the heteroatom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, a nitrogen atom, etc. R’ 201 Specific examples of the aromatic hydrocarbon group in include a group obtained by removing one hydrogen atom from the aromatic ring (aryl group: e.g., phenyl group, naphthyl group, etc.), a group in which one of the hydrogen atoms of the aromatic ring is substituted with an alkylene group (e.g., arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms in the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0207] R’ 201 The cyclic aliphatic hydrocarbon group in includes an aliphatic hydrocarbon group containing a ring in its structure. Examples of the aliphatic hydrocarbon group containing a ring in this structure include an alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring), a group in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group, etc. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 20, and more preferably 3 to 12. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from monocycloalkane is preferable. As the monocycloalkane, those having 3 to 6 carbon atoms are preferable, and specifically, cyclopentane, cyclohexane and the like can be mentioned. As the polycyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from polycycloalkane is preferable, and as the polycycloalkane, those having 7 to 30 carbon atoms are preferable. Among them, as the polycycloalkane, polycycloalkanes having a crosslinked ring system polycyclic skeleton such as adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 decane, tetracyclododecane; polycycloalkanes having a condensed ring system polycyclic skeleton such as a cyclic group having a steroid skeleton are more preferable.

[0208] Among them, 201 as the cyclic aliphatic hydrocarbon group in R’, a group obtained by removing one or more hydrogen atoms from monocycloalkane or polycycloalkane is preferable, a group obtained by removing one hydrogen atom from polycycloalkane is more preferable, an adamantyl group and a norbornyl group are particularly preferable, and an adamantyl group is most preferable.

[0209] The linear or branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specifically, a methylene group [-CH 2 -], an ethylene group [-(CH 2 ) 2 -], a trimethylene group [-(CH 2 ) 3 -], a tetramethylene group [-(CH 2 ) 4 -], a pentamethylene group [-(CH 2 ) 5 -] and the like can be mentioned. As the branched-chain aliphatic hydrocarbon group, a branched-chain alkylene group is preferred. Specifically, -CH(CH 3 )-, -CH(CH 2 CH 3 )-, -C(CH 3 ) 2 -, -C(CH 3 )(CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 2 CH 3 )-, -C(CH 2 CH 3 ) 2 - and other alkylmethylene groups; -CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )-, -C(CH 3 ) 2 CH 2 -, -CH(CH 2 CH 3 )CH 2 -, -C(CH 2 CH 3 ) 2 -CH 2 - and other alkylethylene groups; -CH(CH 3 )CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 - and other alkyltrimethylene groups; -CH(CH 3 )CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 CH 2 - and other alkyltetramethylene groups and other alkylalkylene groups can be mentioned. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0210] Also, R’ 201The cyclic hydrocarbon group in [the compound] may contain a heteroatom such as a heterocyclic ring. Specifically, lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-7) described above, -SO-containing cyclic groups represented by the general formulas (b5-r-1) to (b5-r-4) described later, and heterocyclic groups represented by the following chemical formulas (r-hr-1) to (r-hr-16) are exemplified. 2 As the substituents in the cyclic group of

[0211]

Chemical formula

[0212] R’ 201 , for example, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, etc. are exemplified. As the alkyl group as a substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group are most preferable. As the alkoxy group as a substituent, an alkoxy group having 1 to 5 carbon atoms is preferable, 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 preferable, and a methoxy group and an ethoxy group are most preferable. As the halogen atom as a substituent, a fluorine atom is preferable. As the halogenated alkyl group as a substituent, a group in which part or all of the hydrogen atoms of an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group, are substituted with the halogen atom is exemplified. The carbonyl group as a substituent is a group that substitutes the methylene group (-CH 2 -) constituting the cyclic hydrocarbon group.

[0213] The chain alkyl group which may have a substituent: R’ 201 The chain alkyl group of [the compound] may be either linear or branched. As the linear alkyl group, it is preferably having 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. As the branched alkyl group, it is preferably having 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specifically, for example, 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 and the like can be mentioned.

[0214] Chain alkenyl group which may have a substituent: R’ 201 As the chain alkenyl group of R’, it may be either linear or branched, preferably having 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, further preferably 2 to 4 carbon atoms, and particularly preferably 3 carbon atoms. As the linear alkenyl group, for example, vinyl group, propenyl group (allyl group), butenyl group and the like can be mentioned. As the branched alkenyl group, for example, 1-methylvinyl group, 2-methylvinyl group, 1-methylpropenyl group, 2-methylpropenyl group and the like can be mentioned. Among the above, as the chain alkenyl group, a linear alkenyl group is preferred, a vinyl group and a propenyl group are more preferred, and a vinyl group is particularly preferred.

[0215] R’ 201 Examples of the substituent in the chain alkyl group or alkenyl group of R’ include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and a cyclic group in the above R’ 201 and the like.

[0216] R’ 201The cyclic group which may have a substituent, the chain-like alkyl group which may have a substituent, or the chain-like alkenyl group which may have a substituent, in addition to those described above, as the cyclic group which may have a substituent or the chain-like alkyl group which may have a substituent, those similar to the acid dissociable group represented by the above formula (a1-r-2) are also included.

[0217] Among them, R’ 201 is preferably a cyclic group which may have a substituent, and more preferably a cyclic hydrocarbon group which may have a substituent. More specifically, for example, a group obtained by removing one or more hydrogen atoms from a phenyl group, a naphthyl group, a polycycloalkane; a lactone-containing cyclic group represented by the above general formulas (a2-r-1) to (a2-r-7); -SO 2 -containing cyclic groups represented by the following general formulas (b5-r-1) to (b5-r-4) and the like are preferable.

[0218] In the above general formulas (ca-1) to (ca-3), R 201 ~R 203 、R 206 ~R 207 When they are bonded to each other to form a ring together with the sulfur atom in the formula, heteroatoms such as sulfur atoms, oxygen atoms, nitrogen atoms, and functional groups such as carbonyl groups, -SO-, -SO 2 -, -SO 3 -, -COO-, -CONH- or -N(R N )(wherein R N is an alkyl group having 1 to 5 carbon atoms.) may be bonded through such functional groups. As the formed ring, it is preferable that one ring containing the sulfur atom in the formula in its ring skeleton is a 3- to 10-membered ring including the sulfur atom, and particularly preferably a 5- to 7-membered ring. Specific examples of the formed ring include, for example, thiophene ring, thiazole ring, benzothiophene ring, dibenzothiophene ring, 9H-thioxanthene ring, thioxanthone ring, thianthrene ring, phenoxathiin ring, tetrahydrothiophenium ring, tetrahydrothiopyranium ring and the like.

[0219] R 208 ~R 209Each 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. When it is an alkyl group, they may be bonded to each other to form a ring.

[0220] R 210 is an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a -SO 2 -containing cyclic group. R 210 Examples of the aryl group in R include unsubstituted aryl groups having 6 to 20 carbon atoms, and a phenyl group and a naphthyl group are preferred. 210 Examples of the alkyl group in R include linear or cyclic alkyl groups, preferably those having 1 to 30 carbon atoms. 210 The alkenyl group in R preferably has 2 to 10 carbon atoms. 210 In R 2 any -SO 2 -containing cyclic group can be used without particular limitation. Specifically, groups represented by the following general formulas (b5-r-1) to (b5-r-4) are included. A "-SO

[0221]

Chemical formula

[0222] In the general formulas (b5-r-1) to (b5-r-2), B” is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, or an oxygen atom or a sulfur atom. As B”, an alkylene group having 1 to 5 carbon atoms or -O- is preferable, an alkylene group having 1 to 5 carbon atoms is more preferable, and a methylene group is even more preferable.

[0223] In the general formulas (b5-r-1) to (b5-r-4), Rb’ 51 are each independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR”, -OC(=O)R”, a hydroxyalkyl group or a cyano group, and among them, it is preferable that they are each independently a hydrogen atom or a cyano group.

[0224] Specific examples of the groups represented by the following general formulas (b5-r-1) to (b5-r-4) are given below. “Ac” in the formula represents an acetyl group.

[0225]

Chemical formula

[0226]

Chemical formula

[0227]

Chemical formula

[0228] Specific examples of the preferable cation represented by the formula (ca-1) include cations each represented by the following chemical formulas.

[0229]

Chemical formula

[0230]

Chemical formula

[0231] [Chemical formula] [In the formula, 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.]

[0232] [Chemical formula]

[0233] [Chemical formula]

[0234] [Chemical formula] [In the formula, R” 201 is a hydrogen atom or a substituent, and the substituents are the same as those exemplified as the substituents that R 201 ~R 207 , and R 210 ~R 212 may have.]

[0235] [Chemical formula]

[0236] Specific examples of the preferred cation represented by the formula (ca-2) include diphenyliodonium cation, bis(4-tert-butylphenyl)iodonium cation, and the like.

[0237] Specific examples of the preferred cation represented by the formula (ca-3) include cations respectively represented by the following formulas (ca-3-1) to (ca-3-6).

[0238] [Chemical formula]

[0239] The cationic part ((M’ m+ ) 1 / m ) in the formula (a5-1) is preferably a sulfonium cation, more preferably the cations represented by the formulas (ca-1) to (ca-3), still more preferably the cation represented by the formula (ca-1), and particularly preferably the cations represented by the formulas (ca-1-1) to (ca-1-84). Particularly from the viewpoint of high sensitivity, as the preferred cation represented by the formula (ca-1), those having an electron-withdrawing group such as a fluorine atom, a fluorinated alkyl group, and a sulfonyl group as a substituent are preferred. For example, the cations selected from the group consisting of the cations represented by the above chemical formulas (ca-1-44), (ca-1-71) to (ca-1-84) are particularly preferred.

[0240] Specific preferred examples of the structural unit (a5) are shown below. In the following formulas, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group. m and M’ m+ are the same as m and M’ m+ in the above general formula (a5-1).

[0241]

Chemical formula

[0242]

Chemical formula

[0243]

Chemical formula

[0244] The structural unit (a5) contained in the component (A1) may be one kind or two or more kinds. When the component (A1) has the constitutional unit (a5), the proportion of the constitutional unit (a5) in the component (A1) is preferably 5 to 25 mol%, more preferably 10 to 20 mol%, and still more preferably 15 to 20 mol% with respect to the total (100 mol%) of all the constitutional units constituting the component (A1). When the proportion of the constitutional unit (a5) is at least the lower limit of the above-mentioned preferred range, it becomes easier to achieve further higher sensitivity and improved resolution. On the other hand, when it is at most the upper limit of the above-mentioned preferred range, it becomes easier to balance with other constitutional units.

[0245] Constitutional unit (a6): The constitutional unit (a6) is a constitutional unit having acid diffusion controllability. The component (A1) may or may not have the constitutional unit (a6). Known constitutional units can be used as the constitutional unit (a6). Examples of the constitutional unit (a6) include constitutional units containing the structures described in the following components (D1) and (D2). For example, constitutional units containing the structures represented by any of the following general formulas (d1-1) to (d1-3) can be mentioned.

[0246] The constitutional unit (a6) contained in the component (A1) may be one kind or two or more kinds. When the component (A1) has the constitutional unit (a6), the proportion of the constitutional unit (a6) in the component (A1) is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and still more preferably 3 to 10 mol% with respect to the total (100 mol%) of all the constitutional units constituting the component (A1). When the proportion of the constitutional unit (a6) is at least the lower limit of the above-mentioned preferred range, it becomes easier to achieve further higher sensitivity. On the other hand, when it is at most the upper limit of the above-mentioned preferred range, it becomes easier to balance with other constitutional units.

[0247] Constitutional unit (a0): The component (A1) is a constitutional unit containing the cation (C0). The constitutional unit (a0) is represented by the following general formula (a0-1).

[0248] [Chemical formula] [In the formula, R is a hydrogen atom, a carbon atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. Mc + is the cation (C0). Rx 0- is a group containing an anion. ]

[0249] In the formula (a0-1), R is the same as R in the general formula (a1-1). In the formula (a0-1), Rx 0- includes a group having the structure of the anion part of a compound represented by any of the following general formulas (b-1) to (b-3) and (d1-1) to (d1-3). Rx 0- When Rx includes the structure of the anion part of a compound represented by any of the following general formulas (b-1) to (b-3), the constitutional unit (a0) is a constitutional unit that generates an acid upon exposure. Rx 0- When Rx includes the structure of the anion part of a compound represented by any of the following general formulas (d1-1) to (d1-3), the constitutional unit (a0) is a constitutional unit having acid diffusion control properties.

[0250] Constitutional unit (a0b) that generates an acid upon exposure: The constitutional unit (a0) may be a constitutional unit that generates an acid upon exposure (hereinafter, also referred to as "constitutional unit (a0b)). The constitutional unit (a0b) may have the anion part in the above-mentioned constitutional unit (a5). The constitutional unit (a0b) may be a constitutional unit represented by the following general formula (a0-1b).

[0251] [Chemical formula] [In the formula, R m is an alkyl group having 1 to 5 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogen atom, or a hydrogen atom. La 50 is a divalent linking group or a single bond. Ra 50 is a divalent hydrocarbon group that may have a substituent. n a5 is an integer from 0 to 2. La51 is a divalent linking group. Ya 5 is a divalent linking group which may have a hetero atom, or a single bond. Ra 51 and Ra 52 are each independently a hydrogen atom, a fluorine atom or a fluorinated alkyl group. n5 is an integer of 1 to 4. Mc + is the cation (C0).]

[0252] R m , La 50 , Ra 50 , n a5 , La 51 , Ya 5 , Ra 51 , Ra 52 and n5 are the same as those in the formula (a5-1), respectively.

[0253] Specific examples of the constitutional unit (a0b) include constitutional units having an anion part of the above formulas (a5-1-1) to (a5-1-22) and having a cation represented by the general formula (c0) as a cation part. That is, in the above formulas (a5-1-1) to (a5-1-22), constitutional units in which M’ m+ is a cation represented by the general formula (c0) are included. In this case, m is 1.

[0254] Preferred specific examples of the constitutional unit (a0b) include the following constitutional units. In the following formulas, R α represents a hydrogen atom, a methyl group or a trifluoromethyl group. Mc + is the cation (C0).

[0255]

Chemical formula

[0256] Constitutional unit (a0d) having acid diffusion controllability: The structural unit (a0) may be a structural unit having acid diffusion control properties (hereinafter, also referred to as "structural unit (a0d)"). The structural unit (a0d) may be a structural unit represented by the following general formula (a0-1d).

[0257] [Chemical formula] [In the formula, R m is an alkyl group having 1 to 5 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogen atom or a hydrogen atom. La d0 is a divalent linking group or a single bond. Ra d0 is an optionally substituted divalent hydrocarbon group. n d is an integer from 0 to 2. Mc + is the cation (C0).]

[0258] In the formula (a0-1d), R m is the same as that in the formula (a5-1). In the formula (a0-1d), as the divalent linking group in La d0 , the same ones as the divalent linking group in La 50 in the formula (a5-1) can be mentioned. In the formula (a0-1d), as the optionally substituted divalent hydrocarbon group in Ra d0 , the same ones as the optionally substituted divalent hydrocarbon group in Ra 50 in the formula (a5-1) can be mentioned. In the formula (a0-1d), nd is preferably 1 or 2, and more preferably 1.

[0259] Hereinafter, preferred specific examples of the structural unit (a0d) are shown, but it is not limited thereto. In the following formulas, R α represents a hydrogen atom, a methyl group or a trifluoromethyl group. Mc + is the cation (C0).

[0260] [Chemical formula]

[0261] [Chemical formula]

[0262] (A1) component may have one or more kinds of constituent units (a0). (A1) component may have both constituent unit (a0b) and constituent unit (a0d), or may have only one of them.

[0263] When (A1) component has constituent unit (a0b), the proportion of constituent unit (a0b) in (A1) component is preferably 5 to 25 mol%, more preferably 8 to 20 mol%, based on the total of all constituent units constituting (A1) component (100 mol%). When the proportion of constituent unit (a0b) is at or above the lower limit of the above preferred range, it becomes easier to achieve further higher sensitivity, reduction of roughness, and improvement of resolution. On the other hand, when it is at or below the upper limit of the above preferred range, it becomes easier to balance with other constituent units.

[0264] When (A1) component has constituent unit (a0d), the proportion of constituent unit (a0d) in (A1) component is preferably 1 to 20 mol%, more preferably 3 to 15 mol%, still more preferably 5 to 10 mol%, based on the total of all constituent units constituting (A1) component (100 mol%). When the proportion of constituent unit (a0d) is at or above the lower limit of the above preferred range, it becomes easier to achieve further higher sensitivity, reduction of roughness, and improvement of resolution. On the other hand, when it is at or below the upper limit of the above preferred range, it becomes easier to balance with other constituent units.

[0265] Constituent unit (a8): Constituent unit (a8) is a constituent unit derived from a compound represented by the following general formula (a8-1). (A1) component may or may not have constituent unit (a8).

[0266] [Chemical formula] [In the formula, W 2 is a polymerizable group-containing group. Ya x2 is a single bond or an (n ax2 +1)-valent linking group. Ya x2 and W 2 may form a condensed ring. R 1 is a fluorinated alkyl group having 1 to 12 carbon atoms. R 2 is an organic group having 1 to 12 carbon atoms which may have a fluorine atom or a hydrogen atom. R 2 and Ya x2 may be bonded to each other to form a ring structure. n ax2 is an integer of 1 to 3. ]

[0267] W 2 The "polymerizable group" in the polymerizable group-containing group of W is a group that enables a compound having a polymerizable group to polymerize by radical polymerization or the like, and refers to a group containing a multiple bond between carbon atoms such as an ethylenic double bond.

[0268] The polymerizable group-containing group may be a group composed only of a polymerizable group, or a group composed of a polymerizable group and another group other than the polymerizable group. Examples of the other group other than the polymerizable group include a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a hetero atom, and the like. Examples of the polymerizable group-containing group include, for example, a group represented by the chemical formula: C(R X11 )(R X12 )=C(R X13 )-Ya x0 -. In this chemical formula, R X11 , R X12 and R X13 are each a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, and Ya x0 is a single bond or a divalent linking group.

[0269] Ya x2 and W 2 The condensed ring formed by and is, for the polymerizable group at the W 2 site and Yax2 The condensed ring formed by it, W 2 The other group other than the polymerizable group at the site and Ya x2 Examples thereof include the condensed ring formed by it and Ya. Ya x2 And W 2 The condensed ring formed by it and W may have a substituent.

[0270] Specific examples of the structural unit (a8) are shown below. In the following formula, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0271]

Chemical formula

[0272] Among the above examples, the structural unit (a8) is preferably at least one selected from the group consisting of the structural units represented by chemical formulas (a8-1-01) to (a8-1-04), (a8-1-06), (a8-1-08), (a8-1-09), and (a8-1-10), and more preferably at least one selected from the group consisting of the structural units represented by chemical formulas (a8-1-01) to (a8-1-04) and (a8-1-09).

[0273] The structural unit (a8) contained in the (A1) component may be one kind or two or more kinds. The (A1) component may or may not have the structural unit (a8). The proportion of the structural unit (a8) in the (A1) component is preferably 0 to 50 mol%, more preferably 0 to 30 mol%, based on the total (100 mol%) of all the structural units constituting the (A1) component.

[0274] The (A1) component contained in the resist composition may be used alone or in combination of two or more.

[0275] Examples of the component (A1) include a polymer compound composed of a constitutional unit (a1) and a constitutional unit (a10); a polymer compound composed of a constitutional unit (a1), a constitutional unit (a10), and a constitutional unit (a0), etc.

[0276] In the polymer compound composed of the constitutional unit (a1) and the constitutional unit (a10), the proportion of the constitutional unit (a1) is more preferably 10 to 75 mol%, further preferably 30 to 70 mol%, and still further preferably 40 to 70 mol% with respect to the total of all constitutional units (100 mol%) constituting the polymer compound. The proportion of the constitutional unit (a10) in the polymer compound is preferably 25 to 90 mol%, more preferably 30 to 70 mol%, still more preferably 30 to 60 mol%, and particularly preferably 20 to 50 mol% with respect to the total of all constitutional units (100 mol%) constituting the polymer compound.

[0277] Such a component (A1) can be produced by dissolving monomers that induce each constitutional unit in a polymerization solvent, adding a radical polymerization initiator such as azobisisobutyronitrile (AIBN), dimethyl azobisisobutyrate (e.g., V-601, etc.) thereto, and performing polymerization. Alternatively, such a component (A1) can be produced by dissolving a monomer that induces the constitutional unit (a1) and a monomer that induces an arbitrary constitutional unit (e.g., the constitutional unit (a10), the constitutional unit (a5), etc.) in a polymerization solvent, adding the radical polymerization initiator as described above thereto, performing polymerization, and then performing a deprotection reaction. Note that during polymerization, for example, a chain transfer agent such as HS-CH 2 -CH 2 -CH 2 -C(CF 3 ) 2 -OH may be used in combination. By doing so, a -C(CF 3 ) 2 -OH group may be introduced at the terminal. Thus, a copolymer into which a hydroxyalkyl group in which some hydrogen atoms of the alkyl group are substituted with fluorine atoms is introduced is effective for reducing development defects and LER (line edge roughness: uneven unevenness on the side wall of the line).

[0278] (A1) component's weight-average molecular weight (Mw) (in terms of polystyrene conversion standard by gel permeation chromatography (GPC)) is not particularly limited, preferably 1,000 to 50,000, more preferably 5,000 to 40,000, and even more preferably 5,000 to 30,000. When the Mw of the (A1) component is below the preferred upper limit of this range, it has sufficient solubility in the resist solvent for use as a resist. When it is above the preferred lower limit of this range, the dry etching resistance and the cross-sectional shape of the resist pattern are good. (A1) component's dispersity (Mw / Mn) is not particularly limited, preferably 1.0 to 4.0, more preferably 1.0 to 3.0, and particularly preferably 1.0 to 2.0. Here, Mn represents the number-average molecular weight.

[0279] ·Regarding the (A2) component The resist composition of this embodiment may use, as the (A) component, a base material component (hereinafter referred to as the "(A2) component") that does not correspond to the (A1) component and whose solubility in the developer changes due to the action of an acid. (A2) component is not particularly limited and may be arbitrarily selected from a number of conventionally known base material components for chemically amplified resist compositions. (A2) component may be used alone as one kind of high molecular compound or low molecular compound, or may be used in combination of two or more kinds.

[0280] (A) component's proportion of the (A1) component in the (A) component is preferably 25% by mass or more, more preferably 50% by mass or more, even more preferably 75% by mass or more, and may be 100% by mass, based on the total mass of the (A) component. When the proportion is 25% by mass or more, it is easy to form a resist pattern with excellent various lithography characteristics such as high sensitivity, resolution, and CDU improvement.

[0281] In the resist composition of this embodiment, the content of the (A) component may be adjusted according to the resist film thickness to be formed, etc.

[0282] <Acid generator component (B)> The resist composition of this embodiment may contain an acid generator component (B) that generates an acid upon exposure. Component (B) is not particularly limited, and those that have been proposed as acid generators for chemically amplified resist compositions can be used. Examples of such acid generators include onium salt-based acid generators such as iodonium salts and sulfonium salts, oxime sulfonate-based acid generators; diazomethane-based acid generators such as bisalkyl or bisaryl sulfonyldiazomethanes, poly(bissulfonyl)diazomethanes; nitrobenzyl sulfonate-based acid generators, iminosulfonate-based acid generators, disulfone-based acid generators, and many others. The form of inclusion of component (B) may be in the form of a compound, may be incorporated into component (A1) as the above-described structural unit (a5), or may be in both of these forms.

[0283] Examples of onium salt-based acid generators include, for example, a compound represented by the following general formula (b-1) (hereinafter also referred to as “component (b-1)”), a compound represented by general formula (b-2) (hereinafter also referred to as “component (b-2)”), or a compound represented by general formula (b-3) (hereinafter also referred to as “component (b-3)”).

[0284] Examples of onium salt-based acid generators include, for example, a compound represented by the following general formula (b-1) (hereinafter also referred to as “component (b-1)”), a compound represented by general formula (b-2) (hereinafter also referred to as “component (b-2)”), or a compound represented by general formula (b-3) (hereinafter also referred to as “component (b-3)”).

[0285] [Chemical formula] [In the formula, R 101 and R 104 ~R 108 are each independently a cyclic group that may have a substituent, a chain-like alkyl group that may have a substituent, or a chain-like alkenyl group that may have a substituent. R 104 and R 105may be mutually bonded to form a ring structure. R 102 is a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom. Y 101 is a divalent linking group containing an oxygen atom or a single bond. V 101 ~ V 103 are each independently a single bond, an alkylene group or a fluorinated alkylene group. However, Y 101 and V 101 will not simultaneously be a single bond. L 101 ~ L 102 are each independently a single bond or an oxygen atom. L 103 ~ L 105 are each independently a single bond, -CO- or -SO 2 -. m is an integer of 1 or more, and M’ m+ is an m-valent onium cation. ]

[0286] {Anion part} · Anion in the (b-1) component In formula (b-1), R 101 is a cyclic group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent.

[0287] Cyclic group which may have a substituent: 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. The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. Further, the aliphatic hydrocarbon group is preferably saturated.

[0288] R 101 The aromatic hydrocarbon group in 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, still 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 substituent. R 101Specific examples of the aromatic ring in the aromatic hydrocarbon group include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or an aromatic heterocyclic ring in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms. Examples of the heteroatom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. R 101 Specific examples of the aromatic hydrocarbon group in include a group obtained by removing one hydrogen atom from the aromatic ring (aryl group: for example, phenyl group, naphthyl group, etc.), a group in which one hydrogen atom of the aromatic ring is substituted with an alkylene group (for example, benzyl group, phenethyl group, 1-naphthylmethyl group, etc.). The number of carbon atoms in the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0289] R 101 The cyclic aliphatic hydrocarbon group in includes an aliphatic hydrocarbon group containing a ring in its structure. Examples of the aliphatic hydrocarbon group containing a ring in this structure include an alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring), a group in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from monocycloalkane is preferred. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. As the polycyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from polycycloalkane is preferred, and the polycycloalkane preferably has 7 to 30 carbon atoms. Among them, as the polycycloalkane, adamantane, norbornane, isobornane, tricyclo[5.2.1.02,6 Polycycloalkanes having a crosslinked ring system polycyclic skeleton such as decane and tetracyclododecane; polycycloalkanes having a condensed ring system polycyclic skeleton such as a cyclic group having a steroid skeleton are more preferable.

[0290] Among them, R 101 As the cyclic aliphatic hydrocarbon group in, a group obtained by removing one or more hydrogen atoms from monocycloalkane or polycycloalkane is preferable, a group obtained by removing one hydrogen atom from polycycloalkane is more preferable, an adamantyl group and a norbornyl group are further preferable, and an adamantyl group is particularly preferable.

[0291] The linear aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable. Specifically, a methylene group [-CH 2 -], an ethylene group [-(CH 2 ) 2 -], a trimethylene group [-(CH 2 ) 3 -], a tetramethylene group [-(CH 2 ) 4 -], a pentamethylene group [-(CH 2 ) 5 -] and the like can be mentioned. The branched-chain aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, still more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. As the branched-chain aliphatic hydrocarbon group, a branched-chain alkylene group is preferable. Specifically, -CH(CH 3 )-, -CH(CH 2 CH 3 )-, -C(CH 3 ) 2 -, -C(CH 3 )(CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 2 CH 3)-, -C(CH 2 CH 3 ) 2 - and other alkylmethylene groups; -CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )-, -C(CH 3 ) 2 CH 2 -, -CH(CH 2 CH 3 )CH 2 -, -C(CH 2 CH 3 ) 2 -CH 2 - and other alkylethylene groups; -CH(CH 3 )CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 - and other alkyltrimethylene groups; -CH(CH 3 )CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 CH 2 - and other alkyltetramethylene groups and other alkylalkylene groups can be mentioned. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

[0292] Also, the cyclic hydrocarbon group in R 101 may contain a hetero atom such as a heterocyclic ring. Specifically, the lactone-containing cyclic group represented by the general formulas (a2-r-1) to (a2-r-7), the -SO 2 -containing cyclic group represented by the general formulas (b5-r-1) to (b5-r-4), and other heterocyclic groups represented by the chemical formulas (r-hr-1) to (r-hr-16) can be mentioned.

[0293] R 101Examples of the substituent in the cyclic group include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, and the like. As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable. As the alkoxy group as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferable, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, a tert-butoxy group, and most preferably a methoxy group or an ethoxy group. As the halogen atom as the substituent, a fluorine atom, a bromine atom, or an iodine atom is preferable. Examples of the halogenated alkyl group as the substituent include a group in which some or all of the hydrogen atoms of an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group, are substituted with the halogen atom. The carbonyl group as the substituent is a group that substitutes a methylene group (-CH 2 -) constituting the cyclic hydrocarbon group.

[0294] R 101 The cyclic hydrocarbon group in may be a condensed cyclic group including a condensed ring in which an aliphatic hydrocarbon ring and an aromatic ring are condensed. Examples of the condensed ring include those in which one or more aromatic rings are condensed to a polycycloalkane having a bridged ring system polycyclic skeleton. Specific examples of the bridged ring system polycycloalkane include bicycloalkanes such as bicyclo[2.2.1]heptane (norbornane) and bicyclo[2.2.2]octane. As the condensed ring type, a group including a condensed ring in which two or three aromatic rings are condensed to a bicycloalkane is preferable, and a group including a condensed ring in which two or three aromatic rings are condensed to bicyclo[2.2.2]octane is more preferable. Specific examples of the condensed cyclic group in R 101 include those represented by the following formulas (r-br-1) to (r-br-2). In the formula, * represents a bond that binds to Y in the formula (b-1). 101

[0295]

Chemical formula

[0296] R 101 Examples of the substituent that the condensed cyclic group in R may optionally have include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an aromatic hydrocarbon group, an alicyclic hydrocarbon group, and the like. The alkyl group, alkoxy group, halogen atom, and halogenated alkyl group as the substituent of the condensed cyclic group are the same as those exemplified as the substituent of the cyclic group in the above R 101 and can be exemplified as the same ones. Examples of the aromatic hydrocarbon group as the substituent of the condensed cyclic group include a group obtained by removing one hydrogen atom from an aromatic ring (aryl group: for example, phenyl group, naphthyl group, etc.), a group in which one hydrogen atom of the aromatic ring is substituted with an alkylene group (for example, benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc., arylalkyl groups such as these), a heterocyclic group represented by the above formulas (r-hr-1) to (r-hr-6), and the like. Examples of the alicyclic hydrocarbon group as the substituent of the condensed cyclic group include a group obtained by removing one hydrogen atom from a monocycloalkane such as cyclopentane or cyclohexane; a group obtained by removing one hydrogen atom from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 decane, or tetracyclododecane; a lactone-containing cyclic group represented by the general formulas (a2-r-1) to (a2-r-7); a -SO 2 -containing cyclic group represented by the general formulas (b5-r-1) to (b5-r-4); a heterocyclic group represented by the formulas (r-hr-7) to (r-hr-16), and the like.

[0297] Optionally substituted chain alkyl group: R 101 The chain alkyl group of R may be either linear or branched. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specifically, for example, 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. can be mentioned.

[0298] The chain alkenyl group which may have a substituent: R 101 The chain alkenyl group of may be either linear or branched, preferably has 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, still more preferably 2 to 4 carbon atoms, and particularly preferably 3 carbon atoms. Examples of the linear alkenyl group include vinyl group, propenyl group (allyl group), butenyl group, etc. Examples of the branched alkenyl group include 1-methylvinyl group, 2-methylvinyl group, 1-methylpropenyl group, 2-methylpropenyl group, etc. Among the above, the linear alkenyl group is preferred as the chain alkenyl group, the vinyl group and the propenyl group are more preferred, and the vinyl group is particularly preferred.

[0299] R 101 Examples of the substituent in the chain alkyl group or alkenyl group of include alkoxy group, halogen atom, halogenated alkyl group, hydroxyl group, carbonyl group, nitro group, amino group, cyclic group in the above R 101 etc.

[0300] In formula (b-1), Y 101 is a single bond or a divalent linking group containing an oxygen atom. Y 101 When is a divalent linking group containing an oxygen atom, the Y 101It may contain atoms other than oxygen atoms. Examples of atoms other than oxygen atoms include carbon atoms, hydrogen atoms, sulfur atoms, nitrogen atoms, and the like. Examples of the divalent linking group containing an oxygen atom include the linking groups represented by the above general formulas (L-al-1) to (L-al-8), respectively. In the following general formulas (L-al-1) to (L-al-8), R in the above formula (b-1) 101 binds to V' in the following general formulas (L-al-1) to (L-al-8) 101 is.

[0301] In the formula (b-1), V 101 is a single bond, an alkylene group or a fluorinated alkylene group. Among them, V 101 is preferably a single bond or a linear fluorinated alkylene group having 1 to 4 carbon atoms.

[0302] In the formula (b-1), R 102 is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. R 102 is preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and more preferably a fluorine atom.

[0303] Specific examples of the anion part represented by the formula (b-1) include, for example, when Y 101 is a single bond, fluorinated alkyl sulfonate anions such as trifluoromethanesulfonate anion and perfluorobutanesulfonate anion; when Y 101 is a divalent linking group containing an oxygen atom, anions represented by any of the following formulas (an-1) to (an-3) can be mentioned.

[0304]

Chemical formula

[0305] R” 101 、R” 102 and R” 103 The aliphatic cyclic group which may have a substituent of R”, R” 101 is preferably a group exemplified as the cyclic aliphatic hydrocarbon group in R 101 in the formula (b-1). Examples of the substituent include the same substituents as those which may substitute the cyclic aliphatic hydrocarbon group in R

[0306] R” 101 and R” 103 The aromatic cyclic group which may have a substituent in R” 101 is preferably a group exemplified as the aromatic hydrocarbon group in the cyclic hydrocarbon group in R 101Examples of the substituent that may replace the aromatic hydrocarbon group are the same as those described above.

[0307] R” 101 The linear alkyl group which may have a substituent in is preferably a group exemplified as the linear alkyl group in the formula (b-1) for R 101 above. R” 103 The linear alkenyl group which may have a substituent in is preferably a group exemplified as the linear alkenyl group in the formula (b-1) for R 101 above.

[0308] · Anion in the component (b-2) In the formula (b-2), R 104 , R 105 are each independently a cyclic group which may have a substituent, a linear alkyl group which may have a substituent, or a linear alkenyl group which may have a substituent, and examples thereof are the same as those of R 101 in the formula (b-1). However, R 104 , R 105 may be bonded to each other to form a ring. R 104 , R 105 are preferably linear alkyl groups which may have a substituent, more preferably linear or branched alkyl groups, or linear or branched fluorinated alkyl groups. The number of carbon atoms of the linear alkyl group is preferably 1 to 10, more preferably 1 to 7 carbon atoms, and even more preferably 1 to 3 carbon atoms. The number of carbon atoms of the linear alkyl group for R 104 , R 105 is preferably smaller within the above range of the number of carbon atoms for reasons such as good solubility in the resist solvent. Also, R 104 , R 105In the case of the chain alkyl group, the more hydrogen atoms are substituted with fluorine atoms, the stronger the acid strength becomes, and it is preferable because the transparency to high-energy light or electron beams of 250 nm or less is improved. The ratio of fluorine atoms in the chain alkyl group, that is, the fluorination rate is preferably 70 to 100%, more preferably 90 to 100%, and most preferably a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms. In formula (b-2), V 102 , V 103 are each independently a single bond, an alkylene group, or a fluorinated alkylene group, and examples thereof are the same as V 101 in formula (b-1). In formula (b-2), L 101 , L 102 are each independently a single bond or an oxygen atom.

[0309] · Anion in component (b-3) In formula (b-3), R 106 ~R 108 are each independently a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and examples thereof are the same as R 101 in formula (b-1). In formula (b-3), L 103 ~L 105 are each independently a single bond, -CO- or -SO 2 -.

[0310] Among the above, as the anion part of component (B), the anion in component (b-1) is preferable, and the anion represented by the above formula (an-1) is more preferable.

[0311] {Cation part} In the above formulas (b-1), (b-2), and (b-3), M’ m+ represents an m-valent onium cation. Among these, a sulfonium cation and an iodonium cation are preferable. m is an integer of 1 or more.

[0312] (B) component's cationic part preferably is a sulfonium cation, more preferably cations respectively represented by the formulas (ca-1) to (ca-3), still more preferably the cation represented by the formula (ca-1), and particularly preferably cations respectively represented by the formulas (ca-1-1) to (ca-1-84).

[0313] Compound (B0): (B) component's cationic part may be the cation (C0). In this case, the (B) component becomes the compound (C). The compound (C) as the (B) component is a compound (B0) represented by the following general formula (b0).

[0314]

Chemical formula

[0315]

Chemical formula

[0316] In the formulas (b0-1) to (b0-3), R 101 , R 104 ~R 108 , R 102 , Y 101 , V 101 ~V 103 , L 101 ~L 102 , and L 103 ~L 105 are the same as those in the formulas (b-1) to (b-3), respectively.

[0317] In the formula (b0-1), R 101 is preferably an aromatic hydrocarbon group which may have a substituent, and more preferably a phenyl group which may have a substituent. The aromatic hydrocarbon group preferably has a halogen atom as a substituent, and more preferably has an iodine atom as a substituent. The number of iodine atoms as a substituent is 1 to 4, preferably 1 to 3, and more preferably 2 or 3.

[0318] Specific examples of the compound (B0) are shown below, but are not limited thereto. In the following formulas, Mc + is the cation (C0).

[0319]

Chemical formula

[0320]

Chemical formula

[0321] Specific examples of the compound (B0) are shown below, but are not limited thereto.

[0322] [Chemical formula]

[0323] [Chemical formula]

[0324] In the resist composition of the present embodiment, the component (B) may be used alone or in combination of two or more. When the resist composition contains the component (B), the content of the component (B) in the resist composition is preferably less than 50 parts by mass, more preferably 5 to 45 parts by mass, and even more preferably 10 to 43 parts by mass with respect to 100 parts by mass of the component (A). By setting the content of the component (B) within the above-mentioned preferred range, when each component of the resist composition is dissolved in an organic solvent, a uniform solution is easily obtained, and the storage stability as a resist composition is good, which is preferable.

[0325] When the component (B) contains the compound (B0), the compound (B0) may be used alone or in combination of two or more. When the component (B) contains the compound (B0), the proportion of the compound (B0) in the whole component (B) is, for example, 50% by mass or more, preferably 70% by mass or more, and more preferably 95% by mass or more. The proportion of the compound (B0) in the whole component (B) may be 100% by mass. When the proportion of the compound (B0) in the component (B) is equal to or higher than the lower limit value of the above-mentioned preferred range, it is easy for all of sensitivity, roughness, and resolution to be good.

[0326] <Base component (D)> In addition to the component (A), the resist composition of this embodiment may contain a base component ((D) component) that traps the acid generated by exposure (i.e., controls the diffusion of the acid). The (D) component acts as a quencher (acid diffusion control agent) that traps the acid generated by exposure in the resist composition. Examples of the (D) component include a photo-dissociable base (D1) (hereinafter referred to as the "(D1) component") that decomposes upon exposure and loses acid diffusion controllability, and a nitrogen-containing organic compound (D2) (hereinafter referred to as the "(D2) component") that does not correspond to the (D1) component. Among these, the photo-dissociable base ((D1) component) is preferable because it is easy to enhance the characteristics of high sensitivity, reduction of roughness, and suppression of the occurrence of coating defects. As the form of containing the (D1) component and the (D2) component, it may be in the form of a compound, may be in the form incorporated into the (A1) component as the above-described structural unit (a6), or may be in both of these forms. The compound exemplified as the (D1) component described later may be used as the acid generator component ((B) component) described later in combination with other compounds in some cases.

[0327] ·Regarding the (D1) component The (D1) component is not particularly limited as long as it decomposes upon exposure and loses acid diffusion controllability, and one or more compounds selected from the group consisting of a compound represented by the following general formula (d1-1) (hereinafter referred to as the "(d1-1) component"), a compound represented by the following general formula (d1-2) (hereinafter referred to as the "(d1-2) component"), and a compound represented by the following general formula (d1-3) (hereinafter referred to as the "(d1-3) component") are preferable. The (d1-1) to (d1-3) components do not act as a quencher because they decompose in the exposed portion of the resist film and lose acid diffusion controllability (basicity), and act as a quencher in the unexposed portion of the resist film.

[0328] [Chemical formula] [In the formula, Rd 1 ~Rd 4is a cyclic group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent. However, Rd in the formula (d1-2) 2 shall not have a fluorine atom bonded to the carbon atom adjacent to the S atom in 1 . Yd 1 is a single bond or a divalent linking group. m is an integer of 1 or more, and M m+ are each independently an m-valent organic cation.]

[0329] {(d1-1) component} ·· Anion part In the formula (d1-1), Rd 1 is a cyclic group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent, and examples thereof are the same as those of the above R’ 201 . Among these, as Rd 1 , a aromatic hydrocarbon group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain-like alkyl group which may have a substituent is preferable. Examples of the substituent which these groups may have include a hydroxyl group, an oxo group, an alkyl group, an aryl group, a fluorine atom, a fluorinated alkyl group, a lactone-containing cyclic group represented by the above general formulas (a2-r-1) to (a2-r-8), an ether bond, an ester bond, or a combination thereof. When an ether bond or an ester bond is included as a substituent, it may be via an alkylene group, and in this case, as the substituent, a linking group represented by the above formulas (y-al-1) to (y-al-5) is preferable. In addition, when the aromatic hydrocarbon group, the aliphatic cyclic group, or the chain-like alkyl group in Rd 1 has a linking group represented by the above general formulas (y-al-1) to (y-al-7) as a substituent, in the above general formulas (y-al-1) to (y-al-7), the one bonded to the carbon atom constituting the aromatic hydrocarbon group, the aliphatic cyclic group, or the chain-like alkyl group in Rd 1 in the formula (d3-1) is V’ 101 in the above general formulas (y-al-1) to (y-al-7). Examples of the aromatic hydrocarbon group preferably include a phenyl group, a naphthyl group, and a polycyclic structure containing a bicyclooctane skeleton (a polycyclic structure composed of a bicyclooctane skeleton and another ring structure). Examples of the alicyclic group preferably include a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 decane, or tetracyclododecane. The linear alkyl group preferably has 1 to 10 carbon atoms. Specific examples thereof include linear alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group; and branched-chain alkyl groups such as a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.

[0330] When the linear alkyl group is a fluorinated alkyl group having a fluorine atom or a fluorinated alkyl group as a substituent, the fluorinated alkyl group preferably has 1 to 11 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 4 carbon atoms. The fluorinated alkyl group may contain an atom other than a fluorine atom. Examples of the atom other than a fluorine atom include an oxygen atom, a sulfur atom, and a nitrogen atom.

[0331] Preferred specific examples of the anionic part of the component (d1-1) are shown below.

[0332] [Chemical formula]

[0333] ···Cationic part In formula (d1-1), M m+ is an m-valent organic cation. M m+As the organic cation, those similar to the cations respectively represented by the general formulas (ca-1) to (ca-3) are preferably exemplified, the cation represented by the general formula (ca-1) is more preferable, and the cations respectively represented by the formulas (ca-1-1) to (ca-1-84) are even more preferable. The component (d1-1) may be used alone or in combination of two or more.

[0334] {(component (d1-2))} ··Anion part In the formula (d1-2), Rd 2 is a cyclic group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent, and those similar to the above R' 201 are exemplified. However, it is assumed that a fluorine atom is not bonded (not fluorine-substituted) to the carbon atom adjacent to the S atom in Rd 2 . Thereby, the anion of the component (d1-2) becomes a moderately weak acid anion, and the quenching ability as the component (D) is improved. As Rd 2 , it is preferably a chain-like alkyl group which may have a substituent, or an aliphatic cyclic group which may have a substituent, and more preferably an aliphatic cyclic group which may have a substituent.

[0335] The chain-like alkyl group preferably has 1 to 10 carbon atoms, and more preferably 3 to 10 carbon atoms. Examples of the aliphatic cyclic group include adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 decane, tetracyclododecane, etc. with one or more hydrogen atoms removed (which may have a substituent); and a group with one or more hydrogen atoms removed from camphor is more preferable.

[0336] The hydrocarbon group of Rd 2 may have a substituent, and as the substituent, Rd of the formula (d1-1) 1Examples thereof include the same substituents that the hydrocarbon group (aromatic hydrocarbon group, alicyclic group, or chain alkyl group) may have.

[0337] Specific preferred examples of the anionic part of the component (d1-2) are shown below.

[0338] [Chemical formula]

[0339] ·· Cationic part In formula (d1-2), M m+ is an m-valent organic cation, which is the same as M m+ in the above formula (d1-1). The component (d1-2) may be used alone or in combination of two or more.

[0340] {(d1-3) component} ·· Anionic part In formula (d1-3), Rd 3 is an optionally substituted cyclic group, an optionally substituted chain alkyl group, or an optionally substituted chain alkenyl group, and examples thereof include the same as those of R' 201 , and it is preferably a cyclic group, a chain alkyl group, or a chain alkenyl group containing a fluorine atom. Among them, a fluorinated alkyl group is preferred, and more preferred are the same as the fluorinated alkyl group of Rd 1 .

[0341] In formula (d1-3), Rd 4 is an optionally substituted cyclic group, an optionally substituted chain alkyl group, or an optionally substituted chain alkenyl group, and examples thereof include the same as those of R' 201 . Among them, it is preferably an optionally substituted alkyl group, alkoxy group, alkenyl group, or cyclic group. Rd 4The alkyl group in 4 may have some of the hydrogen atoms of the alkyl group substituted with a hydroxyl group, a cyano group or the like. Rd 4 The alkoxy group in

[0342] Rd 4 The alkenyl group in 201 is the same as the alkenyl group in the above R’, and examples thereof include a vinyl group, a propenyl group (allyl group), a 1-methylpropenyl group, and a 2-methylpropenyl group. These groups may further have, as a substituent, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms.

[0343] Rd 4 The cyclic group in 201 is the same as the cyclic group in the above R’, and examples thereof include an alicyclic group obtained by removing one or more hydrogen atoms from a cycloalkane such as cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 decane, tetracyclododecane, or an aromatic group such as a phenyl group or a naphthyl group. Rd 4 When Rd is an alicyclic group, the resist composition dissolves well in an organic solvent, so that the lithography characteristics are good. Also, Rd 4 When Rd 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.

[0344] In formula (d1-3), Yd1 is a single bond or a divalent linking group. Yd 1 The divalent linking group in is not particularly limited, and examples thereof include a divalent hydrocarbon group (aliphatic hydrocarbon group, aromatic hydrocarbon group) which may have a substituent, a divalent linking group containing a hetero atom, and the like. Each of these is the same as the divalent hydrocarbon group which may have a substituent and the divalent linking group containing a hetero atom, which are mentioned in the description of the divalent linking group in Ya in the above formula (a2-1). 21 The divalent linking group in includes the same ones as the divalent hydrocarbon group which may have a substituent and the divalent linking group containing a hetero atom, which are mentioned in the description of the divalent linking group in Ya in. Yd 1 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 linear or branched alkylene group, and even more preferably a methylene group or an ethylene group.

[0345] Specific preferred examples of the anion part of the component (d1-3) are shown below.

[0346]

Chemical formula

[0347]

Chemical formula

[0348] ·· Cation part In the formula (d1-3), M m+ is an m-valent organic cation, which is the same as M in the above formula (d1-1). m+ and (d1-3) component may be used alone or in combination of two or more.

[0349] (D1) component may use only any one of the above (d1-1) to (d1-3) components, or may use two or more in combination. When the resist composition contains the component (D1), the content of the component (D1) in the resist composition is preferably 0.5 to 15 parts by mass, more preferably 1 to 15 parts by mass, and still more preferably 2 to 15 parts by mass with respect to 100 parts by mass of the component (A).

[0350] (D1) component preferably contains the above (d1-1) component. Among the whole (D1) component, the content of the (d1-1) component is preferably 50% by mass or more, preferably 70% by mass or more, still more preferably 90% by mass or more, and the (D1) component may consist only of the compound (d1-1) component.

[0351] Manufacturing method of (D1) component: The manufacturing methods of the above (d1-1) component and (d1-2) component are not particularly limited and can be manufactured by known methods. Also, the manufacturing method of the (d1-3) component is not particularly limited and is manufactured, for example, in the same manner as the method described in US2012-0149916 Gazette. As an example of the base component ((D) component) that traps the acid generated by exposure, the compound of the (D1) component was shown, but the compound of the (D1) component may be used as the (B) component. For example, in the resist composition of this embodiment, a compound of the (D1) component is used as the (B) component, and as the (D) component, a compound that generates an acid having a lower acidity than the acid generated by exposure of the (D1) component compound may be used. Also, in the resist composition of this embodiment, a compound of the (D1) component is used as the (B) component, and as the (D) component, the (D2) component described later may be used.

[0352] Compound (D0): The cationic part in the (D1) component may be the above cation (C0). In this case, the (D1) component becomes the above compound (C). The compound (C) as the (D1) component is a compound (D0) represented by the following general formula (d0).

[0353]

Chemical formula

[0354] Xd in the formula (d0) - includes the anion moieties of the compounds represented by any of the formulas (d1-1) to (d1-3). Examples of the compound (D0) include compounds represented by any of the following general formulas (d0-1) to (d0-3).

[0355] [Chemical formula] [wherein, Rd 1 to Rd 4 are an optionally substituted cyclic group, an optionally substituted linear alkyl group, or an optionally substituted linear alkenyl group. However, it is assumed that a fluorine atom is not bonded to the carbon atom adjacent to the S atom in Rd 2 in the formula (d1-2). Yd 1 is a single bond or a divalent linking group. Mc + is the cation (C0). ]

[0356] Rd in the formulas (d0-1) to (d0-3) 1 to Rd 4 , Yd 1 are the same as those in the formulas (d1-1) to (d1-3), respectively.

[0357] Specific examples of the anion moiety in the formula (d0-1) include the same ones as the specific examples of the anion moiety in the formula (d1-1) above. Specific examples of the anion moiety in the formula (d0-2) include the same ones as the specific examples of the anion moiety in the formula (d1-2) above. Specific examples of the anion moiety in the formula (d0-3) include the same ones as the specific examples of the anion moiety in the formula (d1-3) above.

[0358] Rd in the formula (d0-1) 1 is preferably an aromatic hydrocarbon group which may have a substituent, and more preferably a phenyl group which may have a substituent. The aromatic hydrocarbon group preferably has a halogen atom as a substituent, and more preferably has an iodine atom as a substituent. The number of iodine atoms as substituents is 1 to 4, preferably 1 to 3, and more preferably 2 or 3. Rd 1 The aromatic hydrocarbon group in may optionally have a hydroxy group as a substituent. Rd 1 is preferably an aromatic hydrocarbon group having an iodine atom as a substituent or an aromatic hydrocarbon group having an iodine atom and a hydroxy group as substituents, and more preferably a phenyl group having an iodine atom as a substituent or a phenyl group having an iodine atom and a hydroxy group as substituents.

[0359] Specific examples of the compound (D0) are shown below, but are not limited thereto. In the following formula, Mc + is the cation (C0).

[0360]

Chemical formula

[0361] Specific examples of the compound (D0) are shown below, but are not limited thereto.

[0362]

Chemical formula

[0363] When the component (D1) contains the compound (D0), the compound (D0) component may be used alone or in combination of two or more. When the (D1) component contains the compound (D0), the proportion of the compound (D0) in the whole (D1) component is, for example, 50% by mass or more, preferably 70% by mass or more, and more preferably 95% by mass or more. The proportion of the (D0) component in the whole (D1) component may be 100% by mass.

[0364] In the resist composition of the present embodiment, the proportion of the compound (D0) in the whole (D) component is, for example, 50% by mass or more, preferably 70% by mass or more, and more preferably 95% by mass or more. The proportion of the compound (D0) in the whole (D) component may be 100% by mass.

[0365] When the proportion of the compound (D0) in the (D) component is equal to or higher than the lower limit value of the above-mentioned preferred range, it is easy for all of sensitivity, roughness, and resolution to be good.

[0366] When the resist composition contains the (D0) component, the content of the (D0) component in the resist composition is preferably 0.5 to 15 parts by mass, more preferably 1 to 15 parts by mass, and even more preferably 2 to 15 parts by mass with respect to 100 parts by mass of the (A) component.

[0367] ·Regarding the (D2) component As the (D) component, a nitrogen-containing organic compound component that does not correspond to the above (D1) component (hereinafter referred to as the "(D2) component") may be contained. The (D2) component is not particularly limited as long as it acts as an acid diffusion control agent and does not correspond to the (D1) component, and may be arbitrarily used from known ones. Among them, aliphatic amines are preferred, and among these, secondary aliphatic amines and tertiary aliphatic amines are more preferred. An aliphatic amine is an amine having one or more aliphatic groups, and the aliphatic group preferably has 1 to 12 carbon atoms. As the aliphatic amine, ammonia NH 3Examples include amines (alkylamines or alkyl alcohol amines) or cyclic amines in which at least one of the hydrogen atoms is substituted with an alkyl group or hydroxyalkyl group having 12 or fewer carbon atoms. Specific examples of alkylamines and alkyl alcohol amines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, etc.; dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine, dicyclohexylamine, etc.; 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, tri-n-dodecylamine, etc.; and alkyl alcohol amines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, tri-n-octanolamine, etc. Among these, trialkylamines having 6 to 30 carbon atoms are more preferred, and tri-n-pentylamine or tri-n-octylamine is particularly preferred.

[0368] Examples of cyclic amines include heterocyclic compounds containing a nitrogen atom as a heteroatom. The heterocyclic compound may be monocyclic (aliphatic monocyclic amine) or polycyclic (aliphatic polycyclic amine). Specific examples of aliphatic monocyclic amines include piperidine, piperazine, etc. As aliphatic polycyclic amines, those having 6 to 10 carbon atoms are preferred, and specific examples include 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, hexamethylenetetramine, 1,4-diazabicyclo[2.2.2]octane, etc.

[0369] Examples of 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.

[0370] Also, as the component (D2), an aromatic amine may be used. Examples of aromatic amines include 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or their derivatives, tribenzylamine, 2,6-diisopropylaniline, N-tert-butoxycarbonylpyrrolidine, 2,6-di-tert-butylpyridine, 2,6-di-tert-butylpyridine, etc.

[0371] The component (D2) may be used alone or in combination of two or more. When the resist composition contains the component (D2), the content of the component (D2) in the resist composition is usually in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the component (A). By setting it within the above range, the resist pattern shape, standing stability over time, etc. are improved.

[0372] <At least one compound (E) selected from the group consisting of an organic carboxylic acid, an oxo acid of phosphorus and its derivatives> In the resist composition of the present embodiment, for the purpose of preventing sensitivity deterioration and improving the resist pattern shape, standing stability over time, etc., at least one compound (E) (hereinafter referred to as "component (E)") selected from the group consisting of an organic carboxylic acid, an oxo acid of phosphorus and its derivatives can be contained as an optional component. Examples of the organic carboxylic acid include acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, etc. Among them, salicylic acid is preferred. Examples of the oxo acid of phosphorus include phosphoric acid, phosphonic acid, phosphinic acid, etc. Among them, phosphonic acid is particularly preferred.

[0373] In the resist composition of the present embodiment, the component (E) may be used alone or in combination of two or more. When the resist composition contains the component (E), the content of the component (E) is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, based on 100 parts by mass of the component (A). By setting the content within the above range, the lithography characteristics can be further improved.

[0374] <Fluorine additive component (F)> The resist composition of the present embodiment may contain a fluorine additive component (hereinafter referred to as "component (F)") as a hydrophobic resin. The component (F) is used to impart water repellency to the resist film, and by using it as a resin different from the component (A), the lithography characteristics can be improved. As the component (F), for example, the fluorine-containing polymer compounds described in JP-A-2010-002870, JP-A-2010-032994, JP-A-2010-277043, JP-A-2011-13569, and JP-A-2011-128226 can be used. (F) More specifically as the component, there may be mentioned polymers having a structural unit (f1) represented by the following general formula (f1-1). As this polymer, there may be mentioned a polymer composed only of the structural unit (f1) represented by the following formula (f1-1) (homopolymer); a copolymer of the structural unit (f1) and the structural unit (a1); preferably a copolymer of the structural unit (f1), a structural unit derived from acrylic acid or methacrylic acid, and the structural unit (a1), and more preferably a copolymer of the structural unit (f1) and the structural unit (a1). Here, as the structural unit (a1) copolymerized with the structural unit (f1), a structural unit derived from 1-ethyl-1-cyclooctyl (meth)acrylate and a structural unit derived from 1-methyl-1-adamantyl (meth)acrylate are preferable, and a structural unit derived from 1-ethyl-1-cyclooctyl (meth)acrylate is more preferable.

[0375]

Chemical formula

[0376] In formula (f1-1), R bonded to the carbon atom at the α-position is the same as described above. As R, a hydrogen atom or a methyl group is preferable. In formula (f1-1), as the halogen atom of Rf 102 and Rf 103 , a fluorine atom is preferable. As the alkyl group having 1 to 5 carbon atoms of Rf 102 and Rf 103 , the same ones as the alkyl group having 1 to 5 carbon atoms of the above R are mentioned, and a methyl group or an ethyl group is preferable. Rf 102 and Rf103 Examples of the alkyl halide group having 1 to 5 carbon atoms include groups in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. As the halogen atom, a fluorine atom is preferable. Among them, Rf 102 and Rf 103 are preferably a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom, a fluorine atom, a methyl group, or an ethyl group, and even more preferably a hydrogen atom. In formula (f1-1), nf 1 is an integer of 0 to 5, preferably an integer of 0 to 3, and more preferably 1 or 2.

[0377] In formula (f1-1), Rf 101 is an organic group containing a fluorine atom, preferably a hydrocarbon group containing a fluorine atom. The hydrocarbon group containing a fluorine atom may be linear, branched, or cyclic, preferably having 1 to 20 carbon atoms, more preferably having 1 to 15 carbon atoms, and particularly preferably having 1 to 10 carbon atoms. Further, in the hydrocarbon group containing a fluorine atom, it is preferable that 25% or more of the hydrogen atoms in the hydrocarbon group are fluorinated, more preferably 50% or more are fluorinated, and particularly preferably 60% or more are fluorinated because the hydrophobicity of the resist film during immersion exposure is increased. Among them, Rf 101 is more preferably a fluorinated hydrocarbon group having 1 to 6 carbon atoms, such as a trifluoromethyl group, -CH 2 -CF 3 、-CH 2 -CF 2 -CF 3 、-CH(CF 3 ) 2 、-CH 2 -CH 2 -CF 3 、-CH 2 -CH 2 -CF 2 -CF 2 -CF 2 -CF3 is particularly preferred.

[0378] (F) The weight average molecular weight (Mw) of the component (in terms of polystyrene conversion standard 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. When it is below the upper limit value of this range, there is sufficient solubility in the resist solvent for use as a resist, and when it is above the lower limit value of this range, the water repellency of the resist film is good. (F) The dispersity (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.

[0379] In the resist composition of the present embodiment, the (F) component may be used alone or in combination of two or more. When the resist composition contains the (F) component, the content of the (F) component is preferably 0.5 to 10 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the (A) component.

[0380] <Organic solvent component (S)> The resist composition of the present embodiment can be produced by dissolving a resist material in an organic solvent component (hereinafter referred to as the "(S) component"). In the resist composition of the present embodiment, the (S) component may be used alone or as a mixed solvent of two or more. Among them, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), γ-butyrolactone, ethyl lactate (EL), and cyclohexanone are preferred.

[0381] Also, as the (S) component, a mixed solvent obtained by mixing PGMEA and a polar solvent is also preferred. The mixing ratio (mass ratio) may be appropriately determined in consideration of the compatibility between PGMEA and the polar solvent. (S) component preferably includes a mixed solvent of at least one selected from PGMEA and EL and γ-butyrolactone. In this case, as the mixing ratio, the mass ratio of the former to the latter is preferably 70:30 to 95:5. (S) The amount of the component used is not particularly limited and is appropriately set according to the coating film thickness at a concentration that can be applied to a substrate or the like. Generally, the (S) component is used so that the solid content concentration of the resist composition is in the range of 0.1 to 20% by mass, preferably 0.2 to 15% by mass.

[0382] After dissolving the above resist material in the (S) component, the resist composition of this embodiment may be subjected to removal of impurities or the like using a polyimide porous membrane, a polyamideimide porous membrane, or the like. For example, the resist composition may be filtered using a filter made of a polyimide porous membrane, a filter made of a polyamideimide porous membrane, a filter made of a polyimide porous membrane and a polyamideimide porous membrane, or the like. Examples of the polyimide porous membrane and the polyamideimide porous membrane include those described in JP-A-2016-155121.

[0383] The resist composition of this embodiment may contain compound (B0) as compound (C). The resist composition of this embodiment may contain component (A1), compound (B0), and component (D). Alternatively, the resist composition of this embodiment may contain component (A1) having structural unit (a6) and compound (B0) component.

[0384] The resist composition of this embodiment may contain compound (D0) as compound (C). The resist composition of this embodiment may contain component (A1), component (B), and compound (D0). Alternatively, the resist composition of this embodiment may contain component (A1) having structural unit (a5) and compound (D0).

[0385] The resist composition of this embodiment may contain, as the compound (C), a resin component having a structural unit (a0). The resin component may be the component (A1). The resist composition of this embodiment may contain the component (A1) having a structural unit (a0b) and the component (D). The resist composition of this embodiment may contain the component (A1) having a structural unit (a0d) and the component (B). The resist composition of this embodiment may contain the component (A1) having a structural unit (a0b) and a structural unit (a0d).

[0386] The resist composition of this embodiment may contain, as the compound (C), the compound (B0) and the compound (D0). The resist composition of this embodiment may contain the component (A1), the compound (B0), and the compound (D0).

[0387] The resist composition of this embodiment may contain, as the compound (C), a resin component having a structural unit (a0) and the compound (B0). The resin component may be the component (A1). The resist composition of this embodiment may contain the component (A1) having a structural unit (a0d) and the component (B0).

[0388] The resist composition of this embodiment may contain, as the compound (C), a resin component having a structural unit (a0) and the compound (D0). The resin component may be the component (A1). The resist composition of this embodiment may contain the component (A1) having a structural unit (a0b) and the compound (D0).

[0389] The resist composition of this embodiment may contain, as the compound (C), a resin component having a structural unit (a0), the compound (B0), and the compound (D0). The resin component may be the component (A1). The resist composition of this embodiment may contain a component (A1) having a constitutional unit (a0b), a compound (B0), and a compound (D0). The resist composition of this embodiment may contain a component (A1) having a constitutional unit (a0d), a compound (B0), and a compound (D0).

[0390] The resist compositions of the above embodiments may each contain a component (S), and optionally may contain either or both of a component (E) and a component (F).

[0391] The resist composition of this embodiment described above contains a compound (compound (C)) containing a cation (C0) represented by the general formula (c0). Z in formula (c0) + (S + or I + ) is directly bonded to an aromatic ring Ar 1 , Ar 2 and Ar 3 are each bonded to at least one iodine atom and at least one acyl group (-C(=O)-Rz 11 , -C(=O)-Rz 12 , or -C(=O)-Rz 13 ). Iodine atoms have a large absorption of EUV with a wavelength of 13.5 nm. Therefore, the compound (C0) is likely to generate secondary electrons during exposure. The secondary electrons generated from the iodine atoms present on Ar 1 , Ar 2 and / or Ar 3 due to exposure are presumed to promote the decomposition of the cation (C0), enhance the sensitivity, suppress process variations, and contribute to improvements such as CDU. Also, generally, when a component containing iodine atoms is introduced into the resist composition, the hydrophobicity of the resist composition increases and the solubility in the developer is likely to decrease. However, the acyl groups (-C(=O)-Rz 1 , Ar 2 and / or Ar 3 present on 11 , -C(=O)-Rz 12、 or -C(=O)-Rz 13 ) has high hydrophilicity, so it is presumed to alleviate the inhibitory effect of the high hydrophobicity of iodine atoms on development solubility and contribute to the improvement of CDU and the like and the improvement of resolution. Furthermore, Ar 1 、 Ar 2 and / or Ar 3 The iodine atoms and acyl groups (-C(=O)-Rz 11 、 -C(=O)-Rz 12 、 or -C(=O)-Rz 13 ) existing on lower the LUMO of the cation (C0) itself. Therefore, it is presumed that the cation (C0) becomes more likely to receive electrons, promotes the decomposition of the cation (C0), and the sensitivity is increased. By the synergistic action of the above-mentioned respective effects, it is presumed that the sensitivity, roughness, and resolution are released from the trade-off relationship, and improvements in sensitivity, CDU, and resolution can all be achieved.

[0392] (Resist pattern forming method) The resist pattern forming method according to the second aspect of the present invention includes a step of forming a resist film on a support using the resist composition according to the first aspect of the present invention described above, a step of exposing the resist film, and a step of developing the exposed resist film to form a resist pattern. As an embodiment of such a resist pattern forming method, for example, a resist pattern forming method performed as follows can be mentioned.

[0393] First, the resist composition of the above-described embodiment is applied on a support with a spinner or the like, and a baking (post-apply bake (PAB)) treatment is performed at a temperature condition of, for example, 80 to 150°C for 40 to 120 seconds, preferably 60 to 90 seconds, to form a resist film. Next, selective exposure is performed on the resist film by exposure through a mask (mask pattern) on which a predetermined pattern is formed or by direct irradiation with an electron beam without using a mask pattern using an exposure apparatus such as an electron beam lithography apparatus or an ArF exposure apparatus. After that, a baking (post-exposure bake (PEB)) process is performed at a temperature condition of, for example, 80 to 150°C for 40 to 120 seconds, preferably 60 to 90 seconds. Next, the resist film is developed. In the case of an alkali development process, an alkali developer is used, and in the case of a solvent development process, a developer containing an organic solvent (organic-based developer) is used.

[0394] After the development process, preferably a rinsing process is performed. In the case of an alkali development process, water rinsing using pure water is preferable, and in the case of a solvent development process, it is preferable to use a rinsing solution containing an organic solvent. In the case of a solvent development process, after the development process or the rinsing process, a process of removing the developer or the rinsing solution adhering to the pattern with a supercritical fluid may be performed. After the development process or the rinsing process, drying is performed. Also, in some cases, a baking process (post-bake) may be performed after the above development process.

[0395] The support is not particularly limited, and conventionally known ones can be used. For example, substrates for electronic components and those on which a predetermined wiring pattern is formed thereon can be mentioned. More specifically, substrates made of metals such as silicon wafers, copper, chromium, iron, and aluminum, and glass substrates can be mentioned. As materials for the wiring pattern, for example, copper, aluminum, nickel, gold, etc. can be used.

[0396] The wavelength used for exposure is not particularly limited, and it can be performed using radiation such as ArF excimer laser, KrF excimer laser, F 2 excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray, soft X-ray, etc. The resist pattern forming method of this embodiment is particularly useful in the process of exposing the resist film to EUV (extreme ultraviolet light) or EB (electron beam).

[0397] The method of exposing the resist film may be normal exposure (dry exposure) performed in an inert gas such as air or nitrogen, or may be liquid immersion lithography. Liquid immersion lithography is an exposure method in which the space between the resist film and the lens at the lowest position of the exposure apparatus is filled with a solvent (liquid immersion medium) having a refractive index greater than that of air in advance, and exposure (immersion exposure) is performed in that state. As the liquid immersion medium, a solvent having a refractive index greater than that of air and smaller than that of the resist film to be exposed is preferable, and examples thereof include water, fluorine-based inert liquids, silicon-based solvents, hydrocarbon-based solvents, and the like. Water is preferably used as the liquid immersion medium.

[0398] Examples of the alkaline developer used for development in the alkaline development process include an aqueous solution of 0.1 to 10% by mass of tetramethylammonium hydroxide (TMAH). The organic solvent contained in the organic developer used for development in the solvent development process may be any one that can dissolve the component (A) (component (A) before exposure), and can be appropriately selected from known organic solvents. Specifically, polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, ether solvents, and hydrocarbon solvents can be mentioned.

[0399] Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butanoate, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.

[0400] Examples of nitrile solvents include acetonitrile, propionitrile, valeronitrile, butyronitrile, and the like.

[0401] Known additives can be incorporated into the organic developer as needed. Examples of such additives include surfactants. The surfactant is not particularly limited, and for example, ionic or non-ionic fluorine-based and / or silicon-based surfactants can be used.

[0402] The development process can be carried out by known development methods. For example, a method of immersing the support in the developer for a certain period of time (dip method), a method of raising the developer on the support surface by surface tension and allowing it to stand for a certain period of time (paddle method), a method of spraying the developer on the support surface (spray method), a method of continuously discharging the developer while scanning a developer discharge nozzle at a constant speed on a support rotating at a constant speed (dynamic dispense method), and the like.

[0403] As the organic solvent contained in the rinse liquid used for the rinse process after the development process in the solvent development process, for example, among the organic solvents listed as the organic solvents used in the organic-based developer, those that are difficult to dissolve the resist pattern can be appropriately selected and used. Usually, at least one solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is used. These organic solvents may be used alone or in combination of two or more. Also, they may be used in mixture with organic solvents other than those described above or water.

[0404] The rinse process (cleaning process) using the rinse liquid can be carried out by a known rinse method. Examples of the method of this rinse process include a method of continuously coating the rinse liquid on a support rotating at a constant speed (spin coating method), a method of immersing the support in the rinse liquid for a certain period of time (dip method), a method of spraying the rinse liquid on the surface of the support (spray method), etc.

[0405] According to the resist pattern forming method of the present embodiment described above, since the resist composition described above is used, when forming a resist pattern, the sensitivity is improved, the CDU of the resist pattern is improved, and a high-resolution resist pattern can be formed.

[0406] In the resist composition of the above-described embodiment and various materials used in the pattern forming method of the above-described embodiment (for example, resist solvents, developers, rinsing liquids, compositions for forming an antireflection film, compositions for forming a top coat, etc.), it is preferable that they do not contain impurities such as metals, metal salts containing halogens, acids, alkalis, components containing sulfur atoms or phosphorus atoms, etc. Here, examples of impurities containing metal atoms include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Cr, Ni, Zn, Ag, Sn, Pb, Li, or salts thereof. As the content of impurities contained in these materials, 200 ppb or less is preferable, 1 ppb or less is more preferable, 100 ppt (parts per trillion) or less is still more preferable, 10 ppt or less is particularly preferable, and it is most preferable that they are substantially not contained (being below the detection limit of the measuring device).

[0407] (Compound) The compound according to the third aspect of the present invention contains a cation (C0) represented by the following general formula (c0).

[0408] [Chemical formula] [In the formula, Z + represents S + or I + . Ar 1 , Ar 2 and Ar 3 each independently represents an aromatic ring. I is an iodine atom. Rz 11 , Rz 21 and Rz 31 each independently represents an alkyl group having 1 to 5 carbon atoms. Rz 12 , Rz 22 and Rz 32 each independently represents a substituent. Rz 12 , Rz 22 and Rz 32 are bonded to each other to form Z in the formula + , Ar 1 , Ar 2 and Ar 3It may form a condensed ring together. lz1, lz2, lz3, mz1, mz2, mz3, nz1, nz2 and nz3 are each independently an integer of 0 or more as long as the valence permits. However, at least one of lz1, mz1 and nz1 is an integer of 1 or more, and at least one of lz2, mz2 and nz2 is an integer of 1 or more. Z + is S + in the case of, nz31 is 1, and Z + is I + in the case of, nz31 is 0.]

[0409] The compound according to this embodiment is the same as the compound (C0) in the first aspect. The compound of this embodiment is useful as a photoacid generator and an acid diffusion controller used in a resist composition. Further, the compound of this embodiment is also useful as a base material component having the structural unit (a0) in the first aspect and a monomer for inducing the structural unit (a0). The compound according to this embodiment may be a photoacid generator represented by the following general formula (b0) or an acid diffusion controller represented by the following general formula (d0).

[0410] [Chemical formula] [In the formula, Mc + is the cation (C0). Xb - is a counter anion.]

[0411] [Chemical formula] [In the formula, Mc + is the cation (C0). Xd - is a counter anion.]

[0412] The photoacid generator represented by the formula (b0) is the same as the component (B0) in the first aspect. The acid diffusion controller represented by the formula (d0) is the same as the component (D0) in the first aspect.

[0413] (Method for producing a compound) The method for producing the compound according to this embodiment is not particularly limited, and it can be produced by appropriately combining known methods.

Example

[0414] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by these examples.

[0415] <Synthesis example of a compound> [Synthesis example 1: Synthesis of compound (B0-1)] (Synthesis of intermediate) 20.0 g of 1-(4-mercaptophenyl)ethanone, 26.2 g of 4-bromoacetophenone, 15.3 g of sodium carbonate (Na 2 CO 3 ), and 0.4 g of copper (Cu) were dissolved in 284.2 g of dimethylformamide (DMF), stirred at 170 °C for 6 hours, and then the reaction solution was poured into an aqueous hydrochloric acid solution and filtered. The obtained crystals were recrystallized with acetonitrile to obtain intermediate 1A. Subsequently, 25.0 g of intermediate 1A, 31.5 g of hydrogen peroxide (H 2 O 2 ), and 2.1 g of palladium (Pd) were dissolved in 264.8 g of methanol (MeOH) and stirred at 60 °C for 5 hours. The solvent was distilled off and purified by column chromatography to obtain intermediate 1B. Next, 20.0 g of intermediate 1B, 17.1 g of iodobenzene, and 173.9 g of dichloromethane (DCM) were stirred at 0 °C, and a solution prepared by dissolving 21.7 g of trifluoromethanesulfonic anhydride (Tf 2 O) in 173.9 g of DCM was added dropwise thereto. The mixture was stirred at 0 °C for 4 hours. It was washed with sodium hydrogen carbonate and water, and the organic layer was distilled off under reduced pressure to obtain intermediate 1C. Furthermore, 15.0 g of intermediate 1C was dissolved in 61.3 g of MeOH and anion-exchanged with a strong base ion exchange resin to obtain intermediate 1D as a solution.

[0416]

Chemical formula

[0417] (Salt exchange reaction) To the solution of Intermediate 1D, 15.6 g of Compound 1a, 109.7 g of DCM, and 109.7 g of water were added, and the mixture was stirred at room temperature. The organic layer was recovered, washed repeatedly with water, and then the organic layer was distilled off under reduced pressure to obtain Compound (B0-1).

[0418] [Chemical formula]

[0419] For the obtained Compound (B0-1), NMR measurement was carried out, and its structure was identified based on the following results.

[0420] (Compound (B0-1)) 1 1H-NMR (DMSO-d6, 400 MHz): 2.50 (6H, s), 4.60 (2H, s), 7.10 (2H, d), 7.44 (4H, d), 7.77 (2H, d), 7.90 (4H, d), 8.00 (1H, s), 8.11 (1H, s)

[0421] [Synthesis Example 2: Synthesis of Compound (B0-2)] (Synthesis of Intermediate) 40.0 g of 4-iodobenzenethiol, 33.7 g of 4-bromoacetophenone, 19.8 g of sodium carbonate (Na 2 2CO 3 3), and 0.5 g of copper (Cu) were dissolved in 480.1 g of dimethylformamide (DMF), stirred at 170 °C for 6 hours, then the reaction solution was poured into an aqueous hydrochloric acid solution and filtered. The obtained crystals were recrystallized from acetonitrile to obtain Intermediate 2A. Subsequently, 30.0 g of Intermediate 2A, 28.8 g of hydrogen peroxide (H 2 2O 2 2), and 2.0 g of palladium (Pd) were dissolved in 313.6 g of methanol (MeOH), stirred at 60 °C for 5 hours. The solvent was distilled off, and purification was carried out by column chromatography to obtain Intermediate 2B. Next, 20.0 g of intermediate 2B, 13.2 g of iodobenzene, and 152.6 g of dichloromethane (DCM) were stirred at 0 °C, and a solution prepared by dissolving 16.8 g of trifluoromethanesulfonic anhydride (Tf 2 O) in 152.6 g of DCM was added dropwise to the solution. The mixture was stirred at 0 °C for 4 hours. It was washed with sodium hydrogen carbonate and water, and the organic layer was distilled off under reduced pressure to obtain intermediate 2C. Furthermore, 15.0 g of intermediate 2C was dissolved in 62.9 g of MeOH, and anion exchange was carried out using a strong base ion exchange resin to obtain intermediate 2D as a solution.

[0422] [Chemical Formula]

[0423] (Salt Exchange Reaction) A salt exchange reaction was carried out in the same manner as in Synthesis Example 1 except that intermediate 2D was used instead of intermediate 1D to obtain compound (B0-2).

[0424] [Chemical Formula]

[0425] For the obtained compound (B0-2), NMR measurement was performed, and its structure was identified based on the following results.

[0426] (Compound (B0-2)) 1 1H-NMR (DMSO-d6, 400 MHz): 2.50 (3H, s), 4.60 (2H, s), 7.10 (4H, d), 7.44 (2H, d), 7.77 (4H, d), 7.90 (2H, d), 8.00 (1H, s), 8.11 (1H, s)

[0427] [Synthesis Example 3: Synthesis of Compound (B0-3)] (Synthesis of Intermediate) 76.0 g of aluminum chloride, 44.7 g of acetyl chloride, and 254.9 g of dichloromethane (DCM) were stirred with a stir bar at 0 °C. A mixed solution of 35.0 g of dibenzothiophene and 254.9 g of DCM was added dropwise thereto. After stirring for 2 hours, the reaction solution was washed with water, and the organic layer was distilled off under reduced pressure. The obtained crystals were recrystallized from acetonitrile to obtain Intermediate 3A. Subsequently, 40.0 g of Intermediate 3A, 50.7 g of hydrogen peroxide (H 2 O 2 ), and 3.4 g of palladium (Pd) were dissolved in 423.8 g of methanol (MeOH), and the mixture was stirred at 60 °C for 5 hours. The solvent was distilled off, and purification by column chromatography was performed to obtain Intermediate 3B. Next, 20.0 g of Intermediate 3B, 17.2 g of iodobenzene, and 174.6 g of dichloromethane (DCM) were stirred at 0 °C, and a solution prepared by dissolving 21.8 g of trifluoromethanesulfonic anhydride (Tf 2 O) in 174.6 g of DCM was added dropwise thereto. The mixture was stirred at 0 °C for 4 hours. It was washed with sodium hydrogen carbonate and water, and the organic layer was distilled off under reduced pressure to obtain Intermediate 3C. Furthermore, 15.0 g of Intermediate 3C was dissolved in 67.8 g of MeOH, and anion exchange was performed using a strong base ion exchange resin to obtain Intermediate 3D as a solution.

[0428]

Chemical formula

[0429] (Salt exchange reaction) A salt exchange reaction was carried out in the same manner as in Synthesis Example 1 except that Intermediate 3D was used instead of Intermediate 1D to obtain Compound (B0-3).

[0430]

Chemical formula

[0431] NMR measurement was performed on the obtained Compound (B0-3), and its structure was identified based on the following results.

[0432] (Compound (B0-3)) 1 1H-NMR (DMSO-d6, 400 MHz): 2.50 (6H, s), 4.60 (2H, s), 7.10 (2H, d), 7.63 (2H, d), 7.77 (2H, d), 7.98 - 8.02 (3H, m), 8.11 (1H, s), 8.51 (2H, d)

[0433] [Synthesis Example 4: Synthesis of Compound (B0-4)] (Synthesis of Intermediate) 20.0 g of 1-(4-mercaptophenyl)ethanone, 26.2 g of 4-bromoacetophenone, 15.3 g of sodium carbonate (Na 2 2CO 3 3), and 0.4 g of copper (Cu) were dissolved in 284.2 g of dimethylformamide (DMF), stirred at 170 °C for 6 hours, then the reaction solution was poured into an aqueous hydrochloric acid solution and filtered. The obtained crystals were recrystallized from acetonitrile to obtain Intermediate 4A. Subsequently, 25.0 g of Intermediate 4A, 31.5 g of hydrogen peroxide (H 2 2O 2 2), and 2.1 g of palladium (Pd) were dissolved in 264.8 g of methanol (MeOH), stirred at 60 °C for 5 hours. The solvent was distilled off, and purification by column chromatography gave Intermediate 4B. Next, 20.0 g of Intermediate 4B, 24.0 g of 2-iodophenol, and 232.1 g of dichloromethane (DCM) were stirred at 0 °C, and a solution prepared by dissolving 28.2 g of trifluoromethanesulfonic anhydride (Tf 2 2O in 232.1 g of DCM was added dropwise thereto. The mixture was stirred at 0 °C for 4 hours, washed with sodium hydrogen carbonate and water, and the organic layer was distilled off under reduced pressure to obtain Intermediate 4C.

[0434] [Chemical Structure]

[0435] (Salt Exchange Reaction) A salt exchange reaction was carried out in the same manner as in Synthesis Example 1 except that Intermediate 4D was used instead of Intermediate 1D to obtain Compound (B0-4).

[0436] [Chemical Formula]

[0437] NMR measurement was performed on the obtained Compound (B0-4), and its structure was identified based on the following results.

[0438] (Compound (B0-4)) 1 1H-NMR (DMSO-d6, 400 MHz): 2.50 (6H, s), 4.60 (2H, s), 6.58 (1H, d), 7.15 (1H, d), 7.44 (4H, d), 7.54 (1H, s), 7.90 (4H, d), 8.00 (1H, s), 8.11 (1H, s)

[0439] [Synthesis Example 5: Synthesis of Compound (B0-5)] (Synthesis of Intermediate) 35.0 g of 1-(4-mercaptophenyl)ethanone, 36.1 g of bromobenzene, 26.8 g of sodium carbonate (Na 2 CO 3 ), and 0.7 g of copper (Cu) were dissolved in 420.0 g of dimethylformamide (DMF), stirred at 170 °C for 6 hours, and then the reaction solution was poured into an aqueous hydrochloric acid solution and filtered. The obtained crystals were recrystallized from acetonitrile to obtain Intermediate 5A. Subsequently, 35.0 g of Intermediate 5A, 52.1 g of hydrogen peroxide (H 2 O 2 ), and 3.5 g of palladium (Pd) were dissolved in 374.5 g of methanol (MeOH), and stirred at 60 °C for 5 hours. The solvent was distilled off, and purification by column chromatography was performed to obtain Intermediate 5B. Next, 20.0 g of Intermediate 5B, 20.0 g of iodobenzene, and 190.0 g of dichloromethane (DCM) were stirred at 0 °C, and trifluoromethanesulfonic anhydride (Tf 2A solution of 25.4 g of O)25.4 g in 190.0 g of DCM was added dropwise. The mixture was stirred at 0 °C for 4 hours. It was washed with sodium hydrogen carbonate and water, and the organic layer was distilled off under reduced pressure to obtain Intermediate 5C. Furthermore, 15.0 g of Intermediate 5C was dissolved in 60.3 g of MeOH, and anion exchange was performed with a strong base ion exchange resin to obtain Intermediate 5D as a solution.

[0440] [Chemical formula]

[0441] (Salt exchange reaction) A salt exchange reaction was carried out in the same manner as in Synthesis Example 1 except that Intermediate 5D was used instead of Intermediate 1D to obtain Compound (B0-5).

[0442] [Chemical formula]

[0443] For the obtained Compound (B0-5), NMR measurement was performed, and its structure was identified based on the following results.

[0444] (Compound (B0-5)) 1 1H-NMR (DMSO-d6, 400 MHz): 2.50 (3H, s), 4.60 (2H, s), 7.10 (2H, d), 7.31 - 7.38 (5H, m), 7.44 (2H, d), 7.77 (2H, d), 7.90 (2H, d), 8.00 (1H, s), 8.11 (1H, s)

[0445] [Synthesis Example 6: Synthesis of Compound (B0-6)] (Synthesis of intermediate) 35.0 g of 1-(4-mercaptophenyl)-1-propanone, 33.1 g of bromobenzene, sodium carbonate (Na 2 CO 3)Dissolve 24.5 g of [substance] and 0.7 g of copper (Cu) in 408.2 g of dimethylformamide (DMF), stir at 170 °C for 6 hours, then pour the reaction solution into an aqueous hydrochloric acid solution and filter. Recrystallize the obtained crystals with acetonitrile to obtain Intermediate 6A. Subsequently, dissolve 25.0 g of Intermediate 6A and 35.1 g of hydrogen peroxide (H 2 O 2 ) and 2.4 g of palladium (Pd) in 266.5 g of methanol (MeOH), stir at 60 °C for 5 hours. Distill off the solvent and purify by column chromatography to obtain Intermediate 6B. Next, stir 20.0 g of Intermediate 6B, 19.0 g of iodobenzene, and 184.1 g of dichloromethane (DCM) at 0 °C, and dropwise add a solution prepared by dissolving 24.0 g of trifluoromethanesulfonic anhydride (Tf 2 O) in 184.1 g of DCM to the solution. Stir at 0 °C for 4 hours. Wash with sodium hydrogen carbonate and water, and distill off the organic layer under reduced pressure to obtain Intermediate 6C. Furthermore, dissolve 15.0 g of Intermediate 6C in 60.7 g of MeOH, and perform anion exchange with a strong base ion exchange resin to obtain Intermediate 6D as a solution.

[0446]

Chemical formula

[0447] (Salt exchange reaction) A salt exchange reaction was carried out in the same manner as in Synthesis Example 1 except that Intermediate 6D was used instead of Intermediate 1D to obtain Compound (B0-6).

[0448]

Chemical formula

[0449] For the obtained Compound (B0-6), NMR measurement was performed, and its structure was identified based on the following results.

[0450] (Compound (B0-6)) 1H-NMR (DMSO-d6, 400 MHz): 1.22 (3H, t), 3.54 (2H, q), 4.60 (2H, s), 7.10 (2H, d), 7.31 - 7.43 (7H, m), 7.77 (2H, d), 7.93 (2H, d), 8.00 (1H, s), 8.11 (1H, s)

[0451] [Synthesis Example 7: Synthesis of Compound (B0-7)] A salt exchange reaction was carried out in the same manner as in Synthesis Example 1, except that Compound 7b was used instead of Compound 1a, to obtain Compound (B0-7).

[0452] [Chemical Formula]

[0453] For the obtained Compound (B0-7), NMR measurement was performed, and its structure was identified based on the following results.

[0454] (Compound (B0-7)) 1 H-NMR (DMSO-d6, 400 MHz): 2.50 (6H, s), 4.60 (2H, s), 7.10 (2H, d), 7.44 (4H, d), 7.55 (2H, t), 7.68 (1H, t), 7.77 (2H, d), 7.90 (4H, d), 8.06 (2H, d)

[0455] [Synthesis Example 8: Synthesis of Compound (a0-m-6)] A salt exchange reaction was carried out in the same manner as in Synthesis Example 1, except that Compound 8c was used instead of Compound 1a, to obtain Compound (a0-m-6).

[0456] [Chemical Formula]

[0457] For the obtained Compound (a0-m-6), NMR measurement was performed, and its structure was identified based on the following results.

[0458] (Compound (a0-m-6)) 1 H-NMR (DMSO-d6, 400 MHz): 2.01 (3H, s), 2.50 (6H, s), 6.18 (1H, s), 6.43 (1H, s), 7.10 (2H, d), 7.42 - 7.51 (5H, m), 7.61 (1H, d), 7.77 (2H, d), 7.83 - 7.92 (5H, m), 8.20 (1H, s)

[0459] [Synthesis Example 9: Synthesis of Compound (D0-1)] To the solution of Intermediate 1D, 2.7 g of Compound 9A, 60.0 g of DCM, 60.0 g of water, and 2.2 g of triethylamine (TEA) were added, and the mixture was stirred at room temperature. The organic layer was recovered, washed with water, and then the organic layer was distilled off under reduced pressure to obtain Compound (D0-1).

[0460] [Chemical Structure Diagram]

[0461] For the obtained Compound (D0-1), NMR measurement was carried out, and its structure was identified based on the following results.

[0462] (Compound (D0-1)) 1 H-NMR (DMSO-d6, 400 MHz): 2.50 (6H, s), 6.96 (1H, d), 7.10 (2H, d), 7.17 (1H, t), 7.42 - 7.48 (5H, m), 7.68 (1H, d), 7.77 (2H, d), 7.90 (4H, d)

[0463] [Synthesis Example 10: Synthesis of Compound (D0-2)] Compound (D0-2) was obtained in the same manner as in Synthesis Example 9, except that Compound 9A was replaced with Compound 10B.

[0464] [Chemical Structure Diagram]

[0465] For the obtained Compound (D0-2), NMR measurement was carried out, and its structure was identified based on the following results.

[0466] (Compound (D0-2)) 1 H-NMR (DMSO-d6, 400 MHz): 2.50 (6H, s), 7.10 (2H, d), 7.44 (4H, d), 7.77 (2H, d), 7.90 (4H, d), 8.01 (1H, s), 8.13 (1H, s)

[0467] [Synthesis Example 11: Synthesis of Compound (D0-3)] Compound (D0-3) was obtained in the same manner as in Synthesis Example 9, except that Compound 9A was replaced with Compound 11C.

[0468]

Chemical Structure

[0469] NMR measurement was performed on the obtained Compound (D0-3), and its structure was identified based on the following results.

[0470] (Compound (D0-3)) 1 H-NMR (DMSO-d6, 400 MHz): 2.50 (6H, s), 7.10 (2H, d), 7.44 (4H, d), 7.77 (2H, d), 7.90 (4H, d), 7.95 (1H, s), 8.07 (1H, s)

[0471] [Synthesis Example 12: Synthesis of Compound (B0-8)] 40.0 g of 4-iodobenzenethiol, 33.7 g of 3-bromoacetophenone, 19.8 g of sodium carbonate (Na 2 CO 3 ), and 0.5 g of copper (Cu) were dissolved in 480.1 g of dimethylformamide (DMF), stirred at 170 °C for 6 hours, then the reaction solution was poured into an aqueous hydrochloric acid solution and filtered. The obtained crystals were recrystallized from acetonitrile to obtain Intermediate 12A. Subsequently, 35.0 g of Intermediate 12A and hydrogen peroxide (H 2 O 2)33.6 g of palladium (Pd) and 2.3 g were dissolved in 365.8 g of methanol (MeOH) and stirred at 60 °C for 5 hours. The solvent was distilled off and purified by column chromatography to obtain Intermediate 12B. Next, 25.0 g of Intermediate 12B, 16.5 g of iodobenzene, and 190.8 g of dichloromethane (DCM) were stirred at 0 °C, and a solution prepared by dissolving 21.0 g of trifluoromethanesulfonic anhydride (Tf 2 O) in 190.8 g of DCM was added dropwise thereto. The mixture was stirred at 0 °C for 4 hours. It was washed with sodium hydrogen carbonate and water, and the organic layer was distilled off under reduced pressure to obtain Intermediate 12C. Furthermore, 20.0 g of Intermediate 12C was dissolved in 83.9 g of MeOH and anion-exchanged with a strong base ion-exchange resin to obtain Intermediate 12D as a solution.

[0472]

Chemical formula

[0473] (Salt exchange reaction) A salt exchange reaction was carried out in the same manner as in Synthesis Example 1 except that Intermediate 12D was used instead of Intermediate 1D to obtain Compound (B0-8).

[0474]

Chemical formula

[0475] NMR measurement was performed on the obtained Compound (B0-8), and its structure was identified based on the following results.

[0476] (Compound (B0-8)) 1 1H-NMR (DMSO-d6, 400 MHz): 2.50 (3H, s), 4.60 (2H, s), 7.10 (4H, d), 7.46 (1H, t), 7.52 (1H, d), 7.77 (4H, d), 7.93 (1H, s), 7.98 - 8.02 (2H, m), 8.11 (1H, s)

[0477] [Synthesis Example 13: Synthesis of Compound (B0-13)] 40.0 g of 4-iodobenzenethiol, 33.7 g of 2-bromoacetophenone, 19.8 g of sodium carbonate (Na 2 CO 3 ), and 0.5 g of copper (Cu) were dissolved in 480.1 g of dimethylformamide (DMF), stirred at 170 °C for 6 hours, and then the reaction solution was poured into an aqueous hydrochloric acid solution and filtered. The obtained crystals were recrystallized from acetonitrile to obtain Intermediate 13A. Subsequently, 25.0 g of Intermediate 13A, 35.1 g of hydrogen peroxide (H 2 O 2 ), and 2.4 g of palladium (Pd) were dissolved in 266.5 g of methanol (MeOH), and stirred at 60 °C for 5 hours. The solvent was distilled off, and purification by column chromatography gave Intermediate 13B. Next, 20.0 g of Intermediate 13B, 19.0 g of iodobenzene, and 184.1 g of dichloromethane (DCM) were stirred at 0 °C, and a solution prepared by dissolving 24.0 g of trifluoromethanesulfonic anhydride (Tf 2 O) in 184.1 g of DCM was added dropwise thereto. The mixture was stirred at 0 °C for 4 hours, washed with sodium hydrogen carbonate and water, and the organic layer was distilled off under reduced pressure to obtain Intermediate 13C. Furthermore, 15.0 g of Intermediate 13C was dissolved in 60.7 g of MeOH, and anion exchange was performed using a strong base ion exchange resin to obtain Intermediate 13D as a solution.

[0478] [Chemical formula]

[0479] (Salt exchange reaction) A salt exchange reaction was carried out in the same manner as in Synthesis Example 1 except that Intermediate 13D was used instead of Intermediate 1D to obtain Compound (B0-9).

[0480] [Chemical formula]

[0481] For the obtained compound (B0-9), NMR measurement was carried out, and its structure was identified based on the following results.

[0482] (Compound (B0-9)) 1 1H-NMR (DMSO-d6, 400 MHz): 2.50 (3H, s), 4.60 (2H, s), 7.10 (4H, d), 7.44 (1H, d), 7.51 - 7.56 (2H, m), 7.77 (4H, d), 7.90 (1H, d), 8.00 (1H, s), 8.11 (1H, s)

[0483] [Synthesis Example 14: Synthesis of Compound (B0-10)] 25.0 g of 1-(4-mercaptophenyl)-2-methyl-1-propanone, 31.2 g of 1-(4-bromophenyl)-2-methyl-1-propanone, 16.2 g of sodium carbonate (Na 2 CO 3 ), and 0.4 g of copper (Cu) were dissolved in 362.2 g of dimethylformamide (DMF), stirred at 170 °C for 6 hours, then the reaction solution was poured into an aqueous hydrochloric acid solution and filtered. The obtained crystals were recrystallized from acetonitrile to obtain Intermediate 14A. Subsequently, 28.0 g of Intermediate 10A, 29.2 g of hydrogen peroxide (H 2 O 2 ), and 2.0 g of palladium (Pd) were dissolved in 293.7 g of methanol (MeOH), stirred at 60 °C for 5 hours. The solvent was distilled off, and purification by column chromatography was performed to obtain Intermediate 14B. Next, 25.0 g of Intermediate 14B, 17.9 g of iodobenzene, and 198.1 g of dichloromethane (DCM) were stirred at 0 °C, and a solution prepared by dissolving 22.7 g of trifluoromethanesulfonic anhydride (Tf 2 O) in 198.1 g of DCM was added dropwise thereto. Stirring was carried out at 0 °C for 4 hours. After washing with sodium hydrogen carbonate and water, the organic layer was distilled off under reduced pressure to obtain Intermediate 14C. Furthermore, 20.0 g of Intermediate 14C was dissolved in 83.3 g of MeOH, and anion exchange was carried out using a strong base ion exchange resin to obtain Intermediate 14D as a solution.

[0484] [Chemical formula]

[0485] (Salt exchange reaction) A salt exchange reaction was carried out in the same manner as in Synthesis Example 1, except that Intermediate 14D was used instead of Intermediate 1D, to obtain Compound (B0-10).

[0486] [Chemical formula]

[0487] NMR measurement was performed on the obtained Compound (B0-10), and its structure was identified based on the following results.

[0488] (Compound (B0-10)) 1 1H-NMR (DMSO-d6, 400 MHz): 1.16 (12H, d), 3.20 (2H, q), 4.60 (2H, s), 7.10 (2H, d), 7.41 (4H, d), 7.77 (2H, d), 7.93 (4H, d), 8.00 (1H, s), 8.11 (1H, s)

[0489] [Synthesis Example 15: Synthesis of Polymer Compound (A1-6)] 150.0 g of compound (a0-m-6), 66.2 g of compound (a10-m-1), 82.8 g of compound (a1-m-1), and 5.7 g of 2,2'-azobis(2-methylbutyronitrile) (V-601) as a polymerization initiator were dissolved in 59.8 g of methyl ethyl ketone (MEK) to prepare a dropping solution. 637.8 g of MEK was added to a three-necked eggplant flask equipped with a thermometer, a reflux tube, and a nitrogen inlet tube, heated to 80°C under a nitrogen atmosphere, and the dropping solution was added dropwise over 4 hours. After the addition, the reaction solution was stirred at 80°C for 1 hour. Then, the reaction solution was cooled to room temperature. After completion of the reaction, the obtained reaction solution was precipitated with 1395.1 g of heptane, and the precipitate was washed. This precipitate was dissolved in 602.3 g of MEK and 56.5 g of MeOH, 177.2 g of acetic acid was added, and the mixture was stirred for 8 hours while heating to 80°C under a nitrogen atmosphere. After completion of the reaction, the obtained reaction solution was precipitated with 1317.5 g of heptane, and the precipitate was washed. The obtained white precipitate was filtered and dried under reduced pressure overnight to obtain a polymer compound (A1-6).

[0490]

Chemical formula

[0491] <Preparation of resist composition> (Examples 1 to 27, Comparative Examples 1 to 4) The resist compositions of each example were prepared by mixing and dissolving the components shown in Tables 1 to 2, respectively.

[0492]

Table 1

[0493]

Table 2

[0494] In Tables 1 to 2, each abbreviation has the following meaning. The numerical value in [ ] is the blending amount (parts by mass). (A1)-1: The following polymer compound (A1-1). The weight-average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement is 7,100, and the molecular weight distribution (Mw / Mn) is 1.72. 13 The copolymerization composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) determined by C-NMR is l / m = 40 / 60. (A1)-2: The following polymer compound (A1-2). The weight-average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement is 6,900, and the molecular weight distribution (Mw / Mn) is 1.73. 13 The copolymerization composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) determined by C-NMR is l / m = 40 / 60. (A1)-3: The following polymer compound (A1-3). The weight-average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement is 7,200, and the molecular weight distribution (Mw / Mn) is 1.68. 13 The copolymerization composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) determined by C-NMR is l / m = 40 / 60. (A1)-4: The following polymer compound (A1-4). The weight-average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement is 7,300, and the molecular weight distribution (Mw / Mn) is 1.74. 13 The copolymerization composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) determined by C-NMR is l / m = 40 / 60. (A1)-5: The following polymer compound (A1-5). The weight-average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement is 7,000, and the molecular weight distribution (Mw / Mn) is 1.71. 13 The copolymerization composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) determined by C-NMR is l / m = 40 / 60. (A1)-6: The following polymer compound (A1-6). The weight-average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement is 6,900, and the molecular weight distribution (Mw / Mn) is 1.69. 13 The copolymerization composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) determined by C-NMR is l / m / n = 35 / 50 / 15.

[0495]

Chemical formula

[0496] (B0)-1 to (B0)-10: Acid generators each consisting of the following compounds (B0-1) to (B0-10).

[0497]

Chemical formula

[0498]

Chemical formula

[0499] (D0)-1 to (D0)-3: Acid diffusion control agents each consisting of the following compounds (D0-1) to (D0-3).

[0500]

Chemical formula

[0501] (B1)-1 to (B1)-4: Acid generators each consisting of the following compounds (B1-1) to (B1-4).

[0502]

Chemical formula

[0503] (D1)-1 to (D1)-2: Acid diffusion control agents each consisting of the following compounds (D1-1) to (D1-2).

[0504]

Chemical formula

[0505] (S)-1: A mixed solvent of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 60 / 40 (mass ratio).

[0506] <Formation of resist pattern> On a silicon substrate treated with hexamethyldisilazane (HMDS), each resist composition of each example was applied using a spinner, and pre-baked (PAB) at a temperature of 110 °C for 60 seconds on a hot plate and dried to form a resist film with a thickness of 60 nm. Next, using an electron beam lithography apparatus JEOL-JBX-9300FS (manufactured by JEOL Ltd.), the resist film was exposed (lithographed) at an acceleration voltage of 100 kV with a target size of a contact hole pattern (CH pattern) having a pitch width of 46 nm and a hole width of 26 nm. Then, post-exposure bake (PEB) treatment was performed at 100 °C for 60 seconds. Subsequently, post-exposure bake (PEB) treatment was performed at 100 °C for 60 seconds. Then, at 23 °C, using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) "NMD-3" (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.), alkali development was carried out for 60 seconds, followed by water rinsing with pure water for 15 seconds. As a result, a CH pattern with a pitch width of 46 nm and a hole width of 26 nm was formed.

[0507] [Evaluation of Optimum Exposure Dose (Eop)] The optimum exposure dose Eop (μC / cm 2 ) at which an LS pattern of the target size was formed by the above-described resist pattern forming method was determined. The results are shown in Tables 3 to 4 as "Eop (μC / cm 2 )".

[0508] [Evaluation of Fine Resolution] Under the evaluation conditions of <formation of resist pattern> above, the minimum pattern size resolvable when the exposure dose was decreased was evaluated as the fine resolution. The results are shown in Tables 3 to 4 as "Resolution (nm)".

[0509] [Evaluation of In-Plane Uniformity of Pattern Dimensions (CDU)] Regarding the CH pattern formed by the above <formation of resist pattern>, observation was made from above the CH pattern using a length-measuring SEM (scanning electron microscope, acceleration voltage 500 V, product name: CG5000, manufactured by Hitachi High-Technologies Corporation), and the hole diameter (nm) of each hole was measured. Then, a three-fold value (3σ) of the standard deviation (σ) calculated from the measurement results was obtained. The results are shown in Tables 3 to 4 as "CDU (nm)". The smaller the value of 3σ obtained in this way, the higher the dimensional (CD) uniformity of the plurality of holes formed in the resist film.

[0510] [Table 3]

[0511] [Table 4]

[0512] As shown in Tables 3 to 4, the resist composition of the example was superior in all of sensitivity, resolution, and CDU as compared with the resist composition of the comparative example.

Claims

1. A resist composition which generates an acid upon exposure and changes its solubility in a developer by the action of the acid, A resist composition comprising a compound containing a cation (C0) represented by the following general formula (c0): 【Chemistry 1】 [In the formula, Z ＋ Is S ＋ Or I ＋ Represents Ar. １ , Ar ２ and Ar ３ each independently represents an aromatic ring; I is an iodine atom; Rz １１ , Rz ２１ and Rz ３１ Rz each independently represents an alkyl group having 1 to 5 carbon atoms. １２ , Rz ２２ and Rz ３２ Rz each independently represents a substituent. １２ , Rz ２２ and Rz ３２ are bonded to each other to form Z in the formula ＋ , Ar １ , Ar ２ and Ar ３ may form a condensed ring together with Z. lz1, lz2, lz3, mz1, mz2, mz3, nz1, nz2 and nz3 are each independently an integer of 0 or more as far as the valence allows. However, at least one of lz1, mz1 and nz1 is an integer of 1 or more, and at least one of lz2, mz2 and nz2 is an integer of 1 or more. Z ＋ S ＋ In the case of ＋ I ＋ In this case, nz31 is 0.

2. a resin component (A1) whose solubility in a developer changes under the action of an acid; and an acid generator component (B) that generates an acid upon exposure to light, The acid generator component (B) contains a compound represented by the following general formula (b0): The resist composition according to claim 1 . 【Chemistry 2】 [In the formula, Mc ＋ is the cation (C0). － is the counter anion.

3. a resin component (A1) whose solubility in a developer changes under the action of an acid; and an acid diffusion controller component (D) that controls the diffusion of acid generated by exposure to light, The acid diffusion controller component (D) contains a compound represented by the following general formula (d0): The resist composition according to claim 1 . 【Chemistry 3】 [In the formula, Mc ＋ is the cation (C0). － is the counter anion.

4. Contains a resin component (A1) whose solubility in a developer changes under the action of an acid, The resin component (A1) has a structural unit (a0) represented by the following general formula (a0-1): The resist composition according to claim 1 . 【Chemistry 4】 [In the formula, R is a hydrogen atom, a carbon atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. ＋ is the cation (C0). ０－ is a group containing an anion.

5. In the general formula (b0), Xb － SO ３ － The resist composition according to claim 2 , wherein the anion comprises

6. In the general formula (d0), Xd － is COO － The resist composition according to claim 3 , wherein the anion is selected from the group consisting of aryl, ... and aryl.

7. In the general formula (c0), Z ＋ Is S ＋ The resist composition according to any one of claims 1 to 6, wherein

8. 13. A method for forming a resist pattern, comprising the steps of: forming a resist film on a support using the resist composition according to claim 1; exposing the resist film; and developing the exposed resist film to form a resist pattern.

9. A compound containing a cation (C0) represented by the following general formula (c0): 【Chemistry 5】 [In the formula, Z ＋ Is S ＋ Or I ＋ Represents Ar. １ , Ar ２ and Ar ３ each independently represents an aromatic ring; I is an iodine atom; Rz １１ , Rz ２１ and Rz ３１ Rz each independently represents an alkyl group having 1 to 5 carbon atoms. １２ , Rz ２２ and Rz ３２ Rz each independently represents a substituent. １２ , Rz ２２ and Rz ３２ are bonded to each other to form Z in the formula ＋ , Ar １ , Ar ２ and Ar ３ may form a condensed ring together with Z. lz1, lz2, lz3, mz1, mz2, mz3, nz1, nz2 and nz3 are each independently an integer of 0 or more as far as the valence allows. However, at least one of lz1, mz1 and nz1 is an integer of 1 or more, and at least one of lz2, mz2 and nz2 is an integer of 1 or more. Z ＋ S ＋ In the case of ＋ I ＋ In this case, nz31 is 0.

10. The compound according to claim 9 , which is a photoacid generator represented by the following general formula (b0): 【Chemistry 6】 [In the formula, Mc ＋ is the cation (C0). － is the counter anion.

11. The compound according to claim 9 , which is an acid diffusion controller represented by the following general formula (d0): 【Chemistry 7】 [In the formula, Mc ＋ is the cation (C0). － is the counter anion.

12. In the general formula (b0), X － SO ３ － The compound of claim 10, wherein the anion comprises:

13. In the general formula (d0), Xd － is COO － The compound of claim 11, wherein the anion is

14. In the general formula (c0), Z ＋ Is S ＋ The compound according to any one of claims 9 to 13,

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