Resist composition, method for forming resist pattern, compound, acid generation agent, and acid diffusion control agent

Abstract

To provide a resist composition or the like that is superior in all of sensitivity, roughness, and resolution.SOLUTION: The present invention provides a resist composition that generates an acid upon exposure and that changes solubility in a developer solution due to the action of the acid, the resist composition comprising a compound containing a cation (C0) represented by general formula (c0). [In the formula, Y0 represents a polar group containing an oxygen atom. Rf0 represents a fluorine atom or a fluorinated alkyl group. R01 represents a substituent (excluding a polar group containing an oxygen atom, a fluorine atom, and a fluorinated alkyl group), and R02 and R03 each independently represent a substituent (excluding an iodine atom)].SELECTED DRAWING: None

Description

Technical Field

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

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] Resist materials are required to have lithography characteristics such as sensitivity to these exposure light sources and resolution capable of reproducing patterns with fine dimensions. As a resist material that satisfies such requirements, a chemically amplified resist composition containing a base material component whose solubility in a developer changes 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 an onium salt containing a sulfonium cation containing a fluorine atom as an acid generator. Patent Document 1 also describes that an acid diffusion controller is contained in the resist composition.

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 any trade-off.

[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, roughness, and resolution, a resist pattern forming method using the resist composition, a compound, an acid generator, and an acid diffusion controller 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 represented by the following general formula (m0).

[0013]

Chemical formula

[0014] A fourth aspect of the present invention is an acid generator containing the compound according to the third aspect.

[0015] A fifth aspect of the present invention is an acid diffusion control agent containing the compound according to the third aspect.

Advantages of the Invention

[0016] According to the present invention, it is possible to provide a resist composition having good sensitivity, roughness, and resolution, a resist pattern forming method using the resist composition, a compound, an acid generator, and an acid diffusion control agent used in the resist composition.

Modes for Carrying Out the Invention

[0017] 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" includes 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" includes 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 polymer 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 (-CH2-) with a divalent group. "Exposure" is a concept that includes all irradiations of radiation.

[0018] The "acid-decomposable group" is a group having acid-decomposability in which 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 (-SO3H), 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).

[0019] The "acid-dissociable group" means both (i) a group having acid-dissociability in which 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 that constitutes the acid-decomposable group needs to be a group with lower polarity than the polar group generated by the dissociation of the acid-dissociable group. Thus, when the acid-dissociable group dissociates due to the action of an acid, a polar group with higher polarity than the acid-dissociable group is generated, increasing the polarity. As a result, the polarity of the entire component (A1) increases. 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.

[0020] The "substrate component" is an organic compound having film-forming ability. The organic compounds used as the substrate component are roughly classified into non-polymers and polymers. As the non-polymer, those usually having a molecular weight of 500 or more and less than 4000 are 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 usually having a molecular weight of 1000 or more are 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.

[0021] 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. Note that the α-position carbon atom of the acrylic acid ester is, unless otherwise specified, the carbon atom to which the carbonyl group of acrylic acid is bonded. Hereinafter, an acrylic ester 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 acrylic ester.

[0022] 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, as well as 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.

[0023] In this specification and the claims of this 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.

[0024] (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).

[0025] 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; or (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.

[0026] 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.

[0027] 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.

[0028] <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).

[0029] [Chemical formula] [In the formula, Y 0 represents a polar group containing an oxygen atom. Rf 0 represents a fluorine atom or a fluorinated alkyl group. R 01 represents a substituent (excluding a polar group containing an oxygen atom, a fluorine atom, and a fluorinated alkyl group), and R 02 and R 03 each independently represent a substituent (excluding an iodine atom). L 01 and L 02 each independently represent a hydrogen atom or a substituent, and L 01 and L 02 may be bonded to each other to form a ring together with the sulfur atom in the formula. n0 and m0 each independently represent an integer of 1 to 4, p01 represents an integer of 0 to 3, and n0 + m0 + p01 ≤ 5. p02 and p03 each independently represent an integer of 0 to 3, q01 and q02 each independently represent an integer of 1 to 4, p02 + q01 ≤ 4, and p03 + q02 ≤ 4. When m0 is an integer of 2 or more, two or more Y 0 may be the same as or different from each other. When n0 is an integer of 2 or more, two or more Rf0 may be the same as or different from each other. When p01 is an integer of 2 or more, two or more Rs 01 may be the same as or different from each other. When p02 is an integer of 2 or more, two or more Rs 02 may be the same as or different from each other. When p03 is an integer of 2 or more, two or more Rs 03 may be the same as or different from each other.]

[0030] In the formula (c0), Y 0 The oxygen atom-containing polar group in is not particularly limited. Examples of the oxygen atom-containing polar group include a hydroxy group-containing group, an oxy group-containing group, a carbonyl group-containing group, and the like. Specific examples of the oxygen atom-containing polar group include a hydroxy group, a hydroxyalkyl group, an alkoxy group, a carbonyl group, a carboxy group, an acyl group, an ester group, and the like. The hydroxyalkyl 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 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. The alkoxy 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 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. The acyl 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 acyl group may be linear or branched. Specific examples of the acyl group include an acetyl group. The ester group is -COOR y (R yA group represented by (wherein the alkyl group) is preferred. 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 R in the above formula y The alkyl group in may be linear or branched. Specific examples of the ester group include a methyl ester group. Y 0 From the viewpoints of improving sensitivity, reducing roughness, and improving resolution, a hydroxy group, a hydroxyalkyl group, or an alkoxy group is preferred, a hydroxy group or an alkoxy group is more preferred, a hydroxy group or a methoxy group is still more preferred, and a hydroxy group is particularly preferred.

[0031] In the formula (c0), the fluorinated alkyl group in Rf 0 Examples thereof include fluorinated alkyl groups having 1 to 10 carbon atoms. The fluorinated alkyl group may be linear or branched. The linear fluorinated 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 branched fluorinated alkyl group preferably has 3 to 6 carbon atoms, more preferably 3 to 5 carbon atoms, and still more preferably 3 carbon atoms. Rf 0 The fluorinated alkyl group in is preferably a perfluoroalkyl group, and more preferably a trifluoromethyl group. Rf 0 Is preferably a fluorine atom or a trifluoromethyl group.

[0032] In the formula (c0), the substituents in R 01 , R 02 And R 03 The substituents in are not particularly limited as long as they are groups that substitute the hydrogen atoms of the phenyl group in the formula (c0). R 01 The substituent in is a substituent other than the substituents selected from the group consisting of an oxygen atom-containing polar group, a fluorine atom, and a fluorinated alkyl group. R 01Examples of the substituent in [compound name] include an alkyl group, a bromine atom, an iodine atom, a cyano group, an amino group, and the like. R 01 The alkyl group as the substituent in [compound name] 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. R 02 and R 03 The substituents in [compound name] are substituents other than an iodine atom. R 02 and R 03 Examples of the substituent in [compound name] include an alkyl group, a hydroxy group, a hydroxyalkyl group, an alkoxy group, a cyano group, an amino group, a carboxy group, a carbonyl group, a nitro group, a fluorine atom, a bromine atom, a halogenated alkyl group, and the like. R 02 and R 03 The alkyl group, hydroxyalkyl group, alkoxy group, and halogenated alkyl group as the substituents in [compound name] preferably have 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, hydroxyalkyl group, alkoxy group, and fluorinated 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. Specific examples of the hydroxyalkyl group include a methylol group and an ethyrol group. Specific examples of the alkoxy group include a methoxy group and an ethoxy group. Examples of the halogen atom in the halogenated alkyl group include a fluorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. Specific examples of the halogenated alkyl group include a trifluoromethyl group.

[0033] In the formula (c0), L 01 and L 02Examples of the substituent in [compound name] include a halogen atom, a halogenated alkyl group, an alkyl group, a hydroxy group, a hydroxyalkyl group, an alkoxy group, a cyano group, an amino group, a carboxy group, a carbonyl group, a nitro group, etc. Examples of the halogenated alkyl group, alkyl group, hydroxyalkyl group, and alkoxy group are the same as those described above. L 01 and L 02 When L and L are bonded to each other to form a ring together with the sulfur atom in the formula, 01 and L 02 Examples of the group formed by the connection of L and L include a single bond, an alkylene group having 1 to 3 carbon atoms, a carbonyl group (-C(=O)-), an ether bond (-O-), etc. L 01 and L 02 are preferably a hydrogen atom or are bonded to each other to form a ring together with the sulfur atom in formula (c0).

[0034] In the above formula (c0), m0 is preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1. In the above formula (c0), n0 is preferably an integer of 1 to 3, more preferably 1 or 2. From the viewpoints of improving sensitivity and reducing roughness, n0 is preferably 2 or 3, and more preferably 2.

[0035] In the above formula (c0), q01 and q02 are preferably integers of 1 to 3. From the viewpoints of improving sensitivity and reducing roughness, q01 and q02 are preferably 1 or 2.

[0036] In the above formula (c0), p01, p02, and p03 are preferably integers of 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0037] In the above formula (c0), Y 0 may be in any of the ortho, meta, and para positions of the sulfur atom in the formula, but at least one is preferably present in the para position. In the above formula (c0), Rf 0It may be in the ortho, meta, or para position of the sulfur atom in the formula, but at least one is preferably present in the ortho or meta position. In the formula (c0), the iodine atom (I) may be in any of the ortho, meta, and para positions of the sulfur atom in the formula, but is preferably present in the para position.

[0038] The cation (C0) is preferably a cation represented by the following general formula (c0-1) or (c0-2).

[0039] [Chemical formula] [In the formula, Y 0 , Rf 0 , R 01 , R 02 , R 03 , n0, m0, and p01 are the same as those in the general formula (c0), respectively. L 03 represents a single bond or a divalent linking group. q011 and q021 each independently represent an integer from 1 to 5, p021 and p031 each independently represent an integer from 0 to 5, p021 + q011 ≤ 5, and p031 + q021 ≤ 5. q012 and q022 each independently represent an integer from 1 to 4, p022 and p032 each independently represent an integer from 0 to 4, p022 + q012 ≤ 4, and p032 + q022 ≤ 4.]

[0040] In the formulas (c0-1) and (c0-2), q011, q021, q012, and q022 are preferably integers from 1 to 3, and more preferably 1 or 2. In the formulas (c0-1) and (c0-2), p021, p031, p022, and p032 are preferably integers from 0 to 2, more preferably 0 or 1, and particularly preferably 0. In the formula (c0-2), L 03Examples of the divalent linking group include an alkylene group having 1 to 3 carbon atoms, a carbonyl group, an oxygen atom, -C(=O)-O-, and -O-C(=O)-. The alkylene group having 1 to 3 carbon atoms is preferably a methylene group or an ethylene group, more preferably a methylene group.

[0041] Specific examples of the cation (C0) are shown below, but are not limited thereto.

[0042]

Chemical formula

[0043]

Chemical formula

[0044] <Substrate component (A)> In the resist composition of this 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.

[0045] In the resist composition of this embodiment, the component (A) may be used alone or in combination of two or more.

[0046] ·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).

[0047] ≪Constituent unit (a1)≫ The constituent unit (a1) is a constituent unit containing an acid-decomposable group whose polarity increases by the action of an acid.

[0048] 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.

[0049] Acetal-type acid-dissociable group: Examples of the acid-dissociable group that protects the carboxy group or hydroxy group among the polar groups include, for example, the acid-dissociable group represented by the following general formula (a1-r-1) (hereinafter sometimes referred to as the "acetal-type acid-dissociable group").

[0050] [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 combine with either Ra’ 1 , Ra’ 2 to form a ring.]

[0051] In formula (a1-r-1), it is preferable that at least one of Ra’ 1 and Ra’ 2 is a hydrogen atom, and it is more preferable that both are hydrogen atoms. Ra’ 1 or Ra’ 2When it is an alkyl group, examples of the alkyl group include the same groups 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.

[0052] 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.

[0053] 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.

[0054] 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 also 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.

[0055] Ra’ 3 When the cyclic hydrocarbon group of 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 some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms, and the like. 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. Ra’ 3 Specific examples of the aromatic hydrocarbon group in 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.

[0056] 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-mentioned 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 an aromatic hydrocarbon ring such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene.

[0057] 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.

[0058] Tertiary alkyl ester type acid dissociable group: Among the above polar groups, examples of the acid dissociable group for protecting a carboxy group include an acid dissociable group 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 group" for convenience.

[0059]

Chemical formula

[0060] Ra’ 4 Examples of the hydrocarbon group of include a linear or branched alkyl group, a linear or cyclic alkenyl group, or a cyclic hydrocarbon group. Ra’ 4 The linear or branched alkyl group, cyclic hydrocarbon group (aliphatic hydrocarbon group which is a monocyclic group, aliphatic hydrocarbon group which is a polycyclic group, aromatic hydrocarbon group) in is the same as those of the above Ra’ 3 . 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.

[0061] Ra’ 5 and Ra’ 6 are bonded to each other to form a ring, the groups represented by the following general formula (a1-r2-1), the groups represented by the following general formula (a1-r2-2), and the groups represented by the following general formula (a1-r2-3) are preferably mentioned. On the other hand, when Ra’ 4 ~Ra’ 6 are not bonded to each other and are independent hydrocarbon groups, the group represented by the following general formula (a1-r2-4) is preferably mentioned.

[0062] [Chemical formula] [In formula (a1-r2-1), Ra’ 10 represents a linear or branched alkyl group having 1 to 12 carbon atoms, a part of which may be 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 each independently represents 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).]

[0063] 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.

[0064] 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.

[0065] 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-, etc.

[0066] In formula (a1-r2-1), Ra’ 11 (Ra’ 10An aliphatic cyclic group formed together with the carbon atom to which it is bonded) is Ra’ in formula (a1-r-1). 3 As the aliphatic hydrocarbon group (alicyclic hydrocarbon group) which is a monocyclic group or polycyclic group of 3 , the group exemplified is preferable. Among them, a monocyclic alicyclic hydrocarbon group is preferable, and specifically, a cyclopentyl group and a cyclohexyl group are more preferable.

[0067] In formula (a1-r2-2), as the cyclic hydrocarbon group formed by Xa together with Ya, the group obtained by further removing one or more hydrogen atoms from the cyclic monovalent hydrocarbon group (aliphatic hydrocarbon group) in Ra’ in the formula (a1-r-1) can be mentioned. 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 which the cyclic hydrocarbon group in the above Ra’ 3 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, polycyclic aliphatic saturated hydrocarbon groups such as an adamantyl group, and the like. Ra 101 ~Ra 103Among 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.

[0068] 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 mentioned above.

[0069] Ra 101 ~Ra 103 Examples of the group containing a carbon-carbon double bond formed by two or more of Ra

[0070] 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.

[0071] In formula (a1-r2-3), the aliphatic cyclic group formed by Xaa together with Yaa is preferably a group exemplified as the aliphatic hydrocarbon group which is a monocyclic group or a polycyclic group of Ra' 3 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 is 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 benzene, and most preferably a group obtained by removing one or more hydrogen atoms from benzene. Ra in formula (a1-r2-3)104 Examples of the substituent that may be included are, 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.

[0072] 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 are the same as those of 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 those of the above Ra x5 for example.

[0073] 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.

[0074] Ra’ 14The linear alkyl group in [description] preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms. Specifically, examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, etc. 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.

[0075] Ra’ 14 The branched alkyl group in [description] preferably has 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms. Specifically, examples include 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., and an isopropyl group is preferred.

[0076] Ra’ 14 When [it] becomes a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may also be a polycyclic group or a monocyclic group. As the aliphatic hydrocarbon group that is a monocyclic group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferred. The monocycloalkane preferably has 3 to 6 carbon atoms, and specifically, examples include cyclopentane, cyclohexane, etc. As the aliphatic hydrocarbon group that is a polycyclic group, a group obtained by removing one hydrogen atom from a polycycloalkane is preferred. The polycycloalkane preferably has 7 to 12 carbon atoms, and specifically, examples include adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 decane, tetracyclododecane, etc.

[0077] Ra’ 14 The aromatic hydrocarbon group in [description] includes 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 may optionally have include 104 the same ones as the substituents that may be possessed.

[0078] Ra’ in formula (a1-r2-4) 14 When it is a naphthyl group, the position bonded 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 formula (a1-r2-4) 14 When it is an anthryl group, the position bonded 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.

[0079] Specific examples of the group represented by the formula (a1-r2-1) are given below.

[0080]

Chemical formula

[0081]

Chemical formula

[0082]

Chemical formula

[0083] Specific examples of the group represented by the formula (a1-r2-2) are given below.

[0084] [Chemistry]

[0085] [Chemistry]

[0086] [Chemistry]

[0087] Specific examples of the group represented by the formula (a1-r2-3) are given below.

[0088] [Chemistry]

[0089] Specific examples of the group represented by the formula (a1-r2-4) are given below.

[0090] [Chemistry]

[0091] Tertiary alkyloxycarbonyl acid dissociable group: Examples of the acid dissociable group for protecting the hydroxyl group among the polar groups include, for example, the acid dissociable group represented by the following general formula (a1-r-3) (hereinafter sometimes referred to as "tertiary alkyloxycarbonyl acid dissociable group" for convenience).

[0092] [Chemistry] [In the formula, Ra’ 7 ~Ra’ 9 are each an alkyl group.]

[0093] In formula (a1-r-3), Ra’ 7 ~Ra’ 9is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. In addition, the total number of carbon atoms of each alkyl group is preferably 3 to 7, more preferably 3 to 5, and most preferably 3 to 4.

[0094] Secondary alkyl ester type acid dissociable group: Among the above polar groups, examples of the acid dissociable group for protecting the carboxy group include an acid dissociable group represented by the following general formula (a1-r-4).

[0095] [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 Ra’ 11a or Ra’ 11b and Ra’ 12 and Ra’ 10

[0096] In the formula, Ra’ 10 and Ra’ 12 The hydrocarbon groups in are the same as those of the above Ra’ 3 In the formula, Ra’ 11a and Ra’ 11b The alkyl groups 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’ 11b ​The alkyl group in may have a substituent. Examples of this substituent include Ra described above. x5 and the like.

[0097] Ra’ 10 and Ra’ 11a or Ra’ 11b may combine with each other to form a ring. The ring may be polycyclic or monocyclic, and may be an alicyclic ring or an aromatic ring. The alicyclic ring and the aromatic ring may contain heteroatoms.

[0098] Ra’ 10 and Ra’ 11a or Ra’ 11b Among the above, the rings formed by combining with each other are preferably monocycloalkene, a ring in which some of the carbon atoms of monocycloalkene are substituted with heteroatoms (such as oxygen atoms, sulfur atoms), and monocycloalkadiene, preferably cycloalkene having 3 to 6 carbon atoms, and preferably cyclopentene or cyclohexene.

[0099] 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.

[0100] 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 described above. x5 and the like.

[0101] 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 combining Ra’ 10 and Ra’ 11a or Ra’ 11b combining with each other.

[0102] Specific examples of the group represented by the formula (a1-r-4) are given below.

[0103] [Chemical formula]

[0104] 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, a structural unit in which at least a part of the hydrogen atoms 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 atoms 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.

[0105] 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 formula (a1-1), (a1-2), or (a1-3).

[0106] [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. Va 1 is a divalent hydrocarbon group which may have an ether bond. n a1 is an integer of 0 to 2. Ra 1 is an acid dissociable group represented by the above general formula (a1-r-1), (a1-r-2), or (a1-r-4). Wa 1 is an n a2 + monovalent hydrocarbon group. n a2 is an integer of 1 to 3. Ra2 is an acid dissociable group represented by the general formula (a1-r-1) or (a1-r-3) above. Ya 001 is a single bond or a divalent linking group. Ya 01 is a single bond or a divalent linking group. Rax 01 is an acid dissociable group represented by the general formula (a1-r-1), (a1-r-2) or (a1-r-4) above. Rz 01 is an alkyl group, a halogen atom, a halogenated alkyl group, a hydroxy group, or an alkoxy group. q is an integer from 0 to 3. n is an integer of 0 or more. However, n ≦ q × 2 + 4.]

[0107] In the formulas (a1-1) to (a1-3) above, the alkyl group having 1 to 5 carbon atoms for R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, and the like. 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.

[0108] In the formula (a1-1), Va 1 The divalent hydrocarbon group in may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0109] Va 1 The aliphatic hydrocarbon group as the divalent hydrocarbon group in may be saturated or unsaturated, and is 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 the structure.

[0110] 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, examples include a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], a pentamethylene group [-(CH2)5-], 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 aliphatic hydrocarbon group, a branched alkylene group is preferred. Specifically, examples include alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-; alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2CH2-, and other alkylalkylene groups. The alkyl group in the alkylalkylene group preferably has 1 to 5 carbon atoms and is a linear alkyl group.

[0111] Examples of the aliphatic hydrocarbon group containing a ring in the 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 are the same as those of the linear aliphatic hydrocarbon group or the branched aliphatic hydrocarbon group described above. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 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 monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specifically includes cyclopentane, cyclohexane, etc. As the polycyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from 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, etc.

[0112] Va 1 The aromatic hydrocarbon group as the divalent hydrocarbon group in Va 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 heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a heteroatom. Examples of the heteroatom in the aromatic heterocycle 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 in the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0113] 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.

[0114] In the formula (a1-2), Wa 1 The n a2 +1-valent 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. The n a2 +1-valent is preferably 2 to 4-valent, and more preferably 2 or 3-valent. In the formula (a1-2), Ra 2 is preferably an acid dissociable group represented by the above general formula (a1-r-1).

[0115] In the formula (a1-3), Ya 001The divalent linking group in is not particularly limited, but examples of suitable ones include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a heteroatom. Ya 001 As , 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. 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 As , a combination of an ester bond [-C(=O)-O-, -O-C(=O)-] and a linear alkylene group, or a single bond is more preferable, and a single bond is still more preferable.

[0116] In the formula (a1-3), Ya 01 The divalent linking group in is not particularly limited, but examples of suitable ones include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a heteroatom. Ya 01 Among these, Ya 01 As , a combination of an ester bond [-C(=O)-O-, -O-C(=O)-] and a linear alkylene group, or a single bond is more preferable, and a single bond is still more preferable.

[0117] 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 still more preferable.

[0118] 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, still 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 As the halogen atom in, an iodine atom is preferable. Rz 01 As the halogen atom of the halogenated alkyl group in, a fluorine atom, iodine atom, or bromine atom is preferable, and a fluorine atom is more preferable. Rz 01 Is preferably an alkoxy group or a hydroxy group, and more preferably a hydroxy group.

[0119] 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 still more preferably 1 or 2. When n is an integer of 2 or more, two or more Rz 01 May be the same as or different from each other. In the formula (a1-3), n ≦ q × 2 + 4. For example, when q is 1 and it is a naphthalene structure, all 6 hydrogen atoms of the naphthalene may be substituted with hydroxy groups. Also, in the naphthalene, Ya 001 , -Ya 01 -C(=O)-O-Ra 01 The substitution positions of the group and the hydroxy group are not particularly limited.

[0120] 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.

[0121]

Chemical formula

[0122] [Chemical]

[0123] [Chemical]

[0124] [Chemical]

[0125] [Chemical]

[0126] [Chemical]

[0127] [Chemical]

[0128] [Chemical]

[0129] [Chemical]

[0130] 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.

[0131] [Chemical]

[0132]

Chem.

[0133]

Chem.

[0134]

Chem.

[0135]

Chem.

[0136] (A1) component's constituent unit (a1) may be one kind or two or more kinds. As the constituent unit (a1), since it is easier to enhance the characteristics (sensitivity, shape, etc.) in lithography using electron beams or EUV, the constituent unit represented by the above formula (a1-1) or the constituent unit represented by the above formula (a1-3) is more preferable. Among them, since it is suitable for enhancing reactivity in EB or EUV applications, the acid-dissociable groups (Ra 1 , Rax 01 ) are preferably acid-dissociable groups represented by the above general formulas (a1-r2-1), (a1-r2-3), (a1-r2-4), or (a1-r-4), respectively, and among them, it is particularly preferable to select those that are cyclic groups.

[0137] Alternatively, as the constituent unit (a1), those containing the constituent unit represented by the following general formula (a1-1-1) may be used.

[0138]

Chem.

[0139] In the above formula (a1-1-1), R, Va 1 and n a1 are the same as R, Va 1 and n a1 in the above formula (a1-1).

[0140] The description of the acid dissociable group represented by 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 applications, it is preferable to select an acid dissociable group that is a cyclic group.

[0141] The proportion of the structural 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 structural units constituting the component (A1). By setting the proportion of the structural unit (a1) to be equal to or higher than the lower limit value of the above-mentioned preferred range, lithography characteristics such as sensitivity, resolution, and CDU improvement are improved. On the other hand, when it is equal to or lower than the upper limit value of the above-mentioned preferred range, a balance with other structural units can be achieved, and various lithography characteristics become good.

[0142] <<Other Structural Units>> The component (A1) may have other structural units in addition to the above-mentioned structural unit (a1) as necessary. Examples of other structural units include, for example, a structural unit (a10) represented by 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 general formula (a8-1) described later, and the like.

[0143] Constituent unit (a10): The constituent unit (a10) is a constituent unit represented by the following general formula (a10-1).

[0144]

Chemical formula

[0145] 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 a hydrogen atom or a methyl group is particularly preferable from the viewpoint of easy availability in industry.

[0146] In the formula (a10-1), Ya x1 is a single bond or a divalent linking group. In the above chemical formula, the divalent linking group for Ya x1 is not particularly limited, but examples of preferable ones include a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a hetero atom, and the like.

[0147] ·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.

[0148] ··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 linear or branched aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups containing a ring in the structure.

[0149] ···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. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferred. Specifically, examples include a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], a pentamethylene group [-(CH2)5-], 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 aliphatic hydrocarbon group, a branched alkylene group is preferred. Specifically, examples include alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-; alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2CH2-, and other alkylalkylene groups. The alkyl group in the alkylalkylene group preferably has 1 to 5 carbon atoms and is linear.

[0150] 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.

[0151] ···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 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.

[0152] 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 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 a group in which part or all of the hydrogen atoms of the alkyl group are substituted with the halogen atoms. In the cyclic aliphatic hydrocarbon group, part of the carbon atoms constituting the ring structure may be substituted with a substituent containing a hetero atom. As the substituent containing a hetero atom, -O-, -C(=O)-O-, -S-, -S(=O)2-, -S(=O)2-O- are preferable.

[0153] ·· 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, 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 part 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.

[0154] In the aromatic hydrocarbon group, the hydrogen atoms contained in 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 substituents 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.

[0155] ·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-Y22 -,-Y 21 -O-,-Y 21 -C(=O)-O-,-C(=O)-O-Y 21 -,-[Y 21 -C(=O)-O] m” -Y 22 -,-Y 21 -O-C(=O)-Y 22 -or -Y 21 -S(=O)2-O-Y 22 -represented by the group [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. can 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 21 is preferably a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, still more preferably a linear alkylene group having 1 to 5 carbon atoms, and particularly preferably a methylene group or an ethylene group. Y 22As 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. Formula -[Y 21 -C(=O)-O] m” -Y 22 In the group represented by, 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, the formula -[Y 21 -C(=O)-O] m” -Y 22 As the group represented by, the group represented by the formula -Y 21 -C(=O)-O-Y 22 - is particularly preferable. Among them, the group represented by the formula -(CH2) a’ -C(=O)-O-(CH2) 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.

[0156] 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.

[0157] In the formula (a10-1) above, Wa x1 is an aromatic hydrocarbon group which may have a substituent. Wa x1 As the aromatic hydrocarbon group in, from an aromatic ring which may have a substituent (n ax1Examples of the group excluding (+1) hydrogen atoms include groups obtained by removing (+1) hydrogen atoms from aromatic compounds containing an aromatic ring which may have two or more substituents (such as biphenyl and fluorene). The aromatic ring herein is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, 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 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 heterocyclic ring include a pyridine ring and a thiophene ring. Also, Wa x1 Examples of the aromatic hydrocarbon group in include groups obtained by removing (n ax1 +1) hydrogen atoms from aromatic compounds containing an aromatic ring which may have two or more substituents (such as biphenyl and fluorene). Among these, Wa x1 is preferably a group obtained by removing (n ax1 +1) hydrogen atoms from benzene, naphthalene, anthracene or biphenyl, more preferably a group obtained by removing (n ax1 +1) hydrogen atoms from benzene or naphthalene, and still more preferably a group obtained by removing (n ax1 +1) hydrogen atoms from benzene.

[0158] Wa x1 The aromatic hydrocarbon group in may 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 are the same as those listed as the substituent of the cyclic aliphatic hydrocarbon group in Ya x1 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 x1The aromatic hydrocarbon group in [it] preferably has no substituent.

[0159] In the 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.

[0160] Specific examples of the structural unit (a10) represented by the formula (a10-1) are shown below. In each of the following formulas, R α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

[0161] [Chemical formula]

[0162] [Chemical formula]

[0163] [Chemical formula]

[0164] The structural unit (a10) contained in the component (A1) may be one kind or two or more kinds. The component (A1) may or may not have the structural unit (a10), but preferably has the structural unit (a10). When the component (A1) has the structural unit (a10), the proportion of the structural unit (a10) in the component (A1) 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 component (A1). 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 increased. 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.

[0165] Constituent unit (a2): The (A1) component may or may not have a constituent unit (a2) containing a lactone-containing cyclic group (however, excluding those corresponding to the constituent unit (a1)). The lactone-containing cyclic group of the constituent 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 constituent unit (a2), lithography characteristics and the like become good due to 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.

[0166] 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 in the case of having another ring structure, it is called a polycyclic group regardless of its structure. The lactone-containing cyclic group may be a monocyclic group or a polycyclic group. As the lactone-containing cyclic group in the constituent unit (a2), any group can be used without particular limitation. Specifically, groups represented by the following general formulas (a2-r-1) to (a2-r-7) can be mentioned.

[0167] [Chemical formula] [In the formula, Ra’ 21 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; R” is a hydrogen atom, an alkyl group, or a lactone-containing cyclic group; A” is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom (-O-) or a sulfur atom (-S-), an oxygen atom or a sulfur atom, n’ is an integer of 0 to 2, and m’ is 0 or 1. * indicates a bond (the same applies hereinafter).]

[0168] In the general formulas (a2-r-1) to (a2-r-7), Ra’ 21As the alkyl group in [description], an alkyl group having 1 to 6 carbon atoms is preferable. The alkyl group is preferably linear or branched. Specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, etc. may 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 [description], an alkoxy group having 1 to 6 carbon atoms is preferable. The alkoxy group is preferably linear or branched. Specifically, the group in which the alkyl group mentioned as the alkyl group in the above Ra’ 21 is linked with an oxygen atom (-O-). Ra’ 21 As the halogen atom in [description], a fluorine atom is preferable. Ra’ 21 As the alkyl halide group in [description], the 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 may be mentioned. As the alkyl halide group, a fluorinated alkyl group is preferable, and a perfluoroalkyl group is particularly preferable.

[0169] Ra’ 21 In -COOR” and -OC(=O)R” in [description], R” is each a hydrogen atom, an alkyl group, or a lactone-containing cyclic group. As the alkyl group in R”, any of linear, branched, and cyclic ones may be used, and the number of carbon atoms is preferably 1 to 15. When R” is a linear or branched alkyl group, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, 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 respectively represented by the general formulas (a2-r-1) to (a2-r-7). Ra’ 21 As the hydroxyalkyl group in, those having 1 to 6 carbon atoms are preferable. 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.

[0170] Ra’ 21 Among the above, each is preferably independently a hydrogen atom or a cyano group.

[0171] 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, and examples thereof include -O-CH2-, -CH2-O-CH2-, -S-CH2-, and -CH2-S-CH2-. 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.

[0172] Specific examples of the groups represented by the general formulas (a2-r-1) to (a2-r-7) are given below.

[0173] [Chemical formula]

[0174] [Chemical formula]

[0175] As the structural unit (a2), among others, 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. Such a structural unit (a2) is preferably a structural unit represented by the following general formula (a2-1).

[0176] [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 21 is a single bond or a divalent linking group. La 21is -O-, -COO-, -CON(R’)-, -OCO-, -CONHCO- or -CONHCS-, and R’ represents a hydrogen atom or a methyl group. However, when La 21 is -O-, Ya 21 will not be -CO-. Ra 21 is a lactone-containing cyclic group.]

[0177] 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.

[0178] 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. The divalent linking group in Ya 21 is the same as the divalent linking group in Ya x1 in the above general formula (a10-1).

[0179] 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.

[0180] In the formula (a2-1), Ya 21 is a single bond, and La 21 is preferably -COO- or -OCO-.

[0181] 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 above general formulas (a2-r-1) to (a2-r-7), respectively.

[0182] (A1) component may have one or more than one kind of structural unit (a2). (A1) component may or may not have the structural unit (a2). When (A1) component has the structural unit (a2), the proportion of the structural 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 structural units (100 mol%) constituting the (A1) component. When the proportion of the structural unit (a2) is equal to or higher than the preferable lower limit value, the effect of containing the structural unit (a2) can be sufficiently obtained by the above-described effect. When it is equal to or lower than the upper limit value, the balance with other structural units can be achieved and various lithography characteristics become good.

[0183] Structural unit (a5): (A1) component may or may not have the structural unit (a5) that generates an acid upon exposure. As the structural unit (a5), known ones can be used. By having the structural unit (a5), the acid generated upon exposure is likely to be uniformly distributed in the resist film. Examples of the structural unit (a5) include structural units containing the structure described in the later-described (B) component. For example, structural units containing the structure represented by any of the following general formulas (b-1) to (b-3) can be mentioned. Examples of the structural unit (a5) preferably include structural units represented by the following general formula (a5-1).

[0184] [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. ]

[0185] {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 of 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. may 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. The halogen atom in the halogenated alkyl group is particularly preferably a fluorine atom. 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 preferred.

[0186] In the formula (a5-1), La 50 is a divalent linking group or a single bond. La 50 The divalent linking group in 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, or 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)-].

[0187] 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.

[0188] ··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 its structure, etc.

[0189] ···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, and specifically includes a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], a pentamethylene group [-(CH2)5-], etc. 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 preferable. Specifically, alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-; alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2CH2- and other alkylalkylene groups. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

[0190] The above linear or branched-chain 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.

[0191] ··· 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-chain aliphatic hydrocarbon group, and a group in which the cyclic aliphatic hydrocarbon group is interposed in the middle of a linear or branched-chain aliphatic hydrocarbon group. Examples of the above linear or branched-chain aliphatic hydrocarbon group are the same as those described above. The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing two 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 two hydrogen atoms from polycycloalkane is preferable, and 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 and the like can be mentioned.

[0192] 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, and a tert-butyl group are 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, and a tert-butoxy group are more preferable, and a methoxy group and an ethoxy group are most preferable. Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, 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, a part of the carbon atoms constituting the ring structure may be substituted with a substituent containing a hetero atom. As the substituent containing a hetero atom, -O-, -C(=O)-O-, -S-, -S(=O)2-, -S(=O)2-O- are preferable.

[0193] ··Ra 50Aromatic 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 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 number of 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 is substituted with a hetero atom, and the like can be mentioned. Examples of the hetero atom 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. 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 (for example, 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 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. 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.

[0194] 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, 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, and a tert-butyl group are most preferable. Examples of the alkoxy group, the halogen atom, and the halogenated alkyl group as the substituent include those exemplified as the substituent that substitutes the hydrogen atom of the cyclic aliphatic hydrocarbon group.

[0195] 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.

[0196] 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.

[0197] 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 (-SO2-) 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.

[0198] [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.]

[0199] 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.

[0200] 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. V' 101 and V' 102As the alkylene group in [the relevant context], specifically, a methylene group [-CH2-]; alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-; an ethylene group [-CH2CH2-]; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-; a trimethylene group (n-propylene group) [-CH2CH2CH2-]; alkyltrimethylene groups such as -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-; a tetramethylene group [-CH2CH2CH2CH2-]; alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2CH2-; a pentamethylene group [-CH2CH2CH2CH2CH2-] and the like can be mentioned. Also, V’ 101 or V’ 102 In [the relevant context], some of the methylene groups in the alkylene group may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms. The said 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’ in the formula (a1-r-1). 3 More preferably, it is a cyclohexylene group, a 1,5-adamantylene group or a 2,6-adamantylene group.

[0201] La 51 As [La], a divalent linking group containing an ester bond or a divalent linking group containing an ether bond is preferable. More preferably, it is a linking group represented by the above formulas (L-al-1) to (L-al-5), (L-al-8), and even more preferably, it is a linking group represented by (L-al-3) or (L-al-8).

[0202] In the formula (a5-1), Ya 5 is a divalent linking group which may have a hetero atom or a single bond. Ya 5The divalent linking group in [description] is not particularly limited, and examples thereof preferably include a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a heteroatom, and the like. Ya 5 Regarding the divalent hydrocarbon group which may have a substituent and the divalent linking group containing a heteroatom in [description], they are 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 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 [description]. Among the above, Ya 5 is preferably a linear or branched alkylene group or a single bond, and more preferably a single bond.

[0203] 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 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), SO3 - At least one of Ra 51 and Ra 52 bonded to the carbon atom adjacent to is preferably a fluorine atom from the viewpoint of acid strength.

[0204] In the formula (a5-1), n5 is an integer of 1 to 4, and 1, 2 or 3 is preferable.

[0205] {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.

[0206] Preferred cation part ((M’ m+ )) 1 / m) Examples thereof include organic cations represented by the following general formulas (ca-1) to (ca-3).

[0207]

Chemical formula

[0208] 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 preferred. Examples of the alkyl group in R 201 ~R 207 are linear or cyclic alkyl groups, preferably those having 1 to 30 carbon atoms. Examples of the alkenyl group in R 201 ~R 207 preferably have 2 to 10 carbon atoms. R 201 ~R 207 , and R 210Examples of the substituent that may be possessed include, 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.

[0209]

Chemical formula

[0210] 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 may be saturated or unsaturated, and is usually preferably saturated.

[0211] R’ 201 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’ 201 Specific examples of the aromatic ring possessed by the aromatic hydrocarbon group in include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or an aromatic heterocyclic ring in which a part of the carbon atoms constituting these aromatic rings is substituted with a hetero atom. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, a nitrogen atom, and the like. R’ 201Specific examples of the aromatic hydrocarbon group in [description] 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 of the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0212] R’ 201 The cyclic aliphatic hydrocarbon group in [description] 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 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 a monocycloalkane is preferred. The monocycloalkane preferably has 3 to 6 carbon atoms, and specifically, cyclopentane, cyclohexane, etc. are included. As the polycyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from a polycycloalkane is preferred, and the polycycloalkane preferably has 7 to 30 carbon atoms. Among them, as the polycycloalkane, polycycloalkanes having a cross-linked ring system polycyclic skeleton such as adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 decane, tetracyclododecane, etc.; polycycloalkanes having a condensed ring system polycyclic skeleton such as a cyclic group having a steroid skeleton are more preferred.

[0213] Among them, R’201 The cyclic aliphatic hydrocarbon group in 201 is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane or a polycycloalkane, more preferably a group obtained by removing one hydrogen atom from a polycycloalkane, particularly preferably an adamantyl group or a norbornyl group, and most preferably an adamantyl group.

[0214] 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. Specifically, a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], a pentamethylene group [-(CH2)5-], etc. may be mentioned. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable. Specifically, alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-; alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2CH2- and other alkylalkylene groups may be mentioned. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0215] Also, R’ 201The cyclic hydrocarbon group in [description] 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, -SO2-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.

[0216]

Chemical formula

[0217] R’ 201 Examples of the substituent in the cyclic group of [description] 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 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. Examples of the halogenated alkyl group as a substituent include an alkyl group having 1 to 5 carbon atoms, for example, a group in which some or all of the hydrogen atoms of a methyl group, an ethyl group, a propyl group, an n-butyl group, a tert-butyl group, etc. are substituted with the halogen atom. The carbonyl group as a substituent is a group that substitutes a methylene group (-CH2-) constituting the cyclic hydrocarbon group.

[0218] Optionally substituted chain alkyl group: R’ 201 The chain alkyl group of [description] may be either linear or branched. As the linear alkyl group, it is preferably an alkyl group 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 an alkyl group 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, etc. can be mentioned.

[0219] Optionally substituted chain alkenyl group: R’ 201 As the chain alkenyl group of, it may be either linear or branched, preferably having 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. As the linear alkenyl group, for example, vinyl group, propenyl group (allyl group), butenyl group, etc. can be mentioned. As the branched alkenyl group, for example, 1-methylvinyl group, 2-methylvinyl group, 1-methylpropenyl group, 2-methylpropenyl group, etc. 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.

[0220] R’ 201 Examples of the substituent in the chain alkyl group or alkenyl group of include, for example, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, a cyclic group in the above R’ 201 etc. can be mentioned.

[0221] 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) can also be mentioned.

[0222] Among them, R’ 201 is preferably a cyclic group which may have a substituent, and more preferably a cyclic hydrocarbon group which may have a substituent. More specifically, for example, a phenyl group, a naphthyl group, a group obtained by removing one or more hydrogen atoms from a polycycloalkane; a lactone-containing cyclic group represented by the above general formulas (a2-r-1) to (a2-r-7); an -SO2-containing cyclic group represented by the following general formulas (b5-r-1) to (b5-r-4), etc. are preferable.

[0223] 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, they may be bonded via a hetero atom such as a sulfur atom, an oxygen atom, a nitrogen atom, or a functional group such as a carbonyl group, -SO-, -SO2-, -SO3-, -COO-, -CONH- or -N(R N )(wherein the R N is an alkyl group having 1 to 5 carbon atoms).). 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, a thiophene ring, a thiazole ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthrene ring, a phenoxathiin ring, a tetrahydrothiophenium ring, a tetrahydrothiopyranium ring, etc.

[0224] 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.

[0225] 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 -SO2-containing cyclic group which may have a substituent. 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. R 210 Examples of the alkyl group in R include linear or cyclic alkyl groups, preferably those having 1 to 30 carbon atoms. R 210 Examples of the alkenyl group in R preferably have 2 to 10 carbon atoms. R 210 The -SO2-containing cyclic group in R is not particularly limited and any one can be used. Specifically, groups represented by the following general formulas (b5-r-1) to (b5-r-4) are exemplified, a "-SO2-containing polycyclic group" is preferred, and a group represented by the general formula (b5-r-1) is more preferred.

[0226]

Chemical formula

[0227] 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.

[0228] In the general formulas (b5-r-1) to (b5-r-4), Rb’ 51 is 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, each is preferably independently a hydrogen atom or a cyano group.

[0229] 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.

[0230]

Chemical formula

[0231]

Chemical formula

[0232]

Chemical formula

[0233] Specific examples of the preferable cation represented by the formula (ca-1) include cations represented by the following chemical formulas respectively.

[0234]

Chemical formula

[0235]

Chemical formula

[0236]

Chem.

[0237]

Chem.

[0238]

Chem.

[0239]

Chem.

[0240]

Chem.

[0241] Specific examples of the preferred cation represented by the formula (ca-2) include diphenyliodonium cation, bis(4-tert-butylphenyl)iodonium cation, and the like.

[0242] Specific examples of the preferred cation represented by the formula (ca-3) include the cations represented by the following formulas (ca-3-1) to (ca-3-6), respectively.

[0243]

Chem.

[0244] 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, or 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.

[0245] Specific preferred examples of the constitutional 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 general formula (a5-1) above.

[0246]

Chemical formula

[0247]

Chemical formula

[0248]

Chemical formula

[0249]

Chemical formula

[0250] (A1) component's constituent unit (a5) may be one type or two or more types. When the (A1) component has the constituent unit (a5), the proportion of the constituent unit (a5) in the (A1) component is preferably 5 to 25 mol%, more preferably 10 to 20 mol%, and even more preferably 15 to 20 mol% with respect to the total (100 mol%) of all the constituent units constituting the (A1) component. When the proportion of the constituent unit (a5) is equal to or higher than the lower limit value of the above-mentioned preferred range, it becomes easier to achieve further increased sensitivity and improved resolution. On the other hand, when it is equal to or lower than the upper limit value of the above-mentioned preferred range, it becomes easier to balance with other constituent units.

[0251] Constituent unit (a6): The constituent unit (a6) is a constituent unit having acid diffusion controllability. The (A1) component may or may not have the constituent unit (a6). Known constituent units can be used for the constituent unit (a6). Examples of the constituent unit (a6) include constituent units containing the structures described in the following (D1) component and (D2) component. For example, constituent units containing the structures represented by any of the following general formulas (d1-1) to (d1-3) can be mentioned.

[0252] (A1) component's constituent unit (a6) may be one type or two or more types. When the (A1) component has the constituent unit (a6), the proportion of the constituent unit (a6) in the (A1) component is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and even more preferably 3 to 10 mol% with respect to the total (100 mol%) of all the constituent units constituting the (A1) component. When the proportion of the constituent unit (a6) is equal to or higher than the lower limit value of the above-mentioned preferred range, it becomes easier to achieve further increased sensitivity. On the other hand, when it is equal to or lower than the upper limit value of the above-mentioned preferred range, it becomes easier to balance with other constituent units.

[0253] Constituent unit (a0): (A1) component is a constituent unit containing the cation (C0). The constituent unit (a0) is represented by the following general formula (a0-1).

[0254] [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.]

[0255] In the formula (a0-1), R is the same as R in the general formula (a1-1). In the formula (a0-1), Rx 0- Examples of Rx include a group containing 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 contains 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 contains 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.

[0256] 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).

[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 50 is a divalent linking group or a single bond. Ra 50is a divalent hydrocarbon group which may have a substituent. n a5 is an integer from 0 to 2. La 51 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 from 1 to 4. Mc + is the cation (C0).]

[0258] 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.

[0259] Specific examples of the structural unit (a0b) include a structural unit having an anion part of any 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), M’ m+ is a cation represented by the general formula (c0). In this case, m is 1.

[0260] Preferred specific examples of the structural unit (a0b) include the following structural units. In the following formulas, R α represents a hydrogen atom, a methyl group or a trifluoromethyl group. Mc + is the cation (C0).

[0261]

Chemical formula

[0262] Preferred specific examples of the structural unit (a0b) are shown below, but are not limited thereto. In the following formulas, R αrepresents a hydrogen atom, a methyl group or a trifluoromethyl group.

[0263] [Chemical formula]

[0264] Constituent unit (a0d) having acid diffusion controllability: The constituent unit (a0) may be a constituent unit having acid diffusion controllability (hereinafter, also referred to as "constituent unit (a0d)"). The constituent unit (a0d) may be a constituent unit represented by the following general formula (a0-1d).

[0265] [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 of 0 to 2. Mc + is the cation (C0).]

[0266] 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.

[0267] Preferred specific examples of the constitutional unit (a0d) are shown below, but are 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).

[0268] [Chemical formula]

[0269] [Chemical formula]

[0270] The constitutional unit (a0) possessed by the component (A1) may be one type or two or more types. The component (A1) may have both the constitutional unit (a0b) and the constitutional unit (a0d), or may have only one of them.

[0271] When the component (A1) has the constitutional unit (a0b), the proportion of the constitutional unit (a0b) in the component (A1) is preferably 5 to 25 mol%, more preferably 8 to 20 mol%, based on the total of all constitutional units constituting the component (A1) (100 mol%). When the proportion of the constitutional unit (a0b) is at least the lower limit of the above preferred range, it becomes easier to achieve further increased sensitivity, reduced roughness, and improved resolution. On the other hand, when it is at most the upper limit of the above preferred range, it becomes easier to balance with other constitutional units.

[0272] When the component (A1) has the constitutional unit (a0d), the proportion of the constitutional unit (a0d) in the component (A1) 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 constitutional units constituting the component (A1) (100 mol%). When the proportion of the constitutional unit (a0d) is at least the lower limit of the above preferred range, it becomes easier to achieve further increased sensitivity, reduced roughness, and improved resolution. On the other hand, when it is at most the upper limit of the above preferred range, it becomes easier to balance with other constitutional units.

[0273] Constituent unit (a8): The constituent unit (a8) is a constituent unit derived from a compound represented by the following general formula (a8-1). The (A1) component may or may not have the constituent unit (a8).

[0274] [Chemical formula] [In the formula, W 2 is a polymerizable group-containing group. Ya x2 is a single bond or a (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.]

[0275] The "polymerizable group" in the polymerizable group-containing group of W 2 is a group that enables a compound having a polymerizable group to polymerize by radical polymerization or the like, and includes, for example, a multiple bond between carbon atoms such as an ethylenic double bond.

[0276] 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 heteroatom, 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 RX13 is 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.

[0277] Ya x2 and W 2 Examples of the condensed ring formed by and include the condensed ring formed by the polymerizable group at the W 2 site and Ya x2 and the condensed ring formed by the polymerizable group at the W 2 site and other groups other than the polymerizable group and Ya x2 and. Ya x2 and W 2 The condensed ring formed by and may have a substituent.

[0278] 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.

[0279]

Chemical formula

[0280] Among the above examples, the structural unit (a8) is preferably at least one selected from the group consisting of 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 structural units represented by chemical formulas (a8-1-01) to (a8-1-04) and (a8-1-09).

[0281] The structural unit (a8) contained in the component (A1) may be one kind or two or more kinds. The component (A1) may or may not have the structural unit (a8). The proportion of the structural unit (a8) in the component (A1) is preferably 0 to 50 mol%, more preferably 0 to 30 mol%, based on the total of all the structural units (100 mol%) constituting the component (A1).

[0282] As the component (A1) contained in the resist composition, one kind may be used alone, or two or more kinds may be used in combination.

[0283] Examples of the component (A1) include a polymer compound composed of the structural unit (a1) and the structural unit (a10); a polymer compound composed of the structural unit (a1), the structural unit (a10), and the structural unit (a0); a polymer compound composed of the structural unit (a1), the structural unit (a10), and the structural unit (a2), and the like.

[0284] In the polymer compound composed of the structural unit (a1) and the structural unit (a10), the proportion of the structural unit (a1) is more preferably 10 to 75 mol%, further preferably 30 to 70 mol%, still further preferably 40 to 70 mol%, based on the total of all the structural units (100 mol%) constituting the polymer compound. The proportion of the structural unit (a10) in the polymer compound is preferably 25 to 90 mol%, more preferably 30 to 70 mol%, further preferably 30 to 60 mol%, particularly preferably 20 to 50 mol%, based on the total of all the structural units (100 mol%) constituting the polymer compound.

[0285] In the polymer compound composed of the structural unit (a1), the structural unit (a10), and the structural unit (a0), the proportion of the structural unit (a1) is more preferably 10 to 85 mol%, further preferably 30 to 70 mol%, still further preferably 40 to 70 mol%, based on the total of all the structural units (100 mol%) constituting the polymer compound. The proportion of the structural unit (a10) in the polymer compound is preferably 10 to 85 mol%, more preferably 30 to 70 mol%, further preferably 30 to 60 mol%, particularly preferably 20 to 50 mol%, based on the total of all the structural units (100 mol%) constituting the polymer compound. The proportion of the structural unit (a0) in the polymer compound is preferably 1 to 50 mol%, more preferably 3 to 30 mol%, still more preferably 5 to 20 mol%, and particularly preferably 5 to 15 mol% with respect to the total of all the structural units (100 mol%) constituting the polymer compound.

[0286] In the polymer compound composed of the structural unit (a1), the structural unit (a10), and the structural unit (a2), the proportion of the structural unit (a1) is more preferably 10 to 85 mol%, still more preferably 30 to 70 mol%, and still more preferably 40 to 70 mol% with respect to the total of all the structural units (100 mol%) constituting the polymer compound. The proportion of the structural unit (a10) in the polymer compound is preferably 10 to 85 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 the structural units (100 mol%) constituting the polymer compound. The proportion of the structural unit (a2) in the polymer compound is preferably 5 to 80 mol%, more preferably 10 to 60 mol%, still more preferably 10 to 40 mol%, and particularly preferably 10 to 30 mol% with respect to the total of all the structural units (100 mol%) constituting the polymer compound.

[0287] Such component (A1) can be produced by dissolving the monomers that induce each structural 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 component (A1) can be produced by dissolving the monomer that induces the structural unit (a1) and the monomer that induces an arbitrary structural unit (e.g., the structural unit (a10), the structural unit (a5), etc.) in a polymerization solvent, adding the radical polymerization initiator as described above thereto, performing polymerization, and then performing a deprotection reaction. In addition, during polymerization, for example, a chain transfer agent such as HS-CH2-CH2-CH2-C(CF3)2-OH may be used in combination to introduce a -C(CF3)2-OH group at the terminal. Thus, a copolymer into which a hydroxyalkyl group in which a part of the hydrogen atoms of the alkyl group is substituted with a fluorine atom is introduced is effective in reducing development defects and LER (Line Edge Roughness: non-uniform unevenness on the side wall of the line).

[0288] The weight average molecular weight (Mw) of the component (A1) (based on polystyrene conversion by gel permeation chromatography (GPC)) is not particularly limited, and is preferably 1000 to 50000, more preferably 5000 to 40000, and even more preferably 5000 to 30000. When the Mw of the component (A1) is below the preferable upper limit of this range, there is sufficient solubility in a resist solvent for use as a resist, and when it is above the preferable lower limit of this range, the dry etching resistance and the cross-sectional shape of the resist pattern are good. The dispersity (Mw / Mn) of the component (A1) is not particularly limited, and is preferably 1.0 to 4.0, more preferably 1.0 to 3.0, and particularly preferably 1.0 to 2.0. Note that Mn represents the number average molecular weight.

[0289] ·Regarding the component (A2) The resist composition of the present embodiment may use, as the component (A), a base material component (hereinafter referred to as the "component (A2)") that does not correspond to the component (A1) and whose solubility in a developer changes by the action of an acid, in combination. The component (A2) is not particularly limited, and may be arbitrarily selected from a number of conventionally known base material components for chemically amplified resist compositions and used. The component (A2) may be used alone as one kind of high molecular compound or low molecular compound, or two or more kinds may be used in combination.

[0290] The proportion of the component (A1) in the component (A) is preferably 25% by mass or more, more preferably 50% by mass or more, still more preferably 75% by mass or more, and may be 100% by mass, based on the total mass of the component (A). When the proportion is 25% by mass or more, a resist pattern excellent in various lithography characteristics such as high sensitivity, resolution, and CDU improvement is likely to be formed.

[0291] In the resist composition of the present embodiment, the content of the component (A) may be adjusted according to the resist film thickness to be formed and the like.

[0292] <Acid generator component (B)> The resist composition of the present embodiment may contain an acid generator component (B) that generates an acid upon exposure. The component (B) is not particularly limited, and those proposed as acid generators for chemically amplified resist compositions heretofore 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 bis-alkyl or bis-aryl sulfonyldiazomethanes and poly(bis-sulfonyl)diazomethanes; nitrobenzyl sulfonate-based acid generators, iminosulfonate-based acid generators, disulfone-based acid generators, and various others. The form of inclusion of the component (B) may be in the form of a compound, may be in the form incorporated into the component (A1) as the above-described structural unit (a5), or may be in both of these forms.

[0293] Examples of the onium salt-based acid generator include a compound represented by the following general formula (b-1) (hereinafter also referred to as the "(b-1) component"), a compound represented by the general formula (b-2) (hereinafter also referred to as the "(b-2) component"), or a compound represented by the general formula (b-3) (hereinafter also referred to as the "(b-3) component").

[0294] Examples of the onium salt-based acid generator include 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)”).

[0295] [Chemical formula] [In the formula, R 101 and R 104 ~R 108 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. R 104 and R 105 may be bonded to each other to form a ring structure. R 102 is a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom. Y 101 is a divalent linking group containing an oxygen atom or a single bond. V 101 ~V 103 are each independently a single bond, an alkylene group or a fluorinated alkylene group. However, Y 101 and V 101 do not simultaneously become 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 -SO2-. m is an integer of 1 or more, and M’ m+ is an m-valent onium cation.]

[0296] {Anion part} ·Anion in component (b-1) In formula (b-1), R 101 is 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.

[0297] 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.

[0298] R 101 The aromatic hydrocarbon group in R 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 101 Specific examples of the aromatic ring of the aromatic hydrocarbon group in R 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 R include a group obtained by removing one hydrogen atom from the aromatic ring (aryl group: for example, phenyl group, naphthyl group, etc.), and 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 of the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0299] R 101 The cyclic aliphatic hydrocarbon group in R includes an aliphatic hydrocarbon group containing a ring in the 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 specifically includes cyclopentane, cyclohexane, etc. 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, polycycloalkanes having a crosslinked ring system polycyclic skeleton such as adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 decane, tetracyclododecane; and polycycloalkanes having a condensed ring system polycyclic skeleton such as a cyclic group having a steroid skeleton are more preferred.

[0300] Among them, 101 as the cyclic aliphatic hydrocarbon group in R, a group obtained by removing one or more hydrogen atoms from monocycloalkane or polycycloalkane is preferred, a group obtained by removing one hydrogen atom from polycycloalkane is more preferred, an adamantyl group and a norbornyl group are further preferred, and an adamantyl group is particularly preferred.

[0301] 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, further 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, and specifically includes a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], a pentamethylene group [-(CH2)5-], etc. The branched aliphatic hydrocarbon group, which may be bonded to the alicyclic hydrocarbon group, preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, 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 preferable. Specifically, alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-; alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2CH2- 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.

[0302] Also, R 101 The cyclic hydrocarbon group in may contain a hetero atom such as a heterocyclic ring. Specifically, lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-7), -SO2-containing cyclic groups represented by the general formulas (b5-r-1) to (b5-r-4), and other heterocyclic groups represented by the chemical formulas (r-hr-1) to (r-hr-16) can be mentioned.

[0303] R 101 Examples of the substituent in the cyclic group of 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 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, 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, a bromine atom, and an iodine atom are preferable. As the halogenated alkyl group as a substituent, a group in which a part or all of 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, a tert-butyl group, etc., are substituted with the halogen atom can be mentioned. The carbonyl group as a substituent is a group that substitutes the methylene group (-CH2-) constituting the cyclic hydrocarbon group.

[0304] 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 cyclic group, 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. R 101 Specific examples of the condensed cyclic group in 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 represents the bond that binds to Y in the formula (b-1).

[0305]

Chemical formula

[0306] R 101Examples of the substituent that the condensed cyclic group may have include, for example, 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. Examples of 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 Examples of the substituent that the condensed cyclic group may have include the same ones as those exemplified as the substituent of the cyclic group in the above R 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, and other arylalkyl groups), and a heterocyclic group represented by the above formulas (r-hr-1) to (r-hr-6), respectively. 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), respectively; a -SO2-containing cyclic group represented by the general formulas (b5-r-1) to (b5-r-4), respectively; and a heterocyclic group represented by the formulas (r-hr-7) to (r-hr-16), respectively.

[0307] A chain alkyl group that may have a substituent: 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. As the branched-chain alkyl group, it 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.

[0308] Optionally substituted linear alkenyl group: R 101 As the linear 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, still more 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, etc. can be mentioned. As the branched-chain alkenyl group, for example, 1-methylvinyl group, 2-methylvinyl group, 1-methylpropenyl group, 2-methylpropenyl group, etc. can be mentioned. Among the above, as the linear 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.

[0309] R 101 Examples of the substituent in the linear 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. 101 etc. can be mentioned.

[0310] In formula (b-1), Y 101 is a single bond or a divalent linking group containing an oxygen atom. Y 101 When Y is a divalent linking group containing an oxygen atom, the Y 101 may contain atoms other than the oxygen atom. Examples of the atoms other than the oxygen atom include a carbon atom, a hydrogen atom, a sulfur atom, a nitrogen atom, etc. 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 is bonded to V' in the following general formulas (L-al-1) to (L-al-8). 101 That is.

[0311] In 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.

[0312] In 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.

[0313] Specific examples of the anion moiety 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).

[0314] [Chemical formula] [In the formula, R'' 101 is an aliphatic cyclic group which may have a substituent, a monovalent heterocyclic group represented by the above chemical formulas (r-hr-1) to (r-hr-6), a condensed cyclic group represented by the formula (r-br-1) or (r-br-2), a chain alkyl group which may have a substituent or an aromatic cyclic group which may have a substituent. R'' 102is an aliphatic cyclic group which may have a substituent, a condensed cyclic group represented by the formula (r-br-1) or (r-br-2), a lactone-containing cyclic group represented by the general formula (a2-r-1), (a2-r-3) to (a2-r-7), or a -SO2-containing cyclic group represented by the general formula (b5-r-1) to (b5-r-4). R” 103 is an aromatic cyclic group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain-like alkenyl group which may have a substituent. V” 101 is a single bond, an alkylene group having 1 to 4 carbon atoms, or a fluorinated alkylene group having 1 to 4 carbon atoms. R 102 is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. v” is each independently an integer of 0 to 3, q” is each independently an integer of 0 to 20, and n” is 0 or 1.]

[0315] R” 101 、R” 102 and R” 103 The aliphatic cyclic group which may have a substituent of R”, R” and R” is preferably a group exemplified as the cyclic aliphatic hydrocarbon group in R 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 in the formula (b-1). 101 in the formula (b-1). The aliphatic cyclic group which may have a substituent of R”, R” and R” is preferably a group exemplified as the cyclic aliphatic hydrocarbon group in R 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 in the formula (b-1). 101 in the formula (b-1).

[0316] R” 101 and R” 103 The aromatic cyclic group which may have a substituent of R” and R” is preferably a group exemplified as the aromatic hydrocarbon group in the cyclic hydrocarbon group in R in the formula (b-1). Examples of the substituent include the same substituents as those which may substitute the aromatic hydrocarbon group in R in the formula (b-1). 101 in the formula (b-1). The aromatic cyclic group which may have a substituent of R” and R” is preferably a group exemplified as the aromatic hydrocarbon group in the cyclic hydrocarbon group in R in the formula (b-1). Examples of the substituent include the same substituents as those which may substitute the aromatic hydrocarbon group in R in the formula (b-1). 101 in the formula (b-1).

[0317] R” 101 The chain-like alkyl group which may have a substituent in R” is preferably a group exemplified as the chain-like alkyl group in R in the formula (b-1). 101 in the formula (b-1). R” 103 The chain alkenyl group which may have a substituent in 103 is preferably the group exemplified as the chain alkenyl group in R in the formula (b-1). 101

[0318] · 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 chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and each is the same as R in the formula (b-1). 101 However, R 104 , R 105 may be bonded to each other to form a ring. R 104 , R 105 is preferably a chain alkyl group which may have a substituent, more preferably a linear or branched alkyl group, or a linear or branched fluorinated alkyl group. The number of carbon atoms of the chain alkyl group is preferably 1 to 10, more preferably 1 to 7 carbon atoms, and still more preferably 1 to 3 carbon atoms. The number of carbon atoms of the chain alkyl group of 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, in the chain alkyl group of R 104 , R 105 , the larger the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid strength, and the more preferable because the transparency to high-energy light or electron beams of 250 nm or less is improved. The ratio of fluorine atoms, that is, the fluorination rate, in the chain alkyl group 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 the formula (b-2), V 102 , V 103 are each independently a single bond, an alkylene group, or a fluorinated alkylene group, and each is the same as V in the formula (b-1).​101 The same ones can be mentioned. In formula (b-2), L 101 , L 102 are each independently a single bond or an oxygen atom.

[0319] · Anion in the (b-3) component In formula (b-3), R 106 ~R 108 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 each is the same as R in formula (b-1) 101 The same ones can be mentioned. In formula (b-3), L 103 ~L 105 are each independently a single bond, -CO- or -SO2-.

[0320] Among the above, as the anion part of the component (B), the anion in the (b-1) component is preferable, and the anion represented by the formula (an-1) is more preferable.

[0321] {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.

[0322] As the cation part of the component (B), a sulfonium cation is preferable, the cations respectively represented by the formulas (ca-1) to (ca-3) are more preferable, the cation represented by the formula (ca-1) is still more preferable, and the cations respectively represented by the formulas (ca-1-1) to (ca-1-84) are particularly preferable.

[0323] Compound (B0): The cation part in the component (B) may be the cation (C0). In this case, the component (B) becomes the compound (C). The compound (C) as the component (B) is a compound (B0) represented by the following general formula (b0).

[0324] [Chemical formula] [wherein, Mc + is the cation (C0). Xb - is a counter anion. ]] Xb in the formula (b0) - includes anions in the compounds represented by any of the formulas (b-1) to (b-3). Examples of the compound (B0) include compounds represented by any of the following general formulas (b0-1) to (b0-3).

[0325] [Chemical formula] [wherein, R 101 and R 104 to R 108 are each independently a cyclic group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent. R 104 and R 105 may be bonded to each other to form a ring structure. R 102 is a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom. Y 101 is a divalent linking group containing an oxygen atom or a single bond. V 101 to V 103 are each independently a single bond, an alkylene group or a fluorinated alkylene group. However, Y 101 and V 101 do not simultaneously become a single bond. L 101 to L 102 are each independently a single bond or an oxygen atom. L 103 to L 105 are each independently a single bond, -CO- or -SO2-. Mc + is the cation (C0). ]]

[0326] R in the formulas (b0-1) to (b0-3) 101 , R104 ~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 above formulas (b-1) to (b-3), respectively.

[0327] R in the above formula (b0-1) 101 is preferably an aromatic hydrocarbon group which may have a substituent, more preferably a phenyl group which may have a substituent. The aromatic hydrocarbon group preferably has a halogen atom as a substituent, more preferably an iodine atom as a substituent. The number of iodine atoms as a substituent may be 1 to 4, preferably 1 to 3, more preferably 2 or 3.

[0328] Specific examples of the compound (B0) are shown below, but are not limited to these. + is the cation (C0).

[0329] [ka]

[0330] [ka]

[0331] Specific examples of the compound (B0) are shown below, but are not limited to these.

[0332] [ka]

[0333] [ka]

[0334] 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), in the resist composition, the content of the component (B) 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 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 preferably good.

[0335] 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 preferred range, it is easy for all of sensitivity, roughness, and resolution to be good.

[0336] <Base component (D)> In addition to the component (A), the resist composition of the present embodiment may contain a base component ((D) component) that traps (i.e., controls the diffusion of) an acid generated by exposure. The component (D) acts as a quencher (acid diffusion controller) that traps an acid generated by exposure in the resist composition. Examples of the component (D) 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, a photo-dissociable base ((D1) component) is preferred because it is easy to enhance all of the characteristics of high sensitivity, reduction of roughness, and suppression of the occurrence of coating defects. (D1) and (D2) components may be in the form of a compound, may be incorporated into the (A1) component as the above-described structural unit (a6), or may be in both of these forms. The compounds exemplified as the (D1) component described below may be used as the acid generator component ((B) component) described below depending on the combination with other compounds.

[0337] ·Regarding the (D1) component The (D1) component is not particularly limited as long as it decomposes upon exposure and loses acid diffusion controllability. 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 in the exposed portion of the resist film because they decompose and lose acid diffusion controllability (basicity), and act as a quencher in the unexposed portion of the resist film.

[0338]

Chemical formula

[0339] {(d1-1) component} ··Anion part In the formula (d1-1), Rd 1is 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, each of which is the above R’ 201 Examples thereof are the same as those of 201 . Among these, as Rd 1 is preferably an 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. 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 substituent containing a linking group represented by the above formulas (L-al-1) to (L-al-8) is preferable. Note that when the aromatic hydrocarbon group, aliphatic cyclic group, or chain-like alkyl group in Rd 1 has a linking group represented by the above general formulas (L-al-1) to (L-al-8) as a substituent, in the above general formulas (L-al-1) to (L-al-8), the one bonded to the carbon atom constituting the aromatic hydrocarbon group, aliphatic cyclic group, or chain-like alkyl group in Rd 1 is V’ 101 in the above general formulas (L-al-1) to (L-al-8). 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 aliphatic cyclic group are more preferably 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, and tetracyclododecane. The linear alkyl group preferably has 1 to 10 carbon atoms. Specifically, linear alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group; branched-chain alkyl groups such as 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, etc. may be mentioned.

[0340] 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 atoms other than fluorine atoms. Examples of atoms other than fluorine atoms include oxygen atom, sulfur atom, nitrogen atom, etc.

[0341] Preferred specific examples of the anionic part of the component (d1-1) are shown below.

[0342]

Chemical formula

[0343] ···Cation part In formula (d1-1), M m+ is an m-valent organic cation. M m+ As the organic cation of M, those similar to the cations respectively represented by the general formulas (ca-1) to (ca-3) are preferably mentioned, 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.

[0344] {(d1-2) component} ··Anion part In formula (d1-2), Rd 2 is 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 the above R’ 201 is the same as that. 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 (d1-2) component becomes a moderately weak acid anion, and the quenching ability as the (D) component is improved. Rd 2 is preferably a linear 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.

[0345] The linear alkyl group preferably has 1 to 10 carbon atoms, and more preferably 3 to 10 carbon atoms. The aliphatic cyclic group includes a group obtained by removing one or more hydrogen atoms from adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 decane, tetracyclododecane, etc. (which may have a substituent); and more preferably a group obtained by removing one or more hydrogen atoms from camphor.

[0346] Rd 2 The hydrocarbon group of may have a substituent, and examples of the substituent include the same substituents as those which the hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, linear alkyl group) in Rd 1 in the formula (d1-1) may have.

[0347] The following shows preferred specific examples of the anion part of the (d1-2) component.

[0348]

Chemical formula

[0349] ··Cation part In formula (d1-2), M m+ is an m-valent organic cation, which is the same as M in the formula (d1-1). m+ The same applies to the above. The component (d1-2) may be used alone or in combination of two or more.

[0350] {(d1-3) component} ·· Anion part In formula (d1-3), Rd 3 is 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 the same as the above R’ 201 is exemplified, and it is preferably a cyclic group, a linear alkyl group, or a linear alkenyl group containing a fluorine atom. Among them, a fluorinated alkyl group is preferable, and the same as the fluorinated alkyl group of the above Rd 1 is more preferable.

[0351] In formula (d1-3), Rd 4 is 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 the same as the above R’ 201 is exemplified. Among them, it is preferably an alkyl group, an alkoxy group, an alkenyl group, or a cyclic group which may have a substituent. Rd 4 The alkyl group in Rd is preferably a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc. are exemplified. The hydrogen atom of the alkyl group of Rd 4 may be partially substituted with a hydroxyl group, a cyano group, etc. Rd 4The alkoxy group in is preferably an alkoxy group having 1 to 5 carbon atoms. Specific examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group. Among them, a methoxy group and an ethoxy group are preferable.

[0352] Rd 4 The alkenyl group in is the same as the alkenyl group in the above R'. 201 Examples of the alkenyl group in include the same ones as the alkenyl group in the above R', and a vinyl group, a propenyl group (allyl group), a 1-methylpropenyl group, and a 2-methylpropenyl group are preferable. 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.

[0353] Rd 4 The cyclic group in is the same as the cyclic group in the above R'. 201 Examples of the cyclic group in include the same ones as the cyclic group in the above R', and an alicyclic group obtained by removing one or more hydrogen atoms from cycloalkanes such as cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 decane, tetracyclododecane, etc., or an aromatic group such as a phenyl group or a naphthyl group is preferable. When Rd 4 is an alicyclic group, the resist composition dissolves well in an organic solvent, and the lithography characteristics become good. Also, when Rd 4 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 the sensitivity and lithography characteristics become good.

[0354] In formula (d1-3), Yd 1 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, etc. Each of these is Ya in the above formula (a2-1). 21Examples thereof include the divalent hydrocarbon group which may have a substituent and the divalent linking group containing a hetero atom, which were mentioned in the description of the divalent linking group in [0000000]. Yd 1 Preferably, it is a carbonyl group, an ester bond, an amide bond, an alkylene group or a combination thereof. As the alkylene group, a linear or branched alkylene group is more preferable, and a methylene group or an ethylene group is even more preferable.

[0355] Specific preferable examples of the anionic part of the component (d1-3) are shown below.

[0356]

Chemical formula

[0357]

Chemical formula

[0358] ···Cationic part In formula (d1-3), M m+ is an m-valent organic cation, which is the same as M in the above formula (d1-1). m+ The component (d1-3) may be used alone or in combination of two or more.

[0359] The component (D1) may use only any one of the above components (d1-1) to (d1-3), or may use a combination of two or more. 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 even more preferably 2 to 15 parts by mass with respect to 100 parts by mass of the component (A).

[0360] The component (D1) preferably contains the above component (d1-1). ​Of the entire (D1) component, the content of the (d1-1) component is preferably 50% by mass or more, 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.

[0361] Production method of the (D1) component: The production methods of the above-mentioned (d1-1) component and (d1-2) component are not particularly limited and can be produced by known methods. Also, the production method of the (d1-3) component is not particularly limited, and for example, it is produced in the same manner as the method described in US2012-0149916. 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 the present embodiment, a compound of the (D1) component is used as the (B) component, and as the (D) component, a compound that generates an acid with a lower acidity than the acid generated by exposure of the (D1) component compound may be used. Also, in the resist composition of the present 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.

[0362] Compound (D0): The cationic part in the (D1) component may be the cation (C0). In this case, the (D1) component becomes the compound (C). The compound (C) as the (D1) component is a compound (D0) represented by the following general formula (d0).

[0363]

Chemical formula

[0364] Xd in the formula (d0) -Examples of the anion part include 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).

[0365] [Chemical formula] [In the formula, Rd 1 ~Rd 4 is an optionally substituted cyclic group, an optionally substituted linear alkyl group, or an optionally substituted linear alkenyl group. However, it is assumed that no fluorine atom is 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).]

[0366] Rd 1 ~Rd 4 , and Yd 1 in the formulas (d0-1) to (d0-3) are the same as those in the formulas (d1-1) to (d1-3), respectively.

[0367] Specific examples of the anion part in the formula (d0-1) are the same as those of the anion part in the formula (d1-1) above. Specific examples of the anion part in the formula (d0-2) are the same as those of the anion part in the formula (d1-2) above. Specific examples of the anion part in the formula (d0-3) are the same as those of the anion part in the formula (d1-3) above.

[0368] Rd 1An aromatic hydrocarbon group which may have a substituent is preferred, and a phenyl group which may have a substituent is more preferred. The aromatic hydrocarbon group preferably has a halogen atom as a substituent, and more preferably has an iodine atom as a substituent. Examples of the number of iodine atoms as a substituent include 1 to 4, preferably 1 to 3, and more preferably 2 or 3. Rd 1 The aromatic hydrocarbon group in 1 may have a hydroxy group as a substituent. Rd 1 Rd 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.

[0369] Specific examples of the compound (D0) are shown below, but are not limited thereto. In the following formula, Mc + is the cation (C0).

[0370]

Chemical formula

[0371] Specific examples of the compound (D0) are shown below, but are not limited thereto.

[0372]

Chemical formula

[0373]

Chemical formula

[0374] 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.

[0375] In the resist composition of this 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.

[0376] When the proportion of the compound (D0) in the (D) component is equal to or higher than the lower limit value of the above-preferred range, it is easy for all of sensitivity, roughness, and resolution to be good.

[0377] ·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. Examples of the aliphatic amine include amines (alkylamines or alkyl alcohol amines) or cyclic amines in which at least one of the hydrogen atoms of ammonia NH3 is substituted with an alkyl group or a hydroxyalkyl group having 12 or fewer carbon atoms. Specific examples of the alkylamine and alkyl alcohol amine 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 preferable, and tri-n-pentylamine or tri-n-octylamine is particularly preferable.

[0378] Examples of the cyclic amine 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 the aliphatic monocyclic amine include piperidine, piperazine, etc. As the aliphatic polycyclic amine, those having 6 to 10 carbon atoms are preferable, 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.

[0379] 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.

[0380] Further, 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.

[0381] 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 the range as above, the resist pattern shape, storage stability over time, etc. are improved.

[0382] <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, storage 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.

[0383] 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.

[0384] <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 the lithography characteristics can be improved by using it as a resin different from the component (A). As the component (F), for example, the fluorine-containing polymer compounds described in JP-A Nos. 2010-002870, 2010-032994, 2010-277043, 2011-13569, and 2011-128226 can be used. (F) More specifically as the component, a polymer having a structural unit (f1) represented by the following general formula (f1-1) can be mentioned. As this polymer, a polymer (homopolymer) consisting only of the structural unit (f1) represented by the following formula (f1-1); a copolymer of the structural unit (f1) and the structural unit (a1); a copolymer of the structural unit (f1), a structural unit derived from acrylic acid or methacrylic acid, and the structural unit (a1) is preferable, and a copolymer of the structural unit (f1) and the structural unit (a1) is more preferable. 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.

[0385]

Chemical formula

[0386] 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), Rf 102 and Rf 103 As the halogen atom, a fluorine atom is preferable. Rf 102 and Rf 103 As the alkyl group having 1 to 5 carbon atoms, the same ones as the alkyl group having 1 to 5 carbon atoms of R described above can be mentioned, and a methyl group or an ethyl group is preferable. Rf 102 and Rf103 As the alkyl halide group having 1 to 5 carbon atoms, specifically, 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 can be mentioned. 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.

[0387] In formula (f1-1), Rf 101 is an organic group containing a fluorine atom, and preferably a hydrocarbon group containing a fluorine atom. The hydrocarbon group containing a fluorine atom may be linear, branched, or cyclic, 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 increases. Among them, Rf 101 is more preferably a fluorinated hydrocarbon group having 1 to 6 carbon atoms, and particularly preferably a trifluoromethyl group, -CH2-CF3, -CH2-CF2-CF3, -CH(CF3)2, -CH2-CH2-CF3, -CH2-CH2-CF2-CF2-CF2-CF3.

[0388] (F) component's weight average molecular weight (Mw) (in terms of polystyrene conversion standard by gel permeation chromatography) is preferably from 1,000 to 50,000, more preferably from 5,000 to 40,000, and most preferably from 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. When it is above the lower limit value of this range, the water repellency of the resist film is good. (F) component's dispersity (Mw / Mn) is preferably from 1.0 to 5.0, more preferably from 1.0 to 3.0, and most preferably from 1.0 to 2.5.

[0389] In the resist composition of this 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 from 0.5 to 10 parts by mass, more preferably from 1 to 10 parts by mass, based on 100 parts by mass of the (A) component.

[0390] <Organic solvent component (S)> The resist composition of this embodiment can be produced by dissolving a resist material in an organic solvent component (hereinafter referred to as "(S) component"). In the resist composition of this 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.

[0391] Also, as the (S) component, a mixed solvent of PGMEA and a polar solvent is also preferred. The blending ratio (mass ratio) may be appropriately determined in consideration of the compatibility between PGMEA and the polar solvent, etc. As the (S) component, a mixed solvent of at least one selected from PGMEA and EL and γ-butyrolactone is also preferred. In this case, as the mixing ratio, the mass ratio of the former to the latter is preferably from 70:30 to 95:5. (S) The amount 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.

[0392] The resist composition of this embodiment may be subjected to removal of impurities and the like using a polyimide porous membrane, a polyamideimide porous membrane, or the like after dissolving the above resist material in the (S) component. 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.

[0393] The resist composition of this embodiment may contain compound (B0) as compound (C). The resist composition of this embodiment may contain the (A1) component, compound (B0), and (D) component. Alternatively, the resist composition of this embodiment may contain the (A1) component having the constitutional unit (a6) and compound (B0) component.

[0394] The resist composition of this embodiment may contain compound (D0) as compound (C). The resist composition of this embodiment may contain the (A1) component, (B) component, and compound (D0). Alternatively, the resist composition of this embodiment may contain the (A1) component having the constitutional unit (a5) and compound (D0).

[0395] The resist composition of this embodiment may contain a resin component having the constitutional unit (a0) as compound (C). The resin component may be the (A1) component. The resist composition of this embodiment may contain the (A1) component having the constitutional unit (a0b) and the (D) component. The resist composition of this embodiment may contain component (A1) having a constitutional unit (a0d) and component (B). The resist composition of this embodiment may contain component (A1) having a constitutional unit (a0b) and a constitutional unit (a0d).

[0396] The resist composition of this embodiment may contain compound (B0) and compound (D0) as compound (C). The resist composition of this embodiment may contain component (A1), compound (B0), and compound (D0).

[0397] The resist composition of this embodiment may contain a resin component having a constitutional unit (a0) and compound (B0) as compound (C). The resin component may be component (A1). The resist composition of this embodiment may contain component (A1) having a constitutional unit (a0d) and component (B0).

[0398] The resist composition of this embodiment may contain a resin component having a constitutional unit (a0) and compound (D0) as compound (C). The resin component may be component (A1). The resist composition of this embodiment may contain component (A1) having a constitutional unit (a0b) and compound (D0).

[0399] The resist composition of this embodiment may contain a resin component having a constitutional unit (a0), compound (B0), and compound (D0) as compound (C). The resin component may be component (A1). The resist composition of this embodiment may contain component (A1) having a constitutional unit (a0b), compound (B0), and compound (D0). The resist composition of this embodiment may contain component (A1) having a constitutional unit (a0d), compound (B0), and compound (D0).

[0400] The resist compositions of the above embodiments may each contain the (S) component, and may optionally contain either or both of the (E) component and the (F) component.

[0401] The resist compositions of the present embodiments described above contain a compound (C) containing a cation (C0) represented by the general formula (c0). Since the acid generator component and / or the quencher component has the cation (C0), a resist composition having good sensitivity, roughness, and resolution is realized. The reason for such an effect is presumed as follows. In the cation (C0), at least two iodine atoms with high absorption efficiency of light (for example, EUV light) to be exposed are introduced into aromatic rings, so it is considered that the generation of secondary electrons increases and the cation is decomposed efficiently. In addition, since a fluorine atom or a fluorinated alkyl group and a polar group containing an oxygen atom are present in the same aromatic ring, a decrease in the cation decomposition efficiency due to an increase in LUMO caused by the electron-donating oxygen atom-containing group can be suppressed by the fluorine atom or the fluorinated alkyl group which is an electron-withdrawing group. Furthermore, the introduction of the polar group containing an oxygen atom relaxes the increase in hydrophobicity due to the iodine atom. It is presumed that by the above-described actions acting synergistically, the sensitivity, roughness, and resolution are freed from the trade-off relationship, and all of the sensitivity, roughness, and resolution become good.

[0402] (Resist pattern formation method) The resist pattern formation method according to the second aspect of the present invention is a method having 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 formation method, for example, a resist pattern formation method performed as follows can be mentioned.

[0403] First, the resist composition of the above-described embodiment is applied onto a support using 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, for example, by exposure through a mask (mask pattern) having a predetermined pattern formed thereon 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)) treatment 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.

[0404] After the development process, preferably a rinsing process is performed. In the case of an alkali development process, water rinsing using pure water is preferred, 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-described development process.

[0405] The support is not particularly limited, and conventionally known ones can be used. For example, substrates for electronic components and those having a predetermined wiring pattern formed thereon can be mentioned. More specifically, silicon wafers, metal substrates such as copper, chromium, iron, and aluminum, and glass substrates can be mentioned. As the material for the wiring pattern, for example, copper, aluminum, nickel, gold, etc. can be used.

[0406] The wavelength used for exposure is not particularly limited, and it can be performed using radiation such as ArF excimer laser, KrF excimer laser, F2 excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray, soft X-ray, etc. The resist pattern forming method of the present embodiment is particularly useful in the method of exposing the resist film to EUV (extreme ultraviolet) or EB (electron beam) in the step of exposing the resist film.

[0407] 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 exposure (Liquid Immersion Lithography). Liquid immersion exposure 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. 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.

[0408] 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.

[0409] 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.

[0410] Examples of nitrile solvents include acetonitrile, propionitrile, valeronitrile, and butyronitrile.

[0411] Known additives can be blended 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.

[0412] 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 still 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), etc. can be mentioned.

[0413] 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. Further, they may be used in mixture with organic solvents other than those described above or water.

[0414] The rinse process (cleaning process) using the rinse liquid can be carried out by a known rinse method. Examples of the method of the 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), and the like.

[0415] According to the resist pattern forming method of the present embodiment described above, since the above-described resist composition is used, when forming a resist pattern, sensitivity, roughness, and resolution can be formed into good resist patterns without being traded off with each other.

[0416] 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 (below the detection limit of the measuring device).

[0417] (Compound) The compound according to the third aspect of the present invention is a compound represented by the following general formula (m0) (hereinafter, also referred to as "compound (M0)").

[0418] [Chemical formula] [In the formula, Y 0 represents a polar group containing an oxygen atom. Rf 0 represents a fluorine atom or a fluorinated alkyl group. R 01 represents a substituent (excluding polar groups containing oxygen atoms, fluorine atoms, and fluorinated alkyl groups), and R 02 and R 03 each independently represents a substituent (excluding iodine atoms). L 01 and L 02 each independently represents a hydrogen atom or a substituent, and L 01 and L 02may be bonded to each other to form a ring together with the sulfur atom in the formula. n0 and m0 each independently represent an integer of 1 to 4, p01 represents an integer of 0 to 3, and n0 + m0 + p01 ≤ 5. p02 and p03 each independently represent an integer of 0 to 3, q01 and q02 each independently represent an integer of 1 to 4, p02 + q01 ≤ 4, and p03 + q02 ≤ 4. When m0 is an integer of 2 or more, two or more Y 0 may be the same as or different from each other. When n0 is an integer of 2 or more, two or more Rf 0 may be the same as or different from each other. When p01 is an integer of 2 or more, two or more R 01 may be the same as or different from each other. When p02 is an integer of 2 or more, two or more R 02 may be the same as or different from each other. When p03 is an integer of 2 or more, two or more R 03 may be the same as or different from each other.]

[0419] {Cation part} The cation part is the same as the cation (C0) represented by the general formula (c0).

[0420] {Anion part} X - is a counter anion. X - Examples of X include those listed as the anion part of the compound represented by the general formula (b0), those listed as the anion part of the compound represented by the general formula (d0), those listed as the anion part of the structural unit represented by the general formula (a0-1), and the like.

[0421] Specific examples of the compound (M0) include those exemplified as the above compounds (B0) and (D0) respectively.

[0422] {Method for producing the compound} The compound (M0) can be produced by appropriately combining known methods as in the <Compound synthesis example> shown in the following [Examples]. The compound (M0) can be produced, for example, by the following reactions (I) to (II).

[0423] <<Reaction (I)>> Compound (a) and compound (b) are reacted in the presence of trifluoromethanesulfonic anhydride to obtain compound (M0-a). Then, an anion exchange of the methanol solution of compound (M0-a) is performed with a strong base ion exchange resin to obtain compound (M0-b).

[0424] [Chemical formula] [In the formula, Y 0 , Rf 0 , R 01 , R 02 , R 03 , L 01 , L 02 , n0, m0, p01, p02, q01, p03 and q02 are the same as those in the above formula (m0), respectively.]

[0425] The temperature condition of reaction (I) is not particularly limited, for example, it is about -80 to 50 °C, preferably -40 to 10 °C, and more preferably -20 to 0 °C. The reaction time of reaction (I) is not particularly limited, for example, it is about 1 to 72 hours, preferably 1 to 24 hours.

[0426] Examples of the reaction solvent for reaction (I) include dichloromethane, dichloroethane, chloroform, tetrahydrofuran, N,N-dimethylformamide, acetonitrile, propionitrile, N,N'-dimethylacetamide, dimethyl sulfoxide, etc.

[0427] <<Reaction (II)>> Compound (M0) represented by the general formula (m0) is obtained by a salt exchange reaction between compound (M0-b) and compound (c).

[0428] [Chemical formula] [In the formula, Y 0 , Rf 0 , R01 , R 02 , R 03 , L 01 , L 02 , n0, m0, p01, p02, q01, p03 and q02 are the same as those in the formula (m0), respectively.

[0429] The temperature condition of the reaction (II) is not particularly limited, and is, for example, about -10 to 120 °C, preferably 0 to 100 °C, and more preferably 10 to 70 °C. The reaction time of the reaction (V) is not particularly limited, and is, for example, about 1 to 72 hours, preferably 1 to 24 hours.

[0430] Examples of the reaction solvent used in the reaction (II) include dichloromethane, dichloroethane, chloroform, tetrahydrofuran, N,N-dimethylformamide, acetonitrile, propionitrile, N,N'-dimethylacetamide, dimethyl sulfoxide and the like.

[0431] In the method for producing the above-mentioned compound (M0), after each reaction is completed, the compound in the reaction solution may be isolated and purified. For isolation and purification, conventionally known methods can be used. For example, concentration, solvent extraction, distillation, crystallization, recrystallization, chromatography and the like can be appropriately combined and used. The structure of the compound obtained as described above can be identified by general organic analysis methods such as 1H-nuclear magnetic resonance (NMR) spectroscopy and 13C-NMR spectroscopy. As the raw materials used in each step, commercially available ones may be used, or synthesized ones may be used.

[0432] The compound of the present embodiment described above can be used in the production of the resist composition according to the first aspect. Further, the compound of the present embodiment can be used as an acid generator according to the fourth aspect and an acid diffusion control agent according to the fifth aspect described later. Further, the compound of the present embodiment can be used in the production of a polymer compound according to the sixth aspect described later.

[0433] (Acid generator) The acid generator according to the fourth aspect of the present invention contains the compound (M0). The compound (M0) as the acid generator is the same as the compound (B0). The acid generator of this embodiment can be used in the production of the resist composition according to the first aspect.

[0434] (Acid diffusion controller) The acid diffusion controller according to the fifth aspect of the present invention contains the compound (M0). The compound (M0) as the acid diffusion controller is the same as the compound (D0). The acid diffusion controller of this embodiment can be used in the production of the resist composition according to the first aspect.

[0435] (Polymer compound) The polymer compound according to the sixth aspect of the present invention has a structural unit (a0) represented by the general formula (a0-1). The structural unit (a0) is the same as that described above. The structural unit (a0) may be the structural unit (a0b) or the structural unit (a0d). The polymer compound contains either one or both of the structural unit (a0b) and the structural unit (a0d). The polymer compound of this embodiment can be used in the production of the resist composition according to the first aspect.

Examples

[0436] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

[0437] <Synthesis example of compound> (Synthesis example of compound (B0-1)) ≪Synthesis of compound (B0-b-1)≫ In a 200 mL three-necked flask, compound B0-a-1 (10.0 g, 0.09 mol), tert-butyldiphenylchlorosilane (27.5 g, 0.11 mol), imidazole (7.3 g, 0.11 mol), and dimethylformamide (DMF) (40 g) were added, and then stirred at room temperature for 24 hours. Heptane (225 g) was added to the reaction solution, and after washing 5 times with a mixed solution of methanol and ultrapure water (70 g), the solvent was distilled off from the organic layer and dried under reduced pressure to obtain 32.9 g of compound (B0-b-1). In the following formula, Ph represents a phenyl group and tBu represents a tert-butyl group.

[0438]

Chemical formula

[0439] ≪Synthesis of compound (B0-1-b)≫ 20.0 g of compound (B0-c-1), 17.0 g of compound (B0-b-1), and 14.9 g of trifluoromethanesulfonic anhydride were stirred in 200 g of dichloromethane (DCM) at -20 °C for 2 hours. 300 g of an aqueous sodium hydrogen carbonate solution was added, and after stirring at room temperature, the organic layer was recovered and the solvent was distilled off. The obtained residue was purified by silica gel column chromatography to obtain 32 g of compound (B0-1-a). A methanol solution of 28 g of compound (B0-1-a) was anion-exchanged with a strong base ion exchange resin to obtain a solution of compound (B0-1-b).

[0440]

Chemical formula

[0441] ≪Synthesis of compound (B0-1)≫ To the solution of compound (B0-1-b), 20.5 g of compound (B0-d-1), 330 g of dichloromethane, and 160 g of ultrapure water were added, and stirred at room temperature. The organic layer was recovered, washed repeatedly with water, and then the solvent was distilled off and dried to obtain 30.8 g of compound (B0-1).

[0442] [Chemical formula]

[0443] (Synthesis Examples of Compounds (B0-2) to (B0-6)) ≪Synthesis of Compounds (B0-b-2) to (B0-b-4)≫ Compounds (B0-b-2) to (B0-b-4) were each synthesized in the same manner as in the above ≪Synthesis of Compound (B0-b-1)≫, except that compounds (B0-a-2) to (B0-b-4) were used instead of compound (B0-a-1).

[0444] [Chemical formula]

[0445] ≪Synthesis of Compounds (B0-2-b) to (B0-4-b), (B0-6-b)≫ Compounds (B0-2-b) to (B0-4-b), (B0-6-b) were each synthesized in the same manner as in the above ≪Synthesis of Compound (B0-1-b)≫, except that compounds (B0-b-2) to (B0-b-4), (B0-b-6) were used instead of compound (B0-b-1).

[0446] [Chemical formula]

[0447] [Chemical formula]

[0448] ≪Synthesis of Compound (B0-5-b)≫ Compound (B0-5-b) was synthesized in the same manner as in the above ≪Synthesis of Compound (B0-1-b)≫, except that compound (B0-c-5) was used instead of compound (B0-c-1).

[0449] [Chemical formula]

[0450] ≪Synthesis of Compounds (B0-2) to (B0-6)≫ Compounds (B0-2) to (B0-6) were synthesized in the same manner as the above ≪Synthesis of Compound (B0-1)≫, except that compounds (B0-2-b) to (B0-6-b) were used instead of compound (B0-1-b).

[0451]

Chemical Structure

[0452] (Synthesis of Compounds (B0-7) to (B0-9)) Compounds (B0-7) to (B0-9) were synthesized in the same manner as the above (Synthesis of Compound (B0-1)), except that compounds (B0-d-7) to (B0-d-9) were used instead of compound (B0-d-1).

[0453]

Chemical Structure

[0454]

Chemical Structure

[0455] (Synthesis Examples of Compounds (D0-1), (D0-4) to (D0-7)) Compounds (D0-1) and (D0-4) to (D0-7) were obtained in the same manner as the above (Synthesis Example of Compound (B0-1)), except that compounds (D0-d-1) and (D0-d-4) to (D0-d-7) were used instead of compound (B0-d-1).

[0456]

Chemical Structure

[0457]

Chemical Structure

[0458] (Synthesis Examples of Compounds (D0-2) and (D0-3)) Compounds (D0-2) and (D0-3) were synthesized in the same manner as in the above-mentioned ≪Synthesis of Compound (B0-1)≫, except that compound (B0-4-b) and (B0-6-b) were used in place of compound (B0-1-b), respectively, and compound (D0-d-1) was used in place of compound (B0-d-1).

[0459] [Chemical Formula]

[0460] NMR measurements were performed on the obtained compounds (B0-1) to (B0-9), (D0-1) to (B0-6), and their structures were identified based on the analysis results shown below.

[0461] Compound (B0-1): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 9.00 (1H, brs), 8.14 - 8.10 (4H, m), 8.07, (1H, d), 7.51 - 7.47 (4H, m), 7.36 (1H, d), 6.95 - 6.77 (3H, m), 5.13 (2H, t).

[0462] Compound (B0-2): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 9.45 (1H, brs), 8.16 - 8.12 (5H, m), 7.55 - 7.51 (4H, m), 7.37 (1H, d), 7.15 - 7.13 (1H, m), 7.00 - 6.98 (1H, m), 6.59 - 6.57 (1H, m), 5.15 (2H, t).

[0463] Compound (B0-3): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 9.58 (1H, brs), 8.21 - 8.17 (4H, m), 8.11, (1H, d), 7.57 - 7.53 (4H, m), 7.33 (1H, d), 6.64 (2H, d), 5.20 (2H, t).

[0464] Compound (B0-4): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 9.68, 8.18 - 8.14 (4H, m), 8.09 (1H, d), 7.55 - 7.51 (4H, m), 7.35 (1H, d), 7.31 (1H, d), 7.18 - 7.16 (1H, m), 6.65 - 6.73 (1H, m), 5.12 (2H, t).

[0465] Compound (B0-5): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 8.99 (1H, brs), 8.12 (1H, d), 8.05 (2H, s), 7.87 (2H, d), 7.36 (1H, d), 7.30 - 7.28 (2H, m), 6.95 - 6.83 (3H, m), 5.11 (2H, t).

[0466] Compound (B0-6): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 8.12 (1H, d), 8.08 - 8.04 (4H, m), 7.45 - 7.41 (4H, m), 7.35 (1H, d), 7.10 - 7.04 (2H, m), 6.95 - 6.93 (1H, m), 5.10 (2H, t), 3.83 (3H, s).

[0467] Compound (B0-7): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 9.00 (1H, brs), 8.14 - 8.10 (4H, m), 7.51 - 7.47 (4H, m), 6.91 - 6.83 (3H, m), 4.96 (2H, t), 2.13 - 2.11 (4H, m), 2.01 - 1.99 (2H, m), 1.90 - 1.75 (9H, m).

[0468] Compound (B0-8): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 9.04 (1H, brs), 8.20 - 8.11 (5H, m), 7.86 - 7.84 (1H, m), 7.61 (1H, dd), 7.50 - 7.46 (5H, m), 6.80 - 6.70 (3H, m), 6.18 (1H, d), 5.92 (1H, d), 2.02 (3H, s).

[0469] Compound (B0-9): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 9.01 (1H, brs), 8.59 (1H, s), 8.30 (1H, s), 8.18 - 8.14 (4H, m), 8.11 - 8.09 (2H, d), 7.73 - 7.71 (2H, d), 7.49 - 7.45 (4H, m), 6.85 - 6.77 (4H, m), 6.10 - 6.06 (1H, m), 5.51 - 5.57 (1H, m), 4.67 (2H, t).

[0470] Compound (D0-1): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 11.01 (1H, brs), 8.14 - 8.10 (4H, m), 7.64 - 7.62 (1H, m), 7.51 - 7.47 (4H, m), 7.12 - 7.08 (1H, m), 6.85 - 6.77 (3H, m), 6.58 - 6.52 (2H, m).

[0471] Compound (D0-2): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 11.90 (1H, brs), 8.18 - 8.14 (4H, m), 7.63 - 7.61 (1H, m), 7.55 - 7.51 (4H, m), 7.35 (1H, d), 7.18 - 7.16 (1H, m), 7.10 - 7.06 (1H, m), 6.73 - 6.71 (1H, m), 6.60 - 6.54 (2H, m)).

[0472] Compound (D0-3): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 11.55 (1H, brs), 8.10 - 8.06 (4H, m), 7.66 - 7.64 (1H, m), 7.50 - 7.46 (4H, m), 7.12 - 7.04 (3H, m), 6.95 - 6.93 (1H, m), 6.62 - 6.56 (2H, m), 3.83 (3H, s).

[0473] Compound (D0-4): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 10.01 (1H, brs), 8.14 - 8.10 (4H, m), 8.00 (1H, d), 7.51 - 7.47 (4H, m), 7.36 (1H, d), 6.95 - 6.87 (3H, m).

[0474] Compound (D0-5): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 12.00 (2H, brs), 8.14 - 8.07 (5H, m), 7.84 (1H, d), 7.51 - 7.47 (4H, m), 6.90 - 6.82 (3H, m).

[0475] Compound (D0-6): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 9.00 (1H, brs), 8.14 - 8.10 (4H, m), 7.51 - 7.47 (4H, m), 6.85 - 6.77 (3H, m), 4.93 (1H, t), 4.37 (2H, t), 2.48 - 2.44 (2H, m), 1.90 - 1.84 (2H, m), 1.78 - 1.74 (10H, m).

[0476] Compound (D0-7): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 9.10 (1H, brs), 8.14 - 8.10 (4H, m), 7.51 - 7.47 (4H, m), 6.99 - 6.89 (3H, m), 3.96 (1H, d), 3.44 (1H, d), 2.23 - 2.04 (3H, m), 1.77 - 1.55 (4H, m), 0.96 (6H, s).

[0477] <Production of Polymer Compound> (Synthesis of Polymer Compound (A1-4)) A dropping solution was prepared by dissolving 16.0 g of Compound (B0-8), 10.6 g of Compound (M10-pre), 20.0 g of Compound (M1-1), and 3.5 g of 2,2'-Azobis(2-methylpropionitrile) (V-601) as a polymerization initiator in 35 g of methyl ethyl ketone (MEK) and 35 g of cyclohexanone. 40 g of MEK was added to a three-necked flask equipped with a thermometer, a reflux condenser, and a nitrogen inlet tube, heated to 80 °C under a nitrogen atmosphere, and the above dropping solution was added dropwise over 4 hours. After completion of the dropping, 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, 140 g of methanol and 9.8 g of acetic acid were added to the obtained reaction solution, and the mixture was stirred at room temperature for 16 hours under a nitrogen atmosphere. After completion of the reaction, the obtained reaction solution was precipitated with 600 g of heptane, and the precipitate was washed. The obtained white solid was filtered and dried under reduced pressure overnight to obtain a polymer compound (A1-4).

[0478]

Chemical Structure

[0479] (Synthesis of Polymer Compound (A1-5)) A polymer compound (A1-5) was synthesized in the same manner as in the above (Synthesis of Polymer Compound (A1-4)), except that Compound (B0-9) was used instead of Compound (B0-8).

[0480] (Synthesis of Polymer Compounds (A1-1) to (A1-3)) Polymer compounds (A1-1) to (A1-3) were synthesized respectively in the same manner as in the synthesis of polymer compound (A1-1), except that the compounds used in the polymerization reaction were changed.

[0481] Polymer compounds (A1-1) to (A1-5) are shown below. In the following formulae, l, m, and n represent the composition ratios (molar ratios) of the respective constitutional units.

[0482]

Chemical Structure

[0483] For the obtained polymer compounds (A1-1) to (A1-5), the weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) were determined by GPC measurement (in terms of standard polystyrene), respectively. Also, for the polymer compounds (A1-1) to (A1-5), the copolymer composition ratio (the ratio of each structural unit in the structural formula (molar ratio)) was determined by carbon-13 nuclear magnetic resonance spectrum (600 MHz, 13 C-NMR). The results are shown below.

[0484] Polymer compound (A1-1): weight average molecular weight (Mw) 5900, molecular weight distribution (Mw / Mn) 1.51, l / m = 50 / 50. Polymer compound (A1-2): weight average molecular weight (Mw) 6100, molecular weight distribution (Mw / Mn) 1.52, l / m / n = 40 / 10 / 50. Polymer compound (A1-3): weight average molecular weight (Mw) 5900, molecular weight distribution (Mw / Mn) 1.48, l / m = 40 / 30 / 30. Polymer compound (A1-4): weight average molecular weight (Mw) 8100, molecular weight distribution (Mw / Mn) 1.56, l / m = 30 / 60 / 10. Polymer compound (A1-5): weight average molecular weight (Mw) 8400, molecular weight distribution (Mw / Mn) 1.55, l / m = 30 / 60 / 10.

[0485] <Preparation of Resist Composition> (Examples 1 to 19, Comparative Examples 1 to 5) By mixing and dissolving the components shown in Tables 1 to 2, the resist compositions of each example were prepared, respectively.

[0486]

Table 1

[0487]

Table 2

[0488] In Tables 1 to 2, each abbreviation has the following meaning. The numerical values in [ ] are the compounding amounts (parts by mass). (A1)-1 to (A1)-5: The above polymer compounds (A1-1) to (A1-5).

[0489] (B0)-1 to (B0)-7: An acid generator composed of the above compounds (B0-1) to (B0-7). (B1)-1 to (B1)-4: An acid generator composed of the following compounds (B1-1) to (B1-4).

[0490]

Chemical formula

[0491] (D0)-1 to (D0)-7: An acid diffusion control agent composed of the above compounds (D0-1) to (D0-7).

[0492] (D1)-1 to (D1)-2: An acid diffusion control agent composed of compounds represented by the following chemical formulas (D1-1) to (D1-2).

[0493]

Chemical formula

[0494] (S)-1: A mixed solvent of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 60 / 40 (mass ratio).

[0495] <Formation of resist pattern> Step of forming a resist film: On an 8-inch silicon substrate subjected to hexamethyldisilazane (HMDS) treatment, each resist composition 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.

[0496] Step of exposing the resist film: Next, using an electron beam lithography apparatus JEOL-JBX-9300FS (manufactured by JEOL Ltd.), the resist film was exposed (drawn) at an acceleration voltage of 100 kV to form a contact hole pattern (CH pattern) with a target size of a pitch width of 46 nm and a hole width of 26 nm. Thereafter, a post-exposure bake (PEB) treatment was performed at 100°C for 60 seconds.

[0497] Step of developing the exposed resist film: Next, at 23°C, using an aqueous solution of 2.38 mass% tetramethylammonium hydroxide (TMAH) "NMD-3" (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.), alkali development was performed for 60 seconds. Thereafter, water rinsing was performed for 15 seconds using pure water. As a result, a CH pattern with a pitch width of 46 nm and a hole width of 26 nm was formed.

[0498] [Evaluation of the optimum exposure dose (Eop)] The optimum exposure dose Eop (μC / cm 2 ) at which the CH pattern of the target size is formed by the above <Formation of resist pattern> was determined. This is shown in Tables 3 to 4 as "Eop (μC / cm 2 )".

[0499] [Evaluation of the in-plane uniformity (CDU) of pattern dimensions] Regarding the CH pattern formed by the above <Formation of resist pattern>, using a length-measuring SEM (scanning electron microscope, acceleration voltage 500 V, trade name: CG5000, manufactured by Hitachi High-Technologies Corporation), observation was made from above the CH pattern, 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 determined. The results are shown in Tables 3 to 4 as "CDU (nm)". The 3σ thus obtained means that the smaller the value, the higher the dimensional (CD) uniformity of the plurality of holes formed in the resist film.

[0500] [Evaluation of fine resolution] The resolution at the optimum exposure dose (Eop) at which the above CH pattern is formed. Specifically, when forming the CH pattern by gradually decreasing the exposure dose from the optimum exposure dose (Eop), the hole diameter (nm) of the pattern to be resolved was determined using a scanning electron microscope S-9380 (manufactured by Hitachi High-Technologies Corporation). The results are shown in Tables 3 to 4 as "resolvability (nm)".

[0501]

Table 3

[0502]

Table 4

[0503] As shown in Tables 3 to 4, it was confirmed that the resist compositions of Examples 1 to 19 were all good in terms of sensitivity, CDU, and resolvability. On the other hand, the resist compositions of Comparative Examples 2, 4, and 5 had good resolvability, but were inferior in sensitivity and CDU compared to the resist compositions of the examples. The resist compositions of Comparative Examples 1 and 3 were inferior in all of sensitivity, CDU, and resolvability compared to the resist compositions of the examples.

Claims

1. A resist composition that generates an acid upon exposure and whose solubility in a developer changes due to the action of the acid, containing a compound containing a cation (C0) represented by the following general formula (c0), resist composition. 【Chemical Formula 1】 [In the formula, Y ０ represents a polar group containing an oxygen atom. Rf ０ represents a fluorine atom or a fluorinated alkyl group. R ０１ represents a substituent (excluding polar groups containing an oxygen atom, fluorine atoms, and fluorinated alkyl groups), and R ０２ and R ０３ each independently represent a substituent (excluding iodine atoms). L ０１ and L ０２ each independently represent a hydrogen atom or a substituent, and L ０１ and L ０２ may be bonded to each other to form a ring together with the sulfur atom in the formula. n0 and m0 each independently represent an integer from 1 to 4, p01 represents an integer from 0 to 3, and n0 + m0 + p01 ≤ 5. p02 and p03 each independently represent an integer from 0 to 3, q01 and q02 each independently represent an integer from 1 to 4, p02 + q01 ≤ 4, and p03 + q02 ≤ 4. When m0 is an integer of 2 or more, two or more Ys ０ may be the same as or different from each other. When n0 is an integer of 2 or more, two or more Rfs ０ may be the same as or different from each other. When p01 is an integer of 2 or more, two or more Rs ０１ may be the same as or different from each other. When p02 is an integer of 2 or more, two or more Rs ０２ may be the same as or different from each other. When p03 is an integer of 2 or more, two or more Rs ０３ may be the same as or different from each other. ]

2. A resin component (A1) whose solubility in a developer changes due to the action of an acid, and an acid generator component (B) that generates an acid upon exposure, The acid generator component (B) contains a compound represented by the following general formula (b0). The resist composition according to claim 1. 【Chemical Formula 2】 [In the formula, M ｂ＋ is the cation (C0). Xb － is a counter anion.]

3. A resin component (A1) whose solubility in a developer changes by the action of an acid, and an acid diffusion control agent component (D) that controls the diffusion of the acid generated by exposure, and contains The acid diffusion control agent component (D) contains a compound represented by the following general formula (d0). The resist composition according to claim 1. 【Chemical Formula 3】 [In the formula, M ｄ＋ is the cation (C0). Xd － is a counter anion.]

4. Contains a resin component (A1) whose solubility in a developer changes by 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. 【Chemical Formula 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. M ａ＋ is the cation (C0). Rx ０－ is a group containing an anion.]

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

6. A compound represented by the following general formula (m0). [Chemical Formula 5] [In the formula, Y ０ represents a polar group containing an oxygen atom. Rf ０ represents a fluorine atom or a fluorinated alkyl group. R ０１ represents a substituent (excluding a polar group containing an oxygen atom, a fluorine atom, and a fluorinated alkyl group), and R ０２ and R ０３ each independently represent a substituent (excluding an iodine atom). L ０１ and L ０２ each independently represent a hydrogen atom or a substituent, and L ０１ and L ０２ may be bonded to each other to form a ring together with the sulfur atom in the formula. n0 and m0 each independently represent an integer from 1 to 4, p01 represents an integer from 0 to 3, and n0 + m0 + p01 ≤ 5. p02 and p03 each independently represent an integer from 0 to 3, q01 and q02 each independently represent an integer from 1 to 4, p02 + q01 ≤ 4, and p03 + q02 ≤ 4. When m0 is an integer of 2 or more, two or more Y ０ may be the same as or different from each other. When n0 is an integer of 2 or more, two or more Rf ０ may be the same as or different from each other. When p01 is an integer of 2 or more, two or more R ０１ may be the same as or different from each other. When p02 is an integer of 2 or more, two or more R ０２ may be the same as or different from each other. When p03 is an integer of 2 or more, two or more R ０３ may be the same as or different from each other. ]

7. An acid generator containing the compound according to claim 6.

8. An acid diffusion control agent containing the compound according to claim 6.

Images