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

Abstract

To provide a resist composition and the like, which is improved in roughness, resolution and the like while maintaining good sensitivity.SOLUTION: A resist composition generates an acid upon light exposure, changes its solubility in a developer by the action of an acid, and comprises a resin component (A1). The resin component (A1) has a constituent unit (a0) derived from a compound represented by formula (a0-m). In the formula (a0-m), W0 represents a polymerizable group-containing group; Ar01 and Ar02 represent aromatic rings; L0 represents a single bond or a divalent linking group; Ra01 and Ra02 represent substituents other than iodine; Rx0 represents a hydrocarbon group; m01 and m02 represent integers of 0 or more; m01+m02≥1; n01 and n02 represent integers of 0 or more; r01 and r02 represent 0 or 1; r01+r02≥1; k0 represents 0 or 1; r02+k0=1; m represents an integer of 1 or more; and Mm+ represents an m-valent cation.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resist composition, a method for forming a resist pattern, a compound, a polymer compound, 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 (the energy is increased).

[0003] Resist materials are required to have lithography characteristics such as sensitivity to these exposure light sources and resolution capable of reproducing patterns with fine dimensions. As a resist material that satisfies such requirements, a chemically amplified resist composition containing a base material component whose solubility in a developer changes 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 regarded as one factor that greatly affects the lithography characteristics. On the other hand, a chemically amplified resist composition having 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 has been proposed.

[0005] In addition, in a chemically amplified resist composition, it has also been proposed to introduce an acid generator component as a structural unit containing an acid generating group into a polymer compound (see, for example, Patent Document 1). Such a polymer compound has both a function as an acid generator and a function as a base material component.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] As the miniaturization of resist patterns progresses, for example, in lithography using EUV (extreme ultraviolet light) or EB (electron beam), the formation of fine patterns with a size of several tens of nm is targeted. Along with such miniaturization of resist patterns, it has become an issue to improve lithography such as roughness and resolution while maintaining good sensitivity. However, these lithography characteristics are usually in a trade-off relationship, and when any one of the characteristics is improved, the other characteristics tend to deteriorate. In the resist composition, it is required to improve both roughness and resolution while maintaining good sensitivity.

[0008] The present invention has been made in view of the above circumstances, and an object thereof is to provide a resist composition having improved roughness and resolution while maintaining good sensitivity, a resist pattern forming method using the resist composition, a compound, a polymer compound, and an acid diffusion control agent that can be 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 resin component (A1) whose solubility in a developer changes by the action of the acid, and the resin component (A1) has a structural unit (a0) derived from a compound represented by the following general formula (a0-m).

[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 (a0-m).

[0013]

Chemical formula

[0014] The fourth aspect of the present invention is a polymer compound having a structural unit derived from the compound according to the third aspect.

[0015] The 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 improved roughness and resolution while maintaining good sensitivity, a resist pattern forming method using the resist composition, a polymer compound, a compound, and an acid diffusion control agent that can be used in the resist composition.

Embodiments for Carrying Out the Invention

[0017] In this specification and the claims, “aliphatic” is a relative concept with respect to aromatic, and is defined to mean a group, compound, etc. having no aromaticity. “Alkyl group” includes linear, branched, and cyclic monovalent saturated hydrocarbon groups unless otherwise specified. The same applies to the alkyl group in an alkoxy group. “Alkylene group” includes linear, branched, and cyclic divalent saturated hydrocarbon groups unless otherwise specified. "Halogen atom" includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. "Constituent unit" means a monomer unit (monomeric unit) that constitutes a polymer compound (resin, polymer, copolymer). When it is described that "it may have a substituent", it includes both the case where a hydrogen atom (-H) is substituted with a monovalent group and the case where a methylene group (-CH2-) is substituted with a divalent group. "Exposure" is a concept that includes all irradiations of radiation.

[0018] "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), and the like. 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] "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, further decarboxylation reaction occurs, whereby the bond between the acid-dissociable group and the atom adjacent to the acid-dissociable group can be cleaved. The acid-dissociable group constituting the acid-decomposable group needs to be a group having a lower polarity than the polar group generated by the dissociation of the acid-dissociable group. Thereby, when the acid-dissociable group is dissociated by the action of an acid, a polar group having a higher polarity than the acid-dissociable group is generated and the polarity increases. As a result, the polarity of the whole of the 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] "Base material component" refers to an organic compound having film-forming ability. The organic compounds used as base material components are roughly classified into non-polymers and polymers. As non-polymers, those having a molecular weight of 500 or more and less than 4000 are usually used. In the following, when referring to a "low molecular compound", it means a non-polymer having a molecular weight of 500 or more and less than 4000. As polymers, those having a molecular weight of 1000 or more are usually used. In the following, when referring to "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] "Derived structural unit" means a structural unit formed by the cleavage of a multiple bond between carbon atoms, for example, an ethylenic double bond. The "acrylate" may have a hydrogen atom bonded to the α-position carbon atom substituted with a substituent. The substituent (R αx ) is an atom or group other than a hydrogen atom. Further, it shall include itaconic acid diesters in which the substituent (R αx ) is substituted with a substituent containing an ester bond, and α-hydroxyacrylates 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 acrylate is, unless otherwise specified, the carbon atom to which the carbonyl group of acrylic acid is bonded. Hereinafter, the acrylate in which the hydrogen atom bonded to the α-position carbon atom is substituted with a substituent may be referred to as an α-substituted acrylate.

[0022] The term "derivative" refers to a concept that includes those in which the 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 their derivatives. Examples of such derivatives include those in which the hydrogen atom of the hydroxyl group of the target compound, where the hydrogen atom at the α-position may be 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, where the hydrogen atom at the α-position may be substituted with a substituent, and the like. Note that 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 R αx the same as those described above.

[0023] In this specification and the claims of this patent, depending on the structure represented by a chemical formula, there may be asymmetric carbons, 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 of this embodiment generates an acid upon exposure, and the solubility in a developer changes due to the action of the acid. Such a resist composition contains a base material component (A) (hereinafter also referred to as the "(A) component") whose solubility in a developer changes due to the action of an acid. The base material component contains a resin component (A1) whose solubility in a developer changes due to the action of an acid, and the resin component (A1) has a structural unit (a0) derived from a compound represented by the general formula (a0-m).

[0025] In the resist composition of this embodiment, the (A) component may generate an acid upon exposure, or an additive component blended separately from the (A) component may generate an acid upon exposure. Specifically, the resist composition of this embodiment may further contain an acid generator component (B) that generates an acid upon exposure (hereinafter referred to as "component (B)"); (2) component (A) may be a component that generates an acid upon exposure; or (3) component (A) may be a component that generates an acid upon exposure and further contains component (B). That is, in the cases of (2) and (3) above, 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 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 component (A1) described later is a resin that generates an acid upon exposure and whose solubility in a developer changes due to the action of the acid. As such a resin, a polymer compound having a structural unit that generates an acid upon exposure can be used. As the structural unit that generates an acid upon exposure, structural unit (a5) described later may 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, in the exposed portion of the resist film, for example, an acid is generated from component (B), and the solubility of component (A) in the developer changes due to the action of the acid. On the other hand, in the unexposed portion of the resist film, the solubility of 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 a positive type, the exposed portion of the resist film is dissolved and removed to form a positive type resist pattern, and when the resist composition is a negative type, the unexposed portion of the resist film is dissolved and removed to form a negative type resist pattern.

[0027] The resist composition of this embodiment may be a positive type resist composition or a negative type resist composition. Further, the resist composition of this embodiment may be for an alkali development process that uses an alkali developer for the development treatment during resist pattern formation, or may be for a solvent development process that uses a developer containing an organic solvent (organic-based developer) for the development treatment.

[0028] <Base material component (A)> In the resist composition of the present embodiment, as the component (A), it is preferable to use a resin component (A1) (hereinafter also referred to as the “(A1) component”) whose solubility in a developer changes by the action of an acid. By using the (A1) component, since the polarity of the base material 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.

[0029] In the resist composition of the present embodiment, the component (A) may be used alone or in combination of two or more.

[0030] ·Regarding the (A1) component The (A1) component is a resin component whose solubility in a developer changes by the action of an acid. The (A1) component has a structural unit (a0) derived from the compound represented by the general formula (a0-m). 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).

[0031] ≪Structural unit (a0)≫ The structural unit (a0) is a structural unit derived from the compound represented by the following general formula (a0-m).

[0032]

Chemical formula

[0033] {Anion part} In the formula (a0-m), W 0 The polymerizable group-containing group in is a group containing a polymerizable group. The "polymerizable group" is a group that enables a compound having the polymerizable group to polymerize by radical polymerization or the like, and for example, refers to a group containing a multiple bond between carbon atoms such as an ethylenic double bond. Examples of the polymerizable group include a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, a fluorovinyl group, a difluorovinyl group, a trifluorovinyl group, a difluorotrifluoromethylvinyl group, a trifluoroallyl group, a perfluoroallyl group, a trifluoromethylacryloyl group, a nonafluorobutylacryloyl group, a vinyl ether group, a fluorine-containing vinyl ether group, an allyl ether group, a fluorine-containing allyl ether group, a styryl group, a vinylnaphthyl group, a fluorine-containing styryl group, a fluorine-containing vinylnaphthyl group, a norbornyl group, a fluorine-containing norbornyl group, a silyl group, and the like. Among them, as the polymerizable group, a vinyl group is preferable.

[0034] The polymerizable group-containing group may be a group composed only of polymerizable groups or a group composed of a polymerizable group and other groups other than the polymerizable group. Examples of the other groups 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 formula: C(RX 11 )(RX 1 2)=C(RX 13 )-Ya x0 -. In the above formula, RX 11 , RX 12 and RX 13 each independently represent 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 represents a single bond or a divalent linking group. Examples of the divalent linking group in Ya x0 include a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a heteroatom, and the like. Examples of the divalent linking group in Ya x0 include an ester bond (-C(=O)-O-), an oxycarbonyl group (-O-C(=O)-), an ether bond (-O-), -C(=O)-NH-, -NH-C(=O)-, a linear or branched alkylene group, or a combination thereof.

[0035] In the above formula (a0-m), the aromatic rings in Ar 01 and Ar 02 are not particularly limited as long as they are cyclic conjugated systems 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 ring, naphthalene ring, anthracene ring, and phenanthrene ring; aromatic heterocyclic rings in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a heteroatom, and the like. Examples of the heteroatom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, a nitrogen atom, and the like. Specific examples of the aromatic heterocyclic ring include a pyridine ring, a thiophene ring, and the like. Ar01 and Ar 02 The aromatic ring in is preferably an aromatic hydrocarbon ring, more preferably a benzene ring or a naphthalene ring, and even more preferably a benzene ring.

[0036] In the formula (a0-m), L 0 Examples of the divalent linking group in include the same groups as the divalent linking group Ya in the formula (a10-1) described below. x1 L 0 As the divalent linking group in, a divalent linking group containing a heteroatom is preferred. 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 or an acyl group), -S-, -S(=O)2-, -S(=O)2-O-, general formula -Y 21 -O-Y 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-O-Y 21 -,, -O-Y 21 -,, -O-Y 21 -C(=O)-, -[Y 21 -C(=O)-O] m” -Y 22 -,, -Y 21 -O-C(=O)-Y 22 - or -Y 21 -S(=O)2-O-Y 22 -represented groups [wherein Y 21 and Y 22 are each independently a divalent hydrocarbon group which may have a substituent, and m” is an integer of 1 to 3.], etc. Among them, as the divalent linking group in L 0 , -S(=O)2-, -C(=O)-, or -O-Y 21 -C(=O)- is preferred. The above Y 21As the [group], a linear or branched alkylene group or a linear or branched halogenated alkylene group is preferable. The alkylene group and the halogenated alkylene group are preferably linear, preferably having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 or 2 carbon atoms. The halogenated alkylene group is preferably a fluorinated alkylene group.

[0037] L 0 As the divalent linking group in [it], a divalent linking group represented by the following general formula (L0) is preferable.

[0038] [Chemical formula] [In the formula, L 01 represents a single bond or a divalent linking group containing a heteroatom, L 02 represents a single bond or an alkylene group which may have a substituent, L 03 represents a single bond or a divalent linking group containing a heteroatom.]

[0039] In the formula (L0), as the divalent linking group containing a heteroatom in L 01 -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 or an acyl group), -S-, -S(=O)2-, -S(=O)2-O-, etc. can be mentioned. L 01 As [it], a single bond, -O-, or -S(=O)2- is preferable.

[0040] In the formula (L0), L 02The alkylene group which may have a substituent in [description] may be linear or branched, but a linear one is preferred. The linear alkylene group which may have a substituent preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, still more preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms. The branched alkylene group which may have a substituent preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, and still more preferably 2 or 3 carbon atoms. L 02 Examples of the substituent which the alkylene group in [description] may have include a halogen atom, a hydroxy group, an amino group, a cyano group, a nitro group, etc. As the halogen atom, a fluorine atom is preferred. L 02 is preferably a single bond, an alkylene group having 1 to 3 carbon atoms, or a halogenated alkylene group having 1 to 3 carbon atoms, and more preferably a single bond, a methylene group, or a difluoromethylene group.

[0041] In the formula (L0), L 03 Examples of the divalent linking group containing a hetero atom in [description] 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 or an acyl group.), -S-, -S(=O)2-, -S(=O)2-O-, etc. L 03 is preferably a single bond, -O-, -C(=O)-, or -S(=O)2-.

[0042] Ra 01 and Ra 02 The substituent in [description] is a substituent that replaces the hydrogen atom of the aromatic ring in Ar 01 and Ar 02 and is not particularly limited. Examples of the substituent include an alkyl group, a halogenated alkyl group, a halogen atom other than an iodine atom, a hydroxy group, an amino group, a cyano group, an acyl group, an alkoxy group, etc. The alkyl group, halogenated alkyl group, acyl group, and alkoxy group are preferably linear or branched. The linear alkyl group, linear halogenated alkyl group, linear acyl group, and linear alkoxy group preferably have 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, still more preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms. The branched alkyl group, branched halogenated alkyl group, branched acyl group, and branched alkoxy group preferably have 3 to 5 carbon atoms, and more preferably 3 or 4 carbon atoms. The halogen atom is preferably a fluorine atom or a bromine atom. The halogenated alkyl group is preferably a fluorinated alkyl group.

[0043] Rx 0 The hydrocarbon group which may have a substituent in Rx may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Examples of the hydrocarbon group include those similar to the hydrocarbon group in Ra’ in the general formula (a1-r-1) described below. 3 are the same as those of the hydrocarbon group in Rx 0 is preferably an aliphatic hydrocarbon group which may have a substituent, more preferably a linear or branched aliphatic hydrocarbon group which may have a substituent, and still more preferably a linear or branched alkyl group which may have a substituent. The linear alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and still more preferably 1 or 2 carbon atoms. The branched alkyl group preferably has 3 to 6 carbon atoms, more preferably 3 or 4 carbon atoms, and still more preferably 3 carbon atoms. Rx 0 The hydrocarbon group in Rx may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an amino group, a cyano group, and the like. Among them, Rx 0A linear or branched halogenated alkyl group is preferred, a linear or branched fluorinated alkyl group is more preferred, and a linear fluorinated alkyl group is even more preferred. The linear halogenated alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, even more preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms. The branched halogenated alkyl group preferably has 3 to 5 carbon atoms, more preferably 3 or 4 carbon atoms. Rx 0 is preferably a trifluoromethyl group.

[0044] In the formula (a0-m), m01 and m02 are preferably integers from 0 to 4, more preferably integers from 0 to 3. Ar 01 When Ar is a benzene ring, m01 is an integer from 0 to 4, preferably an integer from 0 to 3. Ar 01 When Ar is a naphthalene ring, m01 is an integer from 0 to 7, preferably an integer from 0 to 4, more preferably an integer from 0 to 3. Ar 02 When Ar is a benzene ring, m02 is an integer from 0 to 5, preferably an integer from 0 to 4, more preferably an integer from 0 to 3. Ar 02 When Ar is a naphthalene ring, m02 is an integer from 0 to 7, preferably an integer from 0 to 4, more preferably an integer from 0 to 3. From the viewpoint of improving sensitivity, it is preferable that m01 + m02 ≥ 2, and more preferably m01 + m02 ≥ 3. Since sensitivity, roughness, and resolution are all likely to be good, 1 ≤ m01 + m02 ≤ 5 is preferable, 2 ≤ m01 + m02 ≤ 5 is more preferable, and 2 ≤ m01 + m02 ≤ 4 is even more preferable.

[0045] In the formula (a0-m), n01 and n02 are preferably integers from 0 to 3, more preferably integers from 0 to 2, even more preferably 0 or 1, and particularly preferably 0.

[0046] The structural unit (a0) is preferably a structural unit represented by any of the following general formulas (a0-1) to (a0-3).

[0047] [Chemical formula]

[0048] [Chemical formula]

[0049] [Chemical formula] [In the formula, R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. Ar 01 and Ar 02 each independently represents an aromatic ring. L 0 represents a single bond or a divalent linking group. Ra 01 and Ra 02 each independently represents a substituent other than iodine. Rx 0 represents a hydrocarbon group which may have a substituent. m01 and m02 each independently represent an integer of 0 or more as long as the valence allows, and m01 + m02 ≧ 1. n01 and n02 each independently represent an integer of 0 or more as long as the valence allows. r01 and r02 each independently represent 0 or 1, and r01 + r02 ≧ 1. k0 represents 0 or 1, and r02 + k0 = 1. When n01 is an integer of 2 or more, two or more Ra 01 may be the same as or different from each other. When n02 is an integer of 2 or more, two or more Ra 01 may be the same as or different from each other. A 0 represents an oxygen atom or -NH-. m03 represents an integer of 1 or more as long as the valence allows. m is an integer of 1 or more, and M m+ is an m-valent cation.]

[0050] In the formulas (a0-1) to (a0-3), Ar 01 , Ar 02 , L 0 , Ra 01 , Ra 02 , Rx 0, m01, m02, n01, n02, r01, r02, k0, m, and M m+ is the same as that in the formula (a0 - m), respectively.

[0051] In the formulas (a0 - 1) to (a0 - 3), the alkyl group having 1 to 5 carbon atoms in 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 in R is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. As 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.

[0052] In the formula (a0 - 2), A 0 is preferably an oxygen atom.

[0053] In the formula (a0 - 3), m03 is preferably an integer of 1 to 5, more preferably an integer of 1 to 4, and even more preferably an integer of 1 to 3. When Ar 02 is a benzene ring, m03 is an integer of 1 to 5, preferably an integer of 1 to 4, and more preferably an integer of 1 to 3. When Ar 02 is a naphthalene ring, m03 is an integer of 1 to 7, preferably an integer of 1 to 4, and more preferably an integer of 1 to 3.

[0054] The structural unit represented by the formula (a0 - 1) is preferably a structural unit represented by the following general formula (a0 - 11) or (a0 - 12).

[0055]

Chemical formula

[0056] R, Ar in the formulas (a0-11) and (a0-12) 01 , Ar 02 , L 0 , Ra 01 , Ra 02 , Rx 0 , m01, m02, n01, n02, m, and M m+ are the same as those in the formula (a0-1), respectively.

[0057] In the formula (a0-12), m012 is preferably an integer of 1 to 5, more preferably an integer of 1 to 4, and even more preferably an integer of 1 to 3. When Ar 01 is a benzene ring, m012 is an integer of 1 to 4, and an integer of 1 to 3 is preferable. When Ar 01 is a naphthalene ring, m012 is an integer of 1 to 6, an integer of 1 to 4 is preferable, and an integer of 1 to 3 is more preferable.

[0058] The structural unit represented by the formula (a0-2) is preferably a structural unit represented by the following general formula (a0-21) or (a0-22).

[0059] [Chemical formula] [In the formula, R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. Ar 01 and Ar 02 each independently represents an aromatic ring. L 0 represents a single bond or a divalent linking group. Ra 01 and Ra 02 each independently represents a substituent other than iodine. Rx 0 represents a hydrocarbon group which may have a substituent. m01 and m02 each independently represent an integer of 0 or more as long as the valence allows, and m01 + m02 ≧ 1. n01 and n02 each independently represent an integer of 0 or more as long as the valence allows. r01 and r02 each independently represent 0 or 1, and r01 + r02 ≧ 1. k0 represents 0 or 1, and r02 + k0 = 1. When n01 is an integer of 2 or more, two or more Ra 01 may be the same as or different from each other. When n02 is an integer of 2 or more, two or more Ra 01 may be the same as or different from each other. A 0 represents an oxygen atom or -NH-. m012 represents an integer of 1 or more as long as the valence allows. m is an integer of 1 or more, and M m+ is an m-valent cation.]

[0060] R, Ar 01 , Ar 02 , L 0 , Ra 01 , Ra 02 , Rx 0 , m01, m02, n01, n02, A 0 , m, and M m+ are the same as those in the formula (a0-2), respectively. In the formula (a0-22), m012 is the same as that in the formula (a0-12).

[0061] In the (a0-12) and (a0-22), Rx 0 is preferably a linear or branched halogenated alkyl group, and more preferably a linear or branched fluorinated alkyl group. Rx 0 When Rx is a halogenated alkyl group, the sensitivity is likely to be improved. Rx 0 The halogenated alkyl group in Rx preferably has 1 to 3 carbon atoms, and more preferably 1 or 2 carbon atoms. Rx 0 is preferably a trifluoromethyl group.

[0062] Specific examples of the anion part of the structural unit (a0) represented by the formula (a0-1) 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.

[0063]

Chemical formula

[0064]

Chemical formula

[0065]

Chemical formula

[0066]

Chemical formula

[0067]

Chemical formula

[0068] Specific examples of the anion part of the structural unit (a0) represented by the formula (a0-2) 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.

[0069] [Chemical formula]

[0070] [Chemical formula]

[0071] Specific examples of the anion part of the structural unit (a0) represented by the formula (a0-3) 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.

[0072] [Chemical formula]

[0073] {Cation part} In the formula (a0-m), M m+ represents an m-valent cation. m is an integer of 1 or more. As the cation in M m+ , an organic cation is preferable, and an onium cation is more preferable. Among them, M m+ is preferably a sulfonium cation or an iodonium cation.

[0074] Preferred cation parts ((M m+ )) 1 / m ) include organic cations represented by the following general formulas (ca-1) to (ca-3), respectively.

[0075] [Chemical formula] [In the formula, R 201 ~R 207Each independently represents an aryl group which may have a substituent, an alkyl group which may have a substituent, or an alkenyl group which may have a substituent. R 201 ~R 203 、R 206 ~R 207 may be bonded to each other to form a ring together with the sulfur atom in the formula. R 208 ~R 209 Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 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. L 201 represents -C(=O)- or -C(=O)-O-. ]

[0076] In the above general formulas (ca-1) to (ca-3), R 201 ~R 207 Examples of the aryl group include unsubstituted aryl groups having 6 to 20 carbon atoms, and a phenyl group and a naphthyl group are preferred. R 201 ~R 207 Examples of the alkyl group include linear or cyclic alkyl groups, and those having 1 to 30 carbon atoms are preferred. R 201 ~R 207 Examples of the alkenyl group preferably have 2 to 10 carbon atoms. R 201 ~R 207 、およびR 210 Examples of the substituent which may be possessed by 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 each of the following general formulas (ca-r-1) to (ca-r-7), and the like.

[0077]

Chemical formula

[0078] 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. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

[0079] 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 of the aromatic hydrocarbon group in include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or an aromatic heterocyclic ring in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms. Examples of the heteroatom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, a nitrogen atom, etc. R’ 201 Specific examples of the aromatic hydrocarbon group in include a group obtained by removing one hydrogen atom from the aromatic ring (aryl group: 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, 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.

[0080] R' 201 The cyclic aliphatic hydrocarbon group in 201 includes aliphatic hydrocarbon groups containing a ring in the structure. Examples of the aliphatic hydrocarbon group containing a ring in this structure include alicyclic hydrocarbon groups (groups obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, groups in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group, and the like. 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 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 one or more hydrogen atoms from a polycycloalkane is preferable, 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 preferable.

[0081] Among them, as the cyclic aliphatic hydrocarbon group in R' 201 a group obtained by removing one or more hydrogen atoms from a monocycloalkane or a polycycloalkane is preferable, a group obtained by removing one hydrogen atom from a polycycloalkane is more preferable, an adamantyl group and a norbornyl group are particularly preferable, and an adamantyl group is most preferable.

[0082] 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 preferred, and 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 preferred, and specifically, alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-; alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2CH2-, etc. may be mentioned. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0083] Also, R’ 201 The cyclic hydrocarbon group in may contain a hetero atom such as a heterocyclic ring. Specifically, lactone-containing cyclic groups represented by the above general formulas (a2-r-1) to (a2-r-7), -SO2-containing cyclic groups represented by the following general formulas (b5-r-1) to (b5-r-4), and heterocyclic groups represented by the following chemical formulas (r-hr-1) to (r-hr-16) may be mentioned.

[0084]

Chemical formula

[0085] R’ 201 Examples of the substituent in the cyclic group of 201 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 a group in which some or all of the hydrogen atoms of an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group, are substituted with the above halogen atom. The carbonyl group as a substituent is a group that substitutes the methylene group (-CH2-) constituting the cyclic hydrocarbon group.

[0086] A chain alkyl group which may have a substituent: R’ 201 The chain alkyl group of 201 may be either linear or branched. As the linear alkyl group, it 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 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.

[0087] A chain-like alkenyl group which may have a substituent: R’ 201 As the chain-like alkenyl group of 201 , 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. Examples of the linear alkenyl group include a vinyl group, a propenyl group (allyl group), a butenyl group, etc. Examples of the branched alkenyl group include a 1-methylvinyl group, a 2-methylvinyl group, a 1-methylpropenyl group, a 2-methylpropenyl group, etc. Among the above, as the chain-like 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.

[0088] R’ 201 Examples of the substituent in the chain-like alkyl group or alkenyl group of 201 include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and the cyclic group in the above R’ 201 etc.

[0089] R’ 201 The 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, also includes those similar to the acid dissociable group represented by the above formula (a1-r-2).

[0090] Among them, R’ 201 preferably has a cyclic group which may have a substituent, and more preferably is 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; the lactone-containing cyclic groups respectively represented by the above general formulas (a2-r-1) to (a2-r-7); the -SO2-containing cyclic groups respectively represented by the following general formulas (b5-r-1) to (b5-r-4), etc. are preferred.

[0091] 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, or 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 ring formed, 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 ring formed 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, and the like.

[0092] R 208 ~R 209 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and when it is an alkyl group, they may be bonded to each other to form a ring.

[0093] 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. Examples of the aryl group in R 210 include an unsubstituted aryl group having 6 to 20 carbon atoms, and preferably a phenyl group and a naphthyl group. Examples of the alkyl group in R 210 include a linear or cyclic alkyl group having preferably 1 to 30 carbon atoms. Examples of the alkenyl group in R 210 preferably have 2 to 10 carbon atoms. R210 In the formula, as the -SO2-containing cyclic group, any group can be used without particular limitation. Specifically, groups represented by the following general formulas (b5-r-1) to (b5-r-4) can be mentioned, and a "-SO2-containing polycyclic group" is preferred, and a group represented by the general formula (b5-r-1) is more preferred.

[0094]

Chemical formula

[0095] 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, an oxygen atom or a sulfur atom. As B”, an alkylene group having 1 to 5 carbon atoms or -O- is preferred, an alkylene group having 1 to 5 carbon atoms is more preferred, and a methylene group is even more preferred.

[0096] In the general formulas (b5-r-1) to (b5-r-4), Rb’ 51 are each independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR”, -OC(=O)R”, a hydroxyalkyl group or a cyano group, and among them, each is preferably independently a hydrogen atom or a cyano group.

[0097] Specific examples of the groups represented by the general formulas (b5-r-1) to (b5-r-4) are given below. "Ac" in the formula represents an acetyl group.

[0098] [Chemistry]

[0099] [Chemistry]

[0100] [Chemistry]

[0101] Specific examples of the preferred cation represented by the formula (ca-1) include cations represented by the following chemical formulas, respectively.

[0102] [Chemistry]

[0103] [Chemistry]

[0104] [Chemistry] [In the formula, g1, g2, and g3 represent the number of repetitions, g1 is an integer from 1 to 5, g2 is an integer from 0 to 20, and g3 is an integer from 0 to 20.]

[0105] [Chemistry]

[0106] [Chemistry]

[0107] [Chemistry] [In the formula, R” 201is a hydrogen atom or a substituent, and examples of the substituent include the above R 201 ~R 207 , and R 210 ~R 212 are the same as those listed as the substituents that may be possessed.]

[0108]

Chemical formula

[0109] Specific examples of the suitable cation represented by the formula (ca-2) include a diphenyliodonium cation, a bis(4-tert-butylphenyl)iodonium cation, and the like.

[0110] Specific examples of the suitable cation represented by the formula (ca-3) include cations respectively represented by the following formulas (ca-3-1) to (ca-3-6).

[0111]

Chemical formula

[0112] As the cation part ((M m+ )) 1 / m ) in the formula (a0-m), a sulfonium cation is preferable, 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 cations respectively represented by the formulas (ca-1-1) to (ca-1-84) are particularly preferable. Particularly from the viewpoint of high sensitivity, as the suitable cation represented by the formula (ca-1), those having an electron-withdrawing group such as a fluorine atom, a fluorinated alkyl group, and a sulfonyl group as a substituent are preferable. For example, cations selected from the group consisting of cations respectively represented by the above chemical formulas (ca-1-44), (ca-1-71) to (ca-1-84) are particularly preferable.

[0113] Specific examples of the constitutional unit (a0) are shown below, but are not limited thereto.

[0114] [Chem.]

[0115] [Chem.]

[0116] (A1) component's constituent unit (a0) may be one type or two or more types. The proportion of the constituent unit (a6) in the (A1) component is preferably 2 to 20 mol%, more preferably 2 to 15 mol%, still more preferably 2 to 10 mol%, and particularly preferably 3 to 8 mol% with respect to the total (100 mol%) of all the constituent units constituting the (A1) component. When the proportion of the constituent unit (a0) is equal to or higher than the lower limit value of the above-mentioned preferred range, it is easy to improve both sensitivity and roughness while maintaining good sensitivity. On the other hand, when it is equal to or lower than the upper limit value of the above-mentioned preferred range, it is easy to balance with other constituent units.

[0117] ≪Constituent unit (a1)≫ The constituent unit (a1) is a constituent unit containing an acid-dissociable group whose polarity increases by the action of an acid. The (A1) component preferably has the constituent unit (a1).

[0118] 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.

[0119] Acetal-type acid-dissociable group: Examples of the acid dissociable group that protects a carboxy group or a hydroxy group among the polar groups include an acid dissociable group represented by the following general formula (a1-r-1) (hereinafter sometimes referred to as an "acetal-type acid dissociable group").

[0120] [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.]

[0121] 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. When Ra’ 1 or Ra’ 2 is an alkyl group, examples of the alkyl group include the same alkyl groups as those listed as substituents that may be bonded to the α-carbon atom in the description of the above α-substituted acrylic acid ester, and an alkyl group having 1 to 5 carbon atoms is preferable. 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 preferable, and a methyl group is particularly preferable.

[0122] In formula (a1-r-1), examples of the hydrocarbon group of Ra’ 3 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, 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 preferable, and a methyl group or an ethyl group is more preferable.

[0123] The branched alkyl group 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 preferable.

[0124] Ra’ 3 When Ra’ is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group. As the aliphatic hydrocarbon group that is a monocyclic group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferable. 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 preferable. 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.

[0125] Ra’ 3 When the cyclic hydrocarbon group of Ra’ is 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 it may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, still more preferably 6 to 15, and particularly preferably 6 to 12. 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. 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 in 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.

[0126] Ra’ 3 The cyclic hydrocarbon group in may have a substituent. Examples of this 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 chain 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, RP2 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, R P1 and R P2 Some or all of the hydrogen atoms of the linear saturated hydrocarbon group, aliphatic cyclic saturated hydrocarbon group, and aromatic hydrocarbon group may be substituted with fluorine atoms. The above aliphatic cyclic hydrocarbon group may have one or more of the above substituents alone, or may have one or more of a plurality of types of the above substituents. Examples of the monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, and the like. 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, phenanthrene, etc.

[0127] Ra’ 3 When Ra’ 1 is bonded to either Ra’ 2 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, a tetrahydrofuranyl group, and the like.

[0128] Tertiary alkyl ester type acid dissociable group: Among the above polar groups, examples of the acid dissociable group that protects the carboxy group include acid dissociable groups represented by the following general formula (a1-r-2). Among the acid dissociable groups represented by the following formula (a1-r-2), those composed of an alkyl group may be hereinafter referred to as "tertiary alkyl ester type acid dissociable groups" for convenience.

[0129] [Chemical formula] [In the formula, Ra’ 4 ~Ra’ 6 are each a hydrocarbon group, and Ra’ 5 , Ra’ 6 may be bonded to each other to form a ring.]

[0130] 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 Examples of the linear or branched alkyl group and cyclic hydrocarbon group (aliphatic hydrocarbon group which is a monocyclic group, aliphatic hydrocarbon group which is a polycyclic group, aromatic hydrocarbon group) in are the same as those of the above Ra’ 3 Ra’ 4 The linear or cyclic alkenyl group in is preferably an alkenyl group having 2 to 10 carbon atoms. Ra’ 5 , Ra’ 6 Examples of the hydrocarbon group of are the same as those of the above Ra’ 3

[0131] Ra’ 5 When Ra’ 6 and Ra’ On the other hand, Ra’ 4 ~Ra’ 6 ​​When they are hydrocarbon groups that are not bonded to each other and are independent, a group represented by the following general formula (a1-r2-4) is preferably mentioned.

[0132] [Chemical formula] [In formula (a1-r2-1), Ra’ 10 represents a linear or branched alkyl group having 1 to 12 carbon atoms, which may be partially substituted with a halogen atom or a heteroatom-containing group. Ra’ 11 represents a group that forms an aliphatic cyclic group together with the carbon atom to which Ra’ 10 is bonded. In formula (a1-r2-2), Ya is a carbon atom. Xa is a group that forms a cyclic hydrocarbon group together with Ya. Some or all of the hydrogen atoms of this cyclic hydrocarbon group may be substituted. Ra 101 ~Ra 103 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. Ra 104 is an aromatic hydrocarbon group that may have a substituent. In formula (a1-r2-4), Ra’ 12 and Ra’ 13 each independently represents 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 that may have a substituent. * represents a bond (the same applies hereinafter).]

[0133] In the above formula (a1-r2-1), Ra’ 10 is a linear or branched alkyl group having 1 to 12 carbon atoms, which may be partially substituted with a halogen atom or a heteroatom-containing group.

[0134] Ra’ 10 In the case of a linear alkyl group, the number of carbon atoms is 1 to 12, preferably 1 to 10, and particularly preferably 1 to 5. Ra’ 10 In the case of a branched alkyl group, examples thereof include those similar to the above Ra’ 3 and the like.

[0135] Ra’ 10 The alkyl group in 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. Further, 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 herein include an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the heteroatom-containing group include (-O-), -C(=O)-O-, -O-C(=O)-, -C(=O)-, -O-C(=O)-O-, -C(=O)-NH-, -NH-, -S-, -S(=O)2-, -S(=O)2-O- and the like.

[0136] In formula (a1-r2-1), Ra’ 11 (The aliphatic cyclic group formed together with the carbon atom to which Ra’ 10 is bonded) is preferably a group exemplified as the monocyclic group or polycyclic group of Ra’ 3 in formula (a1-r-1), which is an aliphatic hydrocarbon group (alicyclic hydrocarbon group). Among them, a monocyclic alicyclic hydrocarbon group is preferable, and specifically, a cyclopentyl group and a cyclohexyl group are more preferable.

[0137] In formula (a1-r2-2), examples of the cyclic hydrocarbon group formed by Xa and Ya together include a group obtained by further removing one or more hydrogen atoms from the cyclic monovalent hydrocarbon group (aliphatic hydrocarbon group) of Ra’ 3 in the above formula (a1-r-1). The cyclic hydrocarbon group formed by Xa together with Ya may have a substituent. Examples of this substituent include the same substituents as those that the cyclic hydrocarbon group in the above Ra’ 3 may have. In formula (a1-r2-2), examples of the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms in Ra 101 ~Ra 103 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 Ra 2,6 ~Ra 3,7 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; polycyclic aliphatic saturated hydrocarbon groups such as a bicyclo[2.2.2]octanyl group, a tricyclo[5.2.1.0 3,6 .0 2,7 decanyl group, a tricyclo[3.3.1.1 101 decanyl group, a tetracyclo[6.2.1.1 103 ~Ra 101 dodecanyl group, an adamantyl group, and the like.

[0138] Among them, from the viewpoint of ease of synthesis, Ra 103 ~Ra x5 are preferably a hydrogen atom or a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms, and among them, a hydrogen atom, a methyl group, and an ethyl group are more preferable, and a hydrogen atom is particularly preferable.

[0139] Examples of the substituent that the chain saturated hydrocarbon group or the aliphatic cyclic saturated hydrocarbon group represented by the above Ra 101 ~Ra 103 ~Ra 3Examples of the group containing a carbon-carbon double bond formed by two or more of them bonding to 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, and a cyclopentylideneethenyl group are preferable.

[0140] In formula (a1-r2-3), the aliphatic cyclic group formed by Xaa together with Yaa is the Ra' in formula (a1-r-1) 3 The group exemplified as the aliphatic hydrocarbon group which is a monocyclic group or a polycyclic group is preferable. In formula (a1-r2-3), Ra 104 Examples of the aromatic hydrocarbon group in Ra include a group obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring having 5 to 30 carbon atoms. Among them, Ra 104 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 or naphthalene, and most preferably a group obtained by removing one or more hydrogen atoms from benzene.

[0141] Examples of the substituent that Ra in formula (a1-r2-3) 104 may have include, for example, a methyl group, an ethyl group, a propyl group, a hydroxy group, a carboxy group, a halogen atom, an alkoxy group (such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc.), an alkyloxycarbonyl group, and the like.

[0142] In formula (a1-r2-4), Ra' 12 and Ra' 13 are each independently a monovalent chain-like saturated hydrocarbon group having 1 to 10 carbon atoms. Ra' 12 and Ra' 13In the case of a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms, examples of the above Ra 101 ~Ra 103 include the same ones as the monovalent linear saturated hydrocarbon groups having 1 to 10 carbon atoms. Some or all of the hydrogen atoms of this linear saturated hydrocarbon group may be substituted. Ra’ 12 and Ra’ 13 are preferably alkyl groups having 1 to 5 carbon atoms, more preferably alkyl groups having 1 to 5 carbon atoms, still more preferably methyl and ethyl groups, and particularly preferably a methyl group. When the linear saturated hydrocarbon group represented by the above Ra’ 12 and Ra’ 13 is substituted, examples of the substituent include the same groups as the above Ra x5 .

[0143] In formula (a1-r2-4), Ra’ 14 is a hydrocarbon group which may have a substituent. Examples of the hydrocarbon group in Ra’ 14 include linear or branched alkyl groups or cyclic hydrocarbon groups.

[0144] Ra’ 14 The linear alkyl group in preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably 1 or 2 carbon atoms. Specifically, examples include methyl, ethyl, n-propyl, n-butyl, n-pentyl groups, etc. Among these, methyl, ethyl or n-butyl groups are preferred, and methyl or ethyl groups are more preferred.

[0145] Ra’ 14 The branched alkyl group in preferably has 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms. Specifically, examples include isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, 1,1-diethylpropyl, 2,2-dimethylbutyl groups, etc., and isopropyl is preferred.

[0146] Ra’14 When it is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group. As the aliphatic hydrocarbon group which is a monocyclic group, a group obtained by removing one hydrogen atom from monocycloalkane is 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 aliphatic hydrocarbon group which is a polycyclic group, a group obtained by removing one hydrogen atom from polycycloalkane is preferable. As the polycycloalkane, those having 7 to 12 carbon atoms are preferable, and specifically, adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 decane, tetracyclododecane and the like can be mentioned.

[0147] Ra’ 14 Examples of the aromatic hydrocarbon group in Ra’ 104 are the same as those of the aromatic hydrocarbon group in Ra. Among them, Ra’ 14 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 naphthalene or anthracene, and most preferably a group obtained by removing one or more hydrogen atoms from naphthalene. Ra’ 14 Examples of the substituent that Ra’ 104 may have are the same as those of the substituent that Ra

[0148] When Ra’ 14 in the formula (a1-r2-4) is a naphthyl group, the position bonding to the tertiary carbon atom in the formula (a1-r2-4) may be either the 1-position or the 2-position of the naphthyl group. Ra’ 14When it is an anthryl group, the position bonding to the tertiary carbon atom in the formula (a1-r2-4) may be any of the 1-position, 2-position, or 9-position of the anthryl group.

[0149] Specific examples of the group represented by the formula (a1-r2-1) are given below.

[0150]

Chemical formula

[0151]

Chemical formula

[0152]

Chemical formula

[0153] Specific examples of the group represented by the formula (a1-r2-2) are given below.

[0154]

Chemical formula

[0155]

Chemical formula

[0156]

Chemical formula

[0157] Specific examples of the group represented by the formula (a1-r2-3) are given below.

[0158]

Chemical formula

[0159] Specific examples of the group represented by the formula (a1-r2-4) are given below.

[0160] [Chemical formula]

[0161] Tertiary alkyloxycarbonyl acid-dissociable group: Among the above polar groups, examples of the acid-dissociable group that protects the hydroxyl group include 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).

[0162] [Chemical formula] [In the formula, Ra’ 7 ~Ra’ 9 are each an alkyl group.]

[0163] In formula (a1-r-3), Ra’ 7 ~Ra’ 9 are each preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. Also, the total number of carbon atoms of each alkyl group is preferably 3 to 7, more preferably 3 to 5, and most preferably 3 to 4.

[0164] Secondary alkyl ester type acid-dissociable group: Among the above polar groups, examples of the acid-dissociable group that protects the carboxy group include the acid-dissociable group represented by the following general formula (a1-r-4).

[0165] [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’ 12is 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’

[0166] In the formula, Ra’ 10 and Ra’ 12 The hydrocarbon groups in are the same as those of the above Ra’ 3 can be mentioned. In the formula, Ra’ 11a and Ra’ 11b The alkyl groups in are the same as those of the alkyl groups in the above Ra’ 1 can be mentioned. In the formula, Ra’ 10 and Ra’ 12 The hydrocarbon groups in, and Ra’ 11a and Ra’ 11b The alkyl groups in may have substituents. Examples of such substituents include the above-mentioned Ra x5 etc.

[0167] Ra’ 10 and Ra’ 11a or Ra’ 11b and Ra’ The ring formed by bonding with each other may be a polycyclic ring or a monocyclic ring, and may be an alicyclic ring or an aromatic ring.

[0168] Ra’ 10 and Ra’ 11a or Ra’ 11b Among the above, the rings formed by bonding with each other preferably include 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.

[0169] Ra’ 10 and Ra’ 11a or Ra’ 11b The ring formed by the combination of them with each other may be a condensed ring. Specific examples of the condensed ring include indane and the like.

[0170] Ra’ 10 and Ra’ 11a or Ra’ 11b The ring formed by the combination of them with each other may have a substituent. Examples of this substituent include Ra x5 and the like.

[0171] Ra’ 11a or Ra’ 11b and Ra’ 12 and Ra’ 10 and Ra’ 11a or Ra’ 11b and the like, which are the same as the rings formed by the combination of them with each other.

[0172] Specific examples of the group represented by the formula (a1-r-4) are given below.

[0173]

Chemical formula

[0174] Examples of the structural unit (a1) include a structural unit derived from an acrylate 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 by a substituent containing the acid-decomposable group, a structural unit in which at least a part of the hydrogen atoms in the -C(=O)-OH of a structural unit derived from vinylbenzoic acid or a vinylbenzoic acid derivative is protected by a substituent containing the acid-decomposable group, and the like.

[0175] As the constitutional unit (a1), among the above, a constitutional 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 constitutional unit (a1) include constitutional units represented by the following general formula (a1-1), (a1-2), or (a1-3).

[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. 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 n a2 +1-valent hydrocarbon group. n a2 is an integer of 1 to 3. Ra 2 is an acid dissociable group represented by the above general formula (a1-r-1) or (a1-r-3). 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 above general formula (a1-r-1), (a1-r-2), or (a1-r-4). Rz 01 is an alkyl group, a halogen atom, a halogenated alkyl group, a hydroxy group, or an alkoxy group. q is an integer of 0 to 3. n is an integer of 0 or more. However, n ≦ q × 2 + 4.]

[0177] In the formulas (a1-1) to (a1-3), 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 alkyl halide group having 1 to 5 carbon atoms is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. As the halogen atom, a fluorine atom is particularly preferable. Preferably, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms. From the viewpoint of easy availability in industry, a hydrogen atom or a methyl group is most preferable.

[0178] In the formula (a1-1), Va 1 The divalent hydrocarbon group in may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0179] 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 its structure.

[0180] 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 preferable. 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-chain aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, still more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. As the branched-chain aliphatic hydrocarbon group, a branched-chain alkylene group is preferred. Specifically, 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 preferred.

[0181] 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-chain aliphatic hydrocarbon group, and a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched-chain aliphatic hydrocarbon group. Examples of the linear or branched-chain aliphatic hydrocarbon group are the same as those of the linear aliphatic hydrocarbon group or the branched-chain aliphatic hydrocarbon group described above. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be polycyclic or monocyclic. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferred. The monocycloalkane preferably has 3 to 6 carbon atoms, and specifically, cyclopentane, cyclohexane, etc. may be mentioned. As the polycyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a polycycloalkane is preferred, and the polycycloalkane preferably has 7 to 12 carbon atoms, and specifically, adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 decane, tetracyclododecane, etc. may be mentioned.

[0182] Va 1 The aromatic hydrocarbon group as the divalent hydrocarbon group in is a hydrocarbon group having an aromatic ring. Such an aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30 carbon atoms, still more preferably 5 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, and most preferably 6 to 12 carbon atoms. However, the number of carbon atoms does not include the number of carbon atoms in the substituent. Specific examples of the aromatic ring of the aromatic hydrocarbon group include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene; and aromatic heterocyclic rings in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a heteroatom. Examples of the heteroatom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic hydrocarbon group include a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring (arylene group); a group in which one hydrogen atom of a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring (aryl group) is substituted with an alkylene group (for example, a group obtained by further removing one hydrogen atom from the aryl group in an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, and a 2-naphthylethyl group). The number of carbon atoms of the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0183] 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.

[0184] In the formula (a1-2), Wa 1 n in a2 The +1-valent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group 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 above n a2 The +1-valent is preferably divalent to tetravalent, and more preferably divalent or trivalent. In the formula (a1-2), Ra 2 is preferably an acid dissociable group represented by the above general formula (a1-r-1).

[0185] In the formula (a1-3), Ya 001 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 001 is preferably an ester bond [-C(=O)-O-, -O-C(=O)-], an ether bond (-O-), a linear or branched alkylene group, an aromatic hydrocarbon group or a combination thereof, or a single bond. The number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4, and particularly preferably 1 to 3. Among these, Ya 001As the group, 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 even more preferable.

[0186] In the formula (a1-3), Ya 01 The divalent linking group in 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. Ya 01 Among these, Ya is preferably an ester bond [-C(=O)-O-, -O-C(=O)-], an ether bond (-O-), a linear or branched alkylene group, an aromatic hydrocarbon group, a combination thereof, or a single bond. Among these, Ya 01 As the group, 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 even more preferable.

[0187] In the formula (a1-3), Rax 01 is preferably an acid dissociable group represented by the above general formula (a1-r-2) or (a1-r-4). Among these, an acid dissociable group represented by the general formula (a1-r-2) is more preferable, and a group represented by the general formula (a1-r2-1) is even more preferable.

[0188] In the formula (a1-3), Rz 01 The alkyl group, halogenated alkyl group, and alkoxy group in preferably have 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, even more preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms. The alkyl group, 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, an iodine atom, or a bromine atom is preferable, and a fluorine atom is more preferable. Rz01 is preferably an alkoxy group or a hydroxy group, more preferably a hydroxy group.

[0189] 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; 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 six hydrogen atoms of the naphthalene may be substituted with hydroxy groups. Also, in the naphthalene, Ya 001 , -Ya 01 -C(=O)-O-Ra 01 groups, and the substitution positions of the hydroxy groups are not particularly limited.

[0190] Specific examples of the constitutional unit (a1) are shown below. In the following formulas, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0191]

Chemical formula

[0192]

Chemical formula

[0193]

Chemical formula

[0194]

Chemical formula

[0195] [Chemical]

[0196] [Chemical]

[0197] [Chemical]

[0198] [Chemical]

[0199] [Chemical]

[0200] In the following formulas, R α represents a hydrogen atom, a methyl group or a trifluoromethyl group. Rz represents a hydrogen atom, an alkyl group, a halogen atom, a halogenated alkyl group, a hydroxy group, or an alkoxy group.

[0201] [Chemical]

[0202] [Chemical]

[0203] [Chemical]

[0204] [Chemical]

[0205] [Chemical formula]

[0206] (A1) The structural unit (a1) it has may be one kind or two or more kinds. As the structural unit (a1), since the characteristics (sensitivity, shape, etc.) in lithography using an electron beam or EUV can be more easily enhanced, the structural unit represented by the formula (a1-1) or the structural unit represented by the formula (a1-3) is more preferable. Among them, since it is suitable for enhancing reactivity in EB or EUV, 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.

[0207] Alternatively, as the structural unit (a1), those containing the structural unit represented by the following general formula (a1-1-1) may be used.

[0208] [Chemical formula] [In the formula, Ra 1 ” is an acid dissociable group represented by the general formulas (a1-r2-1), (a1-r2-3), (a1-r2-4) or (a1-r-4). * indicates a bond.]

[0209] In the formula (a1-1-1), R, Va 1 and n a1 are the same as R, Va 1 and n a1 in the formula (a1-1).

[0210] The description of the acid dissociable group represented by the general formula (a1-r2-1), (a1-r2-3), (a1-r2-4) or (a1-r-4) is as described above. Among them, since it is suitable for enhancing reactivity in EB or EUV, it is preferable to select an acid dissociable group that is a cyclic group.

[0211] 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 preferable 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 preferable range, a balance with other structural units can be achieved, and various lithography characteristics become good.

[0212] ≪Other Structural Units≫ In addition to the above-described structural unit (a1), the component (A1) may have other structural units as necessary. Examples of other structural units include a structural unit (a10) represented by the general formula (a10-1) described later; a structural unit (a2) containing a lactone-containing cyclic group; a structural unit (a5) that generates an acid upon exposure; a structural unit (a6) having acid diffusion controllability; a structural unit (a8) derived from a compound represented by the general formula (a8-1) described later, and the like.

[0213] Structural unit (a10): The structural unit (a10) is a structural unit represented by the following general formula (a10-1).

[0214]

Chemical Formula

[0215] In the formula (a10-1), R is the same as R in the general formula (a1-1). As R, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms is preferable, and from the viewpoint of industrial availability, a hydrogen atom or a methyl group is particularly preferable.

[0216] In the formula (a10-1), Ya x1 is a single bond or a divalent linking group. In the above chemical formula, Ya x1 The divalent linking group in is not particularly limited, but examples of preferable ones include a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a hetero atom, and the like.

[0217] ·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.

[0218] ··Aliphatic hydrocarbon group The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated. Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, or an aliphatic hydrocarbon group containing a ring in the structure.

[0219] ···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 a linear alkyl group.

[0220] 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.

[0221] ···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, and a group in which the cyclic aliphatic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the 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, cyclopentane, cyclohexane, etc. are mentioned. 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, adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 decane, tetracyclododecane, etc. are mentioned.

[0222] 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, etc. 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, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and even more preferably a methoxy group or an ethoxy group. As the halogen atom as the substituent, a fluorine atom is preferable. Examples of the halogenated alkyl group as the substituent include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with the halogen atoms. In the cyclic aliphatic hydrocarbon group, some of the carbon atoms constituting the ring structure may be substituted with a substituent containing a hetero atom. Preferred examples of the substituent containing a hetero atom include -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0223] ··Aromatic hydrocarbon group The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. This aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, 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. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocyclic rings in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with hetero atoms, and the like. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocyclic ring include a pyridine ring and a thiophene ring. Specific examples of the aromatic hydrocarbon group include a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocyclic ring (arylene group or heteroarylene group); a group obtained by removing two hydrogen atoms from an aromatic compound containing two or more aromatic rings (such as biphenyl, fluorene, etc.); a group in which one hydrogen atom of a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocyclic ring (aryl group or heteroaryl group) is substituted with an alkylene group (for example, a group obtained by further removing one hydrogen atom from the aryl group in an arylalkyl group such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms of the alkylene group bonded to the aryl group or heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0224] In the aromatic hydrocarbon group, the hydrogen atoms of the aromatic hydrocarbon group may be substituted with substituents. For example, the hydrogen atoms bonded to the aromatic ring in the aromatic hydrocarbon group may be substituted with substituents. Examples of the 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.

[0225] · 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 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 1 to 3.], etc. are exemplified. 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 are the same as those 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 1 to 3, preferably 1 or 2, and more 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.

[0226] 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.

[0227] In the formula (a10-1), 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 where a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom; aromatic heterocyclic rings, etc. The hetero atom in the aromatic heterocyclic ring includes an oxygen atom, a sulfur atom, a nitrogen atom, etc. Specific examples of the aromatic heterocyclic ring include a pyridine ring, a thiophene ring, etc. The aromatic ring 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; aromatic heterocyclic rings where a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom, etc. Also, Wa x1 Examples of the aromatic hydrocarbon group in include aromatic compounds containing an aromatic ring which may have two or more substituents (for example, biphenyl, fluorene, etc.) from which (n ax1 +1) hydrogen atoms have been removed. Among the above, 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.

[0228] Wa x1 The aromatic hydrocarbon group in Wa 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, etc. The alkyl group, alkoxy group, halogen atom, and halogenated alkyl group as the substituent are the same as those exemplified 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.

[0229] In the above formula (a10-1), n ax1 is an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 5, still more preferably 1, 2 or 3, and particularly preferably 1 or 2.

[0230] Specific examples of the structural unit (a10) represented by the above 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.

[0231]

Chemical formula

[0232]

Chemical formula

[0233]

Chemical formula

[0234] 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.

[0235] Constituent unit (a2): (A1) The 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. Also, 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.

[0236] The "lactone-containing cyclic group" refers to a cyclic group containing a ring (lactone ring) containing -O-C(=O)- in its ring skeleton. Counting the lactone ring as the first ring, in the case of only the lactone ring, it is a monocyclic group, and when it further has other ring structures, 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.

[0237] [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).]

[0238] In the general formulas (a2-r-1) to (a2-r-7), Ra’ 21As the alkyl group in [reference], 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 [reference], an alkoxy group having 1 to 6 carbon atoms is preferable. The alkoxy group is preferably linear or branched. Specifically, the groups in which the alkyl groups mentioned as the alkyl group in the above Ra’ 21 are linked with an oxygen atom (-O-). Ra’ 21 As the halogen atom in [reference], a fluorine atom is preferable. Ra’ 21 As the alkyl halide group in [reference], the groups in which some or all of the hydrogen atoms of the alkyl group in the above Ra’ 21 are substituted with the halogen atom. As the alkyl halide group, a fluorinated alkyl group is preferable, and a perfluoroalkyl group is particularly preferable.

[0239] Ra’ 21 In -COOR” and -OC(=O)R” in [reference], R” is each a hydrogen atom, an alkyl group, or a lactone-containing cyclic group. As the alkyl group in R”, it may be linear, branched, or cyclic, and preferably has 1 to 15 carbon atoms. When R” is a linear or branched alkyl group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably a methyl group or an ethyl group. When “R” is a cyclic alkyl group, it preferably has 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, a group obtained by removing one or more hydrogen atoms from a monocycloalkane which may or may not be substituted with a fluorine atom or a fluorinated alkyl group; a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as a bicycloalkane, a tricycloalkane, or a tetracycloalkane can be exemplified. More specifically, a group obtained by removing one or more hydrogen atoms from a monocycloalkane such as cyclopentane or cyclohexane; adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 decane, a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as tetracyclododecane, etc. can be mentioned. Examples of the lactone-containing cyclic group in R” include the same groups as those represented by the general formulas (a2-r-1) to (a2-r-7) respectively. Ra’ 21 As the hydroxyalkyl group in, those having 1 to 6 carbon atoms are preferable. Specifically, a group in which at least one hydrogen atom of the alkyl group in the above Ra’ 21 is substituted with a hydroxyl group can be mentioned.

[0240] Ra’ 21 Among the above, each is preferably independently a hydrogen atom or a cyano group.

[0241] In the general formulas (a2-r-2), (a2-r-3), and (a2-r-5), the alkylene group having 1 to 5 carbon atoms in A” is preferably a linear or branched alkylene group, 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.

[0242] Specific examples of the groups represented by the general formulas (a2-r-1) to (a2-r-7) are given below.

[0243]

Chemical formula

[0244]

Chemical formula

[0245] As the structural unit (a2), among others, a structural unit derived from an acrylate ester in which a hydrogen atom bonded to the 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).

[0246]

Chemical formula

[0247] 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.

[0248] 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 general formula (a10-1) above.

[0249] 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.

[0250] In the formula (a2-1), Ya 21 is a single bond, and La 21 is preferably -COO- or -OCO-.

[0251] 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 respectively represented by the above general formulas (a2-r-1) to (a2-r-7).

[0252] (A1) component may have one or more than two kinds of structural units (a2). (A1) component may or may not have the structural unit (a2). When the (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, and when it is equal to or lower than the upper limit value, the balance with other structural units can be taken, and various lithography characteristics become good.

[0253] Structural unit (a5): (A1) component may or may not have a 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 by exposure is likely to be uniformly distributed in the resist film. Examples of the structural unit (a5) include structural units containing the structures described in the later-described (B) component. For example, structural units containing the structures represented by any of the following general formulas (b-1) to (b-3) can be mentioned. As the structural unit (a5), for example, the structural unit represented by the following general formula (a5-1) is preferably mentioned.

[0254] [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 hetero atom, or a single bond. Ra 51 and Ra 52 are each independently a hydrogen atom, a fluorine atom or a fluorinated alkyl group. n5 is an integer of 1 to 4. m is an integer of 1 or more, and M’ m+ is an m-valent onium cation. ]

[0255] {Anion part} In the formula (a5-1), R m is an alkyl group having 1 to 5 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogen atom or a hydrogen atom. R m The alkyl group having 1 to 5 carbon atoms is preferably a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, etc. can be mentioned. The halogenated alkyl group having 1 to 5 carbon atoms is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. 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. From the viewpoint of easy availability in industry, a hydrogen atom or a methyl group is most preferred.

[0256] In the formula (a5-1), La 50 is a divalent linking group or a single bond. La 50 The divalent linking group in La is not particularly limited, but a divalent hydrocarbon group which may have a substituent and a divalent linking group containing a hetero atom are preferably mentioned. Each is the same as the divalent hydrocarbon group which may have a substituent and the divalent linking group containing a hetero atom exemplified as the divalent linking group in the above Ya x1 ​ 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)-].

[0257] In the formula (a5-1), Ra 50 is a divalent hydrocarbon group which may have a substituent. Ra 50 The divalent hydrocarbon group in Ra may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0258] ··Ra 50 The aliphatic hydrocarbon group in Ra The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated. Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, or an aliphatic hydrocarbon group containing a ring in the structure, etc.

[0259] ···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 preferred. Specifically, alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-; 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 preferred.

[0260] The 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.

[0261] ··· an aliphatic hydrocarbon group containing a ring in the structure Examples of the aliphatic hydrocarbon group containing a ring in the structure include a cyclic aliphatic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring) which may contain a substituent containing a hetero atom in the ring structure, a group in which the cyclic aliphatic hydrocarbon group is bonded to the 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 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.

[0262] 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, 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, 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.

[0263] ··Ra 50Aromatic hydrocarbon group The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. This aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, 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 heteroatom, etc. may be mentioned. Examples of the heteroatom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specifically, as the aromatic heterocyclic ring, a pyridine ring, a thiophene ring, etc. may 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, a 2-naphthylethyl group, etc.). The number of carbon atoms in the alkylene group bonded to the aryl group or heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0264] In the aromatic hydrocarbon group, the hydrogen atom possessed by the aromatic hydrocarbon group may be substituted with a substituent. For example, the hydrogen atom bonded to the aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, etc. As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group are most 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.

[0265] 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 which may contain a substituent containing a hetero atom in the ring structure, and still more preferably an alicyclic hydrocarbon group which 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.

[0266] n a5 When it is 2, the two Ra 50 may both be alicyclic hydrocarbon groups which may have a substituent, may both be aromatic hydrocarbon groups, or may be a combination of an alicyclic hydrocarbon group which may have a substituent and an aromatic hydrocarbon group.

[0267] 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 binds to V' in the following general formulas (L-al-1) to (L-al-8). 101 That is.

[0268] [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.]

[0269] 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.

[0270] 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, 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, some of the methylene groups in the alkylene group may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms. The aliphatic cyclic group is preferably a 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), more preferably a cyclohexylene group, a 1,5-adamantylene group or a 2,6-adamantylene group. 3 The aliphatic cyclic group is preferably a divalent group obtained by further removing one hydrogen atom from the cyclic aliphatic hydrocarbon group (monocyclic aliphatic hydrocarbon group, polycyclic aliphatic hydrocarbon group) of Ra’ in the formula (a1-r-1), more preferably a cyclohexylene group, a 1,5-adamantylene group or a 2,6-adamantylene group.

[0271] La 51 As, a divalent linking group containing an ester bond or a divalent linking group containing an ether bond is preferable, the linking groups represented by the above formulas (L-al-1) to (L-al-5), (L-al-8) are more preferable, and the linking group represented by (L-al-3) or (L-al-8) is still more preferable.

[0272] 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 [the relevant context] is not particularly limited, but 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 [the relevant context], 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 in [the relevant context]. Among the above, Ya 5 is preferably a linear or branched alkylene group or a single bond, and more preferably a single bond.

[0273] 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 [the relevant context] 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), for Ra - and Ra 51 and Ra 52 bonded to the carbon atom adjacent to SO3

[0274] at least one of them is preferably a fluorine atom from the viewpoint of acid strength.

[0275] {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.

[0276] Preferred cation part ((M’ m+ )) 1 / mExamples thereof include organic cations represented by the above general formulas (ca-1) to (ca-3).

[0277] The cation part ((M’ m+ ) 1 / m ) in the formula (a5-1) is preferably a sulfonium cation, more preferably a cation represented by the above general formulas (ca-1) to (ca-3), still more preferably a cation represented by the formula (ca-1), and particularly preferably a cation represented by the formulas (ca-1-1) to (ca-1-84). From the viewpoint of particularly 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 preferable. For example, a cation selected from the group consisting of cations represented by the above chemical formulas (ca-1-44), (ca-1-71) to (ca-1-84) is particularly preferable.

[0278] Preferred specific 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 above general formula (a5-1).

[0279]

Chemical formula

[0280]

Chemical formula

[0281]

Chemical formula

[0282]

Chemical formula

[0283] (A1) component may have one or more than two kinds of structural units (a5). When the (A1) component has the structural unit (a5), the proportion of the structural unit (a5) in the (A1) component is preferably 5 to 25 mol%, more preferably 10 to 20 mol%, still more preferably 15 to 20 mol% with respect to the total of all the structural units (100 mol%) constituting the (A1) component. When the proportion of the structural unit (a5) is at least the lower limit of the above-mentioned preferred range, it becomes easier to achieve further higher sensitivity and improved resolution. On the other hand, when it is at most the upper limit of the above-mentioned preferred range, it becomes easier to balance with other structural units.

[0284] Structural unit (a6): The structural unit (a6) is a structural unit having acid diffusion controllability (however, those corresponding to the structural unit (a0) are excluded). The (A1) component may or may not have the structural unit (a6). Known structural units can be used as the structural unit (a6). Examples of the structural unit (a6) include structural units containing the structures described in the following (D1) component and (D2) component. For example, structural units containing the structures represented by any of the following general formulas (d1-1) to (d1-3) can be mentioned.

[0285] (A1) component may have one or more than two kinds of structural units (a6). When the (A1) component has the structural unit (a6), the proportion of the structural unit (a6) in the (A1) component is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, still more preferably 3 to 10 mol% with respect to the total of all the structural units (100 mol%) constituting the (A1) component. When the proportion of the structural unit (a6) is at least the lower limit of the above-mentioned preferred range, it becomes easier to achieve further higher sensitivity. On the other hand, when it is at most the upper limit of the above-mentioned preferred range, it becomes easier to balance with other structural units.

[0286] Structural unit (a8): The structural unit (a8) is a structural unit derived from a compound represented by the following general formula (a8-1). The component (A1) may or may not have the structural unit (a8).

[0287] [Chemical formula] [In the formula, W 2 is a polymerizable group-containing group. Ya x2 is a single bond or an (n ax2 +1)-valent linking group. Ya x2 and W 2 may form a condensed ring. R 1 is a fluorinated alkyl group having 1 to 12 carbon atoms. R 2 is an organic group having 1 to 12 carbon atoms which may have a fluorine atom or a hydrogen atom. R 2 and Ya x2 may be bonded to each other to form a ring structure. n ax2 is an integer from 1 to 3.]

[0288] The "polymerizable group" in the polymerizable group-containing group 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 group containing a multiple bond between carbon atoms such as an ethylenic double bond.

[0289] The polymerizable group-containing group may be a group composed only of a polymerizable group or a group composed of a polymerizable group and another group other than the polymerizable group. Examples of the other group other than the polymerizable group include a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a hetero atom, and the like. Examples of the polymerizable group-containing group include, for example, a group represented by the chemical formula: C(R X11 )(R X12 )=C(R X13 )-Ya x0 -. In this chemical formula, R X11 , R X12 and R X13is 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.

[0290] Ya x2 and W 2 Examples of the condensed ring formed by and are 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 the condensed ring formed by and. Ya x2 and W 2 The condensed ring formed by and may have a substituent.

[0291] 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.

[0292] [Chemical formula]

[0293] 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), (a8-1-09).

[0294] 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 (100 mol%) of all the structural units constituting the component (A1).

[0295] As for the component (A1) contained in the resist composition, one kind may be used alone, or two or more kinds may be used in combination.

[0296] Examples of the component (A1) include a polymer compound having a structural unit (a0), a structural unit (a1), and a structural unit (a10); a polymer compound having a structural unit (a0), a structural unit (a1), a structural unit (a10), and a structural unit (a5), and the like.

[0297] In the polymer compound composed of the structural unit (a0), the structural unit (a1), and the structural unit (a10), the proportion of the structural unit (a1) is preferably 2 to 20 mol%, more preferably 2 to 15 mol%, still more preferably 2 to 10 mol%, and particularly preferably 3 to 8 mol% with respect to the total (100 mol%) of all the structural units constituting the polymer compound. The proportion of the structural unit (a1) in the polymer compound is more preferably 10 to 75 mol%, still more preferably 30 to 70 mol%, and still more preferably 40 to 70 mol% with respect to the total (100 mol%) of all the structural units constituting the polymer compound. The proportion of the structural unit (a10) in the polymer compound is preferably 20 to 80 mol%, more preferably 20 to 70 mol%, still more preferably 25 to 60 mol%, and particularly preferably 25 to 50 mol% with respect to the total (100 mol%) of all the structural units constituting the polymer compound.

[0298] In the polymer compound composed of the structural unit (a0), the structural unit (a1), the structural unit (a10), and the structural unit (a5), the proportion of the structural unit (a1) is preferably 2 to 20 mol%, more preferably 2 to 15 mol%, still more preferably 2 to 10 mol%, and particularly preferably 3 to 8 mol% with respect to the total (100 mol%) of all the structural units constituting the polymer compound. The proportion of the structural unit (a1) in the polymer compound is more preferably 10 to 75 mol%, still more preferably 30 to 70 mol%, and still more preferably 40 to 70 mol%. The proportion of the structural unit (a10) in the polymer compound is preferably 10 to 70 mol%, more preferably 20 to 70 mol%, still more preferably 25 to 60 mol%, and particularly preferably 25 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 (a5) in the polymer compound is more preferably 10 to 20 mol%, and still more preferably 15 to 20 mol% with respect to the total of all the structural units (100 mol%) constituting the polymer compound.

[0299] Such component (A1) can be produced by dissolving the monomers that induce each structural unit in a polymerization solvent, and adding a radical polymerization initiator such as azobisisobutyronitrile (AIBN), dimethyl azobisisobutyrate (e.g., V-601, etc.) thereto and carrying out polymerization. Alternatively, such component (A1) can be produced by dissolving the monomer that induces the structural unit (a1) and the monomers that induce arbitrary structural units (e.g., the structural unit (a10), the structural unit (a5), etc.) in a polymerization solvent, adding the radical polymerization initiator as described above thereto and carrying out polymerization, and then performing a deprotection reaction. In addition, during the 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 some of the hydrogen atoms of the alkyl group are substituted with fluorine atoms is introduced is effective for reducing development defects and LER (line edge roughness: uneven irregularities on the sidewall of the line).

[0300] The weight average molecular weight (Mw) (in terms of polystyrene conversion by gel permeation chromatography (GPC)) of component (A1) is not particularly limited, and is preferably 1000 to 50000, more preferably 5000 to 40000, and still more preferably 5000 to 30000. When the Mw of the component (A1) is equal to or less than the preferable upper limit value of this range, it has sufficient solubility in a resist solvent for use as a resist, and when it is equal to or higher than the preferable lower limit value 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, 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.

[0301] The proportion of the component (A1) in the component (A) is preferably 10% by mass or more, more preferably 15% by mass or more, and may be 100% by mass, based on the total mass of the component (A). When the proportion is 10% 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.

[0302] ·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 polymer compound as the component (A2) is a polymer compound that does not have the structural unit (a0). Examples of the component (A2) include a polymer compound having the structural unit (a1); a polymer compound having the structural unit (a1) and the structural unit (a10); a polymer compound having the structural unit (a1), the structural unit (a10), and the structural unit (a5), and the like. Examples of the proportion of these structural units in the component (A2) include the same as those described above.

[0303] The component (A2) may be used alone as one kind of polymer compound or low molecular compound, or in combination of two or more kinds. When the (A) component contains the (A2) component, the proportion of (A2) in the (A) component is, based on the total mass of the (A) component, 10 to 90% by mass, may be 20 to 85% by mass, or may be 50 to 85% by mass.

[0304] In the resist composition of this embodiment, the content of the (A) component may be adjusted according to the resist film thickness to be formed or the like.

[0305] <Acid generator component (B)> The resist composition of this embodiment may contain an acid generator component (B) that generates an acid upon exposure. The (B) component is not particularly limited, and those proposed as acid generators for chemically amplified resist compositions can be used. Examples of such acid generators include onium salt-based acid generators such as iodonium salts and sulfonium salts, oxime sulfonate-based acid generators; diazomethane-based acid generators such as bisalkyl or bisaryl sulfonyldiazomethanes and poly(bissulfonyl)diazomethanes; nitrobenzyl sulfonate-based acid generators, iminosulfonate-based acid generators, and disulfone-based acid generators. The form of the content of the (B) component may be in the form of a compound, may be incorporated into the (A1) component as the above-described structural unit (a5), or may be in both of these forms.

[0306] 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").

[0307] 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").

[0308] [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. ]

[0309] {Anion part} ·Anion in the component (b-1) In the 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.

[0310] 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.

[0311] R101 The aromatic hydrocarbon group in 101 is a hydrocarbon group having an aromatic ring. The number of carbon atoms in the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, 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 101 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, and a nitrogen atom. R 101 Specific examples of the aromatic hydrocarbon group in 101 include a group obtained by removing one hydrogen atom from the aromatic ring (aryl group: for example, phenyl group, naphthyl group, etc.), a group in which one hydrogen atom of the aromatic ring is substituted with an alkylene group (for example, benzyl group, phenethyl group, 1-naphthylmethyl group, etc.). The number of carbon atoms of the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0312] R 101 The cyclic aliphatic hydrocarbon group in 101 includes an aliphatic hydrocarbon group containing a ring in its structure. Examples of the aliphatic hydrocarbon group containing a ring in this structure include an alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring), a group in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. The number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 20, more preferably 3 to 12. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from monocycloalkane is preferable. As the monocycloalkane, those having 3 to 6 carbon atoms are preferable, and specifically, cyclopentane, cyclohexane and the like can be mentioned. As the polycyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from polycycloalkane is preferable, and as the polycycloalkane, those having 7 to 30 carbon atoms are preferable. Among them, as the polycycloalkane, polycycloalkanes having a crosslinked ring system polycyclic skeleton such as adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 decane, tetracyclododecane; and polycycloalkanes having a condensed ring system polycyclic skeleton such as a cyclic group having a steroid skeleton are more preferable.

[0313] Among them, the cyclic aliphatic hydrocarbon group in R 101 is preferably a group obtained by removing one or more hydrogen atoms from monocycloalkane or polycycloalkane, more preferably a group obtained by removing one hydrogen atom from polycycloalkane, still more preferably an adamantyl group or a norbornyl group, and particularly preferably an adamantyl group.

[0314] The linear aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specifically, methylene group [-CH2-], ethylene group [-(CH2)2-], trimethylene group [-(CH2)3-], tetramethylene group [-(CH2)4-], pentamethylene group [-(CH2)5-] and the like can be mentioned. The branched aliphatic hydrocarbon group, which may be bonded to an 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 preferred. Specifically, alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-; 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 preferred.

[0315] 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.

[0316] 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 a substituent, an alkyl group having 1 to 5 carbon atoms is preferred. 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 above halogen atoms can be mentioned. The carbonyl group as a substituent is a group that substitutes the methylene group (-CH2-) constituting the cyclic hydrocarbon group.

[0317] R 101 The cyclic hydrocarbon group in may be a condensed ring type group containing a condensed ring in which an aliphatic hydrocarbon ring and an aromatic ring are condensed. Examples of the condensed ring include those in which one or more aromatic rings are condensed to a polycycloalkane having a bridged ring system polycyclic skeleton. Specific examples of the bridged ring system polycycloalkane include bicycloalkanes such as bicyclo[2.2.1]heptane (norbornane) and bicyclo[2.2.2]octane. As the condensed ring type, a group containing a condensed ring in which two or three aromatic rings are condensed to a bicycloalkane is preferable, and a group containing 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 ring type 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 a bond that binds to Y in the formula (b-1).

[0318]

Chemical formula

[0319] R 101Examples of the substituent that the condensed cyclic group in [compound name] 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. The alkyl group, alkoxy group, halogen atom, and halogenated alkyl group as the substituent of the condensed cyclic group are the same as those exemplified as the substituent of the cyclic group in the above R 101 and can be exemplified as the same ones. Examples of the aromatic hydrocarbon group as the substituent of the condensed cyclic group include a group obtained by removing one hydrogen atom from an aromatic ring (aryl group: for example, phenyl group, naphthyl group, etc.), a group in which one hydrogen atom of the aromatic ring is substituted with an alkylene group (for example, arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.), and heterocyclic groups represented by the above formulas (r-hr-1) to (r-hr-6), respectively. 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; lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-7), respectively; -SO2-containing cyclic groups represented by the general formulas (b5-r-1) to (b5-r-4), respectively; and heterocyclic groups represented by the formulas (r-hr-7) to (r-hr-16), respectively.

[0320] The chain alkyl group which may have a substituent: R 101 The chain alkyl group of may be either linear or branched. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. The branched-chain alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specifically, examples include 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, and the like.

[0321] A chain alkenyl group which may have a substituent: R 101 The chain alkenyl group of R may be linear or branched, preferably has 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, still more preferably 2 to 4 carbon atoms, and particularly preferably 3 carbon atoms. Examples of the linear alkenyl group include vinyl group, propenyl group (allyl group), butenyl group, and the like. Examples of the branched-chain alkenyl group include 1-methylvinyl group, 2-methylvinyl group, 1-methylpropenyl group, 2-methylpropenyl group, and the like. Among the above, the linear alkenyl group is preferred as the chain alkenyl group, the vinyl group and the propenyl group are more preferred, and the vinyl group is particularly preferred.

[0322] R 101 Examples of the substituent in the chain alkyl group or alkenyl group of R include alkoxy group, halogen atom, halogenated alkyl group, hydroxyl group, carbonyl group, nitro group, amino group, and the cyclic group in the above R 101 and the like.

[0323] 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 carbon atom, hydrogen atom, sulfur atom, nitrogen atom, and the like. Examples of the divalent linking group containing an oxygen atom include the linking groups represented by the above general formulas (L-al-1) to (L-al-8), respectively. In the following general formulas (L-al-1) to (L-al-8), R in the above formula (b-1) 101 is bonded to V' in the following general formulas (L-al-1) to (L-al-8). 101 That is.

[0324] In the formula (b-1), V 101 is a single bond, an alkylene group or a fluorinated alkylene group. Among them, V 101 is preferably a single bond or a linear fluorinated alkylene group having 1 to 4 carbon atoms.

[0325] In the formula (b-1), R 102 is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. R 102 is preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and more preferably a fluorine atom.

[0326] Specific examples of the anion part represented by the formula (b-1) include, for example, when Y 101 is a single bond, fluorinated alkyl sulfonate anions such as trifluoromethanesulfonate anion and perfluorobutanesulfonate anion; when Y 101 is a divalent linking group containing an oxygen atom, anions represented by any of the following formulas (an-1) to (an-3) can be mentioned.

[0327] [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 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. Each v” is independently an integer of 0 to 3, each q” is independently an integer of 0 to 20, and n” is 0 or 1.]

[0328] 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). 101 in the formula (b-1).

[0329] 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). 101 in the formula (b-1).

[0330] R” 101 The chain alkyl group which may have a substituent in R” is preferably a group exemplified as the chain 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

[0331] · 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 even more preferably 1 to 3 carbon atoms. For the chain alkyl groups of R 104 , R 105 , the smaller the number of carbon atoms within the above range of the number of carbon atoms, the better the solubility in the resist solvent and other reasons. Also, in the chain alkyl groups of R 104 , R 105 , the higher the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid strength, and the better the transparency to high-energy light or electron beams of 250 nm or less. The ratio of fluorine atoms in the chain alkyl group, that is, the fluorination rate, is preferably 70 to 100%, more preferably 90 to 100%, and most preferably a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms. In 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 cited. In formula (b-2), L 101 , L 102 is each independently a single bond or an oxygen atom.

[0332] · Anion in component (b-3) In formula (b-3), R 106 ~R 108 is 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 cited. In formula (b-3), L 103 ~L 105 is each independently a single bond, -CO- or -SO2-.

[0333] Among the above, as the anion part of component (B), the anion in component (b-1) is preferable, and the anion represented by the above formula (an-1) is more preferable.

[0334] {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.

[0335] As the cation part of component (B), a sulfonium cation is preferable, the cations respectively represented by the above formulas (ca-1) to (ca-3) are more preferable, the cation represented by the above formula (ca-1) is still more preferable, and the cations respectively represented by the above formulas (ca-1-1) to (ca-1-84) are particularly preferable.

[0336] In the resist composition of this embodiment, 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 still more preferably 10 to 43 parts by mass with respect to 100 parts by mass of the component (A). By setting the content of the component (B) within the above-mentioned preferred range, when each component of the resist composition is dissolved in an organic solvent, a uniform solution is easily obtained, and the storage stability as a resist composition is good, which is preferable.

[0337] <Base component (D)> The resist composition of the present embodiment may contain, in addition to the component (A), a base component ((D) component) that traps the acid generated by exposure (that is, controls the diffusion of the acid). The component (D) acts as a quencher (acid diffusion controller) that traps the 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 control properties, 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 preferable because it is easy to enhance the characteristics of high sensitivity, reduction of roughness, and suppression of the occurrence of coating defects. The forms of containing the (D1) component and the (D2) component may be in the form of a compound, may be in the form incorporated into the (A1) component as the above-mentioned structural unit (a6), or may be in both of these forms. The compound exemplified as the (D1) component described below may be used as the above-mentioned acid generator component ((B) component) in combination with other compounds in some cases.

[0338] ·Regarding the (D1) component (D1) The component is not particularly limited as long as it decomposes upon exposure and loses acid diffusion controllability, and one or more compounds selected from the group consisting of a compound represented by the following general formula (d1-1) (hereinafter referred to as "(d1-1) component"), a compound represented by the following general formula (d1-2) (hereinafter referred to as "(d1-2) component"), and a compound represented by the following general formula (d1-3) (hereinafter referred to as "(d1-3) component") are preferred. In the exposed portion of the resist film, the (d1-1) to (d1-3) components decompose and lose acid diffusion controllability (basicity), so they do not act as quenchers, and in the unexposed portion of the resist film, they act as quenchers.

[0339] [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. m is an integer of 1 or more, and M m+ are each independently an m-valent organic cation.]

[0340] {(d1-1) component} ·· Anion part In the formula (d1-1), Rd 1 is an optionally substituted cyclic group, an optionally substituted linear alkyl group, or an optionally substituted linear alkenyl group, and examples thereof are the same as those of the above R' 201 . Among these, Rd 1Examples thereof preferably include an aromatic hydrocarbon group which may have a substituent, an alicyclic group which may have a substituent, or a linear 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 each of the 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, a linking group represented by each of the above formulas (L-al-1) to (L-al-5) is preferable as the substituent. Note that Rd 1 When the aromatic hydrocarbon group, alicyclic group, or linear alkyl group in Rd 1 has a linking group represented by each of the general formulas (L-al-1) to (L-al-7) as a substituent, in the general formulas (L-al-1) to (L-al-7), Rd in the formula (d3-1) 101 is such that it is bonded to a carbon atom constituting the aromatic hydrocarbon group, alicyclic group, or linear alkyl group in Rd Examples of the aromatic hydrocarbon group preferably include a phenyl group, a naphthyl group, and a polycyclic structure containing a bicyclooctane skeleton (a polycyclic structure composed of a bicyclooctane skeleton and another ring structure). Examples of the alicyclic group preferably include a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 decane, or tetracyclododecane. The linear alkyl group preferably has 1 to 10 carbon atoms. 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.

[0341] 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 an oxygen atom, a sulfur atom, a nitrogen atom, etc.

[0342] Specific preferred examples of the anionic part of the component (d1-1) are shown below.

[0343]

Chemical formula

[0344] ···Cation part In formula (d1-1), M m+ is an m-valent organic cation. M m+ Examples of the organic cation of M preferably include the same cations as those represented by the general formulas (ca-1) to (ca-3) respectively. The cation represented by the general formula (ca-1) is more preferable, and the cations 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.

[0345] {(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 those mentioned above. 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 . As a result, 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.

[0346] The linear alkyl group preferably has 1 to 10 carbon atoms, and more preferably 3 to 10 carbon atoms. Examples of the aliphatic cyclic group include groups 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 groups obtained by removing one or more hydrogen atoms from camphor are more preferred.

[0347] Rd 2 The hydrocarbon group of may have a substituent, and examples of the substituent include the same substituents as those that the hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, linear alkyl group) in Rd 1 in formula (d1-1) may have.

[0348] Preferred specific examples of the anion part of the (d1-2) component are shown below.

[0349]

Chemical formula

[0350] ·· 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+ is the same as above. The component (d1-2) may be used alone or in combination of two or more.

[0351] {(component (d1-3))} ··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 examples thereof are the same as those of the above R', 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 those similar to the fluorinated alkyl group of the above Rd 201 are more preferable. 1 is the same as above.

[0352] 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 examples thereof are the same as those of the above R'. 201 is the same as above. 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, 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. A part of the hydrogen atoms of the alkyl group of Rd 4 may be 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 preferred.

[0353] Rd 4 The alkenyl group in is the same as the alkenyl group in the above R'. 201 Examples thereof include a vinyl group, a propenyl group (allyl group), a 1-methylpropenyl group, and a 2-methylpropenyl group. These groups may further have, as a substituent, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms.

[0354] Rd 4 The cyclic group in is the same as the cyclic group in the above R'. 201 Examples thereof include an alicyclic group obtained by removing one or more hydrogen atoms from a cycloalkane such as cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 decane, tetracyclododecane, or an aromatic group such as a phenyl group or a naphthyl group. When Rd 4 is an alicyclic group, the resist composition dissolves well in an organic solvent, resulting in good lithography characteristics. 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 good sensitivity and lithography characteristics.

[0355] 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, and the like. Each of these is the same as Ya in the above formula (a2-1). 21Examples of the divalent linking group in the description include the same as the divalent hydrocarbon group which may have a substituent and the divalent linking group containing a heteroatom, which were mentioned in the description of the divalent linking group. 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.

[0356] Specific preferred examples of the anionic part of the component (d1-3) are shown below.

[0357]

Chemical formula

[0358]

Chemical formula

[0359] ··· 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+ and the same as above. The component (d1-3) may be used alone or in combination of two or more.

[0360] 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).

[0361] The component (D1) preferably contains the above component (d1-1). Among the whole component (D1), the content of the component (d1-1) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more. The component (D1) may consist only of the compound (d1-1) component.

[0362] Production method of component (D1): The production methods of the above-mentioned components (d1-1) and (d1-2) are not particularly limited and can be produced by known methods. Also, the production method of the component (d1-3) is not particularly limited and is produced, for example, 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 component (D1) was shown, but the compound of the component (D1) may be used as the component (B). For example, in the resist composition of the present embodiment, a compound of the component (D1) is used as the component (B), and a compound that generates an acid with a lower acidity than the acid generated by exposure of the compound of the component (D1) is used as the component (D). Also, in the resist composition of the present embodiment, a compound of the component (D1) is used as the component (B), and the component (D2) described later may be used as the component (D).

[0363] ·Regarding the component (D2) As the component (D), a nitrogen-containing organic compound component that does not correspond to the above-mentioned component (D1) (hereinafter referred to as "component (D2)") may be contained. The component (D2) is not particularly limited as long as it acts as an acid diffusion control agent and does not correspond to the component (D1), and can 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 an amine (alkylamine or alkyl alcohol amine) in which at least one hydrogen atom of ammonia NH3 is substituted with an alkyl group or hydroxyalkyl group having 12 or less carbon atoms, or a cyclic amine. Specific examples of the alkylamine and alkyl alcohol amine include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine; dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine, dicyclohexylamine; trialkylamines such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, tri-n-dodecylamine; and alkyl alcohol amines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, tri-n-octanolamine. Among these, trialkylamines having 6 to 30 carbon atoms are more preferable, and tri-n-pentylamine or tri-n-octylamine is particularly preferable.

[0364] Examples of the cyclic amine include, for example, a heterocyclic compound 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, and the like. 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, and the like.

[0365] 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.

[0366] Also, as the component (D2), an aromatic amine may be used. Examples of aromatic amines include 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or their derivatives, tribenzylamine, 2,6-diisopropylaniline, N-tert-butoxycarbonylpyrrolidine, 2,6-di-tert-butylpyridine, etc.

[0367] The component (D2) may be used alone or in combination of two or more. When the resist composition contains the component (D2), in the resist composition, the content of the component (D2) is usually used in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the component (A). By setting it within the above range, the resist pattern shape, standing time stability, etc. are improved.

[0368] Since the resist composition of this embodiment has the component (A1) having the structural unit (a0), it is preferably free of the components (D1) and (D2).

[0369] <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 this embodiment, for the purpose of preventing sensitivity deterioration and improving the resist pattern shape, stability over time during standing, etc., as optional components, an organic carboxylic acid and at least one compound (E) selected from the group consisting of oxo acids of phosphorus and their derivatives (hereinafter referred to as the “(E) component”) can be contained. Specific 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.

[0370] In the resist composition of this embodiment, the (E) component may be used alone or in combination of two or more. When the resist composition contains the (E) component, the content of the (E) component 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 (A) component. By setting the content within the above range, the lithography characteristics can be further improved.

[0371] <Fluorine additive component (F)> The resist composition of this embodiment may contain a fluorine additive component (hereinafter referred to as the “(F) component”) as a hydrophobic resin. The (F) component is used to impart water repellency to the resist film, and by using it as a resin different from the (A) component, the lithography characteristics can be improved. As the (F) component, for example, the fluorine-containing polymer compounds described in JP-A-2010-002870, JP-A-2010-032994, JP-A-2010-277043, JP-A-2011-13569, and JP-A-2011-128226 can be used. (F) More specifically as the component, polymers having a structural unit (f1) represented by the following general formula (f1-1) can be mentioned. As this polymer, a polymer consisting only of the structural unit (f1) represented by the following formula (f1-1) (homopolymer); a copolymer of the structural unit (f1) and the structural unit (a1); 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.

[0372]

Chemical formula

[0373] 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 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.

[0374] 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.

[0375] (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, and 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.

[0376] 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.

[0377] <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 the "(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.

[0378] 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. 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, the mixing ratio is preferably such that the mass ratio of the former to the latter is 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.

[0379] For the resist composition of this embodiment, after dissolving the above resist material in the (S) component, impurities and the like may be removed using a polyimide porous membrane, a polyamideimide porous membrane, or the like. For example, the resist composition may be filtered using a filter made of a polyimide porous membrane, a filter made of a polyamideimide porous membrane, a filter made of a polyimide porous membrane and a polyamideimide porous membrane, or the like. Examples of the polyimide porous membrane and the polyamideimide porous membrane include those described in JP-A-2016-155121.

[0380] The resist composition of this embodiment described above contains the (A1) component having the structural unit (a0). By containing the (A1) component having the structural unit (a0), the resist composition of this embodiment has the effect of improving roughness (for example, CDU) and resolution while maintaining good sensitivity. The reason for such an effect is presumed as follows. The structural unit (a0) is a structural unit having acid diffusion controllability, and has a structure in which an iodine atom bonded to an aromatic ring and an anion moiety containing a sulfonamide group are incorporated into the (A1) component. Since the anion moiety of the structural unit (a0) is supported by the (A1) component, the acid diffusion control component can be uniformly dispersed in the resist film. In addition, since the structural unit (a0) contains an iodine atom bonded to an aromatic ring, the EUV absorption efficiency is improved and the sensitivity to EUV is enhanced. On the other hand, having iodine increases the hydrophobicity, but since the (A1) component has the structural unit (a0), the affinity for an alkaline developer is increased, and the occurrence of development defects is suppressed. In addition, the sulfonamide group in the structural unit (a0) has an appropriate acidity and can function as an acid generator in the exposed area. Therefore, the sensitivity is further enhanced. It is presumed that by the synergistic action of each of the above-described operations, it is possible to improve roughness and resolution while maintaining good sensitivity.

[0381] (Resist pattern forming method) The resist pattern forming method according to the second aspect of the present invention includes a step of forming a resist film on a support using the resist composition according to the first aspect of the present invention described above, a step of exposing the resist film, and a step of developing the exposed resist film to form a resist pattern. As an embodiment of such a resist pattern forming method, for example, a resist pattern forming method performed as follows can be mentioned.

[0382] 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 by, for example, exposure through a mask (mask pattern) in which a predetermined pattern is formed or direct irradiation with an electron beam without passing through a mask pattern using an exposure apparatus such as an electron beam drawing 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.

[0383] After the development process, a rinsing process is preferably performed. In the case of an alkali development process, water rinsing using pure water is preferable, and in the case of a solvent development process, it is preferable to use a rinsing liquid containing an organic solvent. In the case of a solvent development process, after the development process or the rinse process, a process of removing the developer or the rinse liquid adhering to the pattern with a supercritical fluid may be performed. After the development process or the rinse process, drying is performed. Further, in some cases, a baking process (post-bake) may be performed after the development process.

[0384] The support is not particularly limited, and a conventionally known one can be used. For example, a substrate for electronic components, a substrate having a predetermined wiring pattern formed thereon, etc. can be mentioned. More specifically, a silicon wafer, a metal substrate such as copper, chromium, iron, aluminum, a glass substrate, etc. can be mentioned. As the material of the wiring pattern, for example, copper, aluminum, nickel, gold, etc. can be used.

[0385] The wavelength used for exposure is not particularly limited, and it can be performed using radiation such as an ArF excimer laser, a KrF excimer laser, an F2 excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray, 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.

[0386] The exposure method of the resist film may be normal exposure (dry exposure) performed in an inert gas such as air or nitrogen, or 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 larger 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 larger than that of air and smaller than that of the resist film to be exposed is preferable. For example, water, a fluorine-based inert liquid, a silicon-based solvent, a hydrocarbon-based solvent, etc. can be mentioned. Water is preferably used as the liquid immersion medium.

[0387] As the alkaline developer used for development in an alkaline development process, for example, an aqueous solution of 0.1 to 10% by mass of tetramethylammonium hydroxide (TMAH) can be mentioned. As the organic solvent contained in the organic developer used for development in a solvent development process, any one can be used as long as it can dissolve the component (A) (component (A) before exposure), and it 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.

[0388] 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.

[0389] Examples of nitrile solvents include acetonitrile, propionitrile, valeronitrile, and butyronitrile.

[0390] 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.

[0391] The development process can be carried out by known development methods. For example, a method of immersing the support in a developer solution for a certain period of time (dip method), a method of raising the developer solution on the support surface by surface tension and allowing it to stand for a certain period of time (paddle method), a method of spraying the developer solution on the support surface (spray method), a method of continuously discharging the developer solution while scanning a developer solution discharge nozzle at a constant speed on a support rotating at a constant speed (dynamic dispensing method), etc. can be mentioned.

[0392] As the organic solvent contained in the rinse solution used for the rinse treatment after the development process in the solvent development process, for example, among the organic solvents mentioned as the organic solvents used in the organic developer solution, those that are difficult to dissolve the resist pattern can be appropriately selected and used. Usually, at least one solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is used. These organic solvents may be used alone or in combination of two or more. Also, they may be used in mixture with organic solvents other than those described above or water.

[0393] The rinse treatment (cleaning treatment) using the rinse solution can be carried out by known rinse methods. Examples of the method of this rinse treatment include a method of continuously discharging the rinse solution on a support rotating at a constant speed (spin coating method), a method of immersing the support in the rinse solution for a certain period of time (dip method), a method of spraying the rinse solution on the support surface (spray method), etc.

[0394] According to the resist pattern forming method of the present embodiment described above, since the above-described resist composition is used, it is possible to form a resist pattern with low roughness and high resolution while maintaining good sensitivity.

[0395] 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 solvent, developer, rinse liquid, composition for forming an antireflection film, composition 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. 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. The content of impurities contained in these materials is preferably 200 ppb or less, more preferably 1 ppb or less, still more preferably 100 ppt (parts per trillion) or less, particularly preferably 10 ppt or less, and most preferably substantially not contained (being below the detection limit of the measuring device).

[0396] (Compound) The compound according to the third aspect of the present invention is a compound represented by the following general formula (a0-m) (hereinafter, also referred to as "compound (M0)").

[0397] [Chemical formula] [In the formula, W 0 represents a polymerizable group-containing group. Ar 01 and Ar 02 each independently represents an aromatic ring. L 0 represents a single bond or a divalent linking group. Ra 01 and Ra 02 each independently represents a substituent other than iodine. Rx 0 represents a hydrocarbon group which may have a substituent. m01 and m02 each independently represent an integer of 0 or more as long as the valence allows, and m01 + m02 ≧ 1. n01 and n02 each independently represent an integer of 0 or more as long as the valence allows. r01 and r02 each independently represent 0 or 1, and r01 + r02 ≧ 1. k0 represents 0 or 1, and r02 + k0 = 1. When n01 is an integer of 2 or more, two or more Ra 01may be the same as or different from each other. When n02 is an integer of 2 or more, two or more Ra 01 may be the same as or different from each other. m is an integer of 1 or more, and M m+ is an m-valent cation. ]

[0398] The description of the general formula (a0-m) is as described above.

[0399] The compound (M0) is preferably a compound represented by the following general formulas (a0-m1), (a0-m2), and (a0-m3).

[0400] [Chemical formula]

[0401] [Chemical formula]

[0402] [Chemical formula] [In the formula, R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. Ar 01 and Ar 02 each independently represents an aromatic ring. L 0 represents a single bond or a divalent linking group. Ra 01 and Ra 02 each independently represents a substituent other than iodine. Rx 0 represents a hydrocarbon group which may have a substituent. m01 and m02 each independently represent an integer of 0 or more as long as the valence allows, and m01 + m02 ≧ 1. n01 and n02 each independently represent an integer of 0 or more as long as the valence allows. r01 and r02 each independently represent 0 or 1, and r01 + r02 ≧ 1. k0 represents 0 or 1, and r02 + k0 = 1. When n01 is an integer of 2 or more, two or more Ra 01 may be the same as or different from each other. When n02 is an integer of 2 or more, two or more Ra01 may be the same as or different from each other. A 0 represents an oxygen atom or -NH-. m03 represents an integer of 1 or more as long as the valence permits. m is an integer of 1 or more, and M m+ is an m-valent cation. ]

[0403] R, Ar in the formulas (a0-m1), (a0-m2), and (a0-m3) 01 Ar 02 L 0 Ra 01 Ra 02 Rx 0 m01, m02, n01, n02, r01, r02, k0, A 0 m03, m and M m+ are the same as those in the formulas (a0-1), (a0-2), and (a0-3), respectively.

[0404] The compound represented by the formula (a0-m1) is preferably a compound represented by the following general formula (a0-m11) or (a0-m12).

[0405]

Chemical formula

[0406] R, Ar in the formulas (a0 - m11) and (a0 - m12) 01 Ar 02 L 0 Ra 01 Ra 02 Rx 0 m01, m02, n01, n02, m012, m, and M m+ are the same as those in the formulas (a0 - 11) and (a0 - 12), respectively.

[0407] The compound represented by the formula (a0 - m2) is preferably a compound represented by the following general formula (a0 - m21) or (a0 - m22).

[0408]

Chemical formula

[0409] R, Ar in the formulas (a0-m21) and (a0-m22) 01 Ar 02 L 0 Ra 01 Ra 02 Rx 0 m01, m02, n01, n02, A 0 m012, m, and M m+ are the same as those in the formulas (a0-21) and (a0-22), respectively.

[0410] Specific examples of the anion part of the compound (M0) represented by the formula (a0-m1) are given below, but are not limited thereto. In the following formulas, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0411]

Chemical formula

[0412]

Chemical formula

[0413]

Chemical formula

[0414]

Chemical formula

[0415]

Chemical formula

[0416] Specific examples of the compound (M0) represented by the formula (a0-m2) 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.

[0417]

Chemical formula

[0418]

Chemical formula

[0419] Specific examples of the compound (M0) represented by the formula (a0-m3) 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.

[0420]

Chemical formula

[0421] <Method for producing the compound> The compound (M0) can be produced by appropriately combining known methods, as in the <Compound synthesis example> shown in [Examples] described later. The compound (M0) can be produced, for example, by the following reactions (I) to (II).

[0422] ≪Reaction (I)≫ The compound (Pre-0) is obtained by reacting the compound (MCA-0) with the compound (SA-0).

[0423]

Chemical formula

[0424] The temperature condition of reaction (I) is not particularly limited and is, for example, about 0 to 70 °C, preferably 0 to 50 °C, and more preferably 0 to 30 °C. The reaction time of reaction (I) is not particularly limited and is, for example, about 1 to 24 hours, preferably 2 to 12 hours.

[0425] Examples of the reaction solvent for reaction (I) include dichloromethane, dichloroethane, chloroform, tetrahydrofuran, N,N-dimethylformamide, acetonitrile, propionitrile, N,N'-dimethylacetamide, dimethyl sulfoxide, and the like.

[0426] Reaction (I) may be carried out under basic conditions. Examples of the base include organic bases such as triethylamine, 4-dimethylaminopyridine, pyridine, ethyl diisopropylaminocarbodiimide (EDCI) hydrochloride, dicyclohexylcarbodiimide (DCC), N,N'-diisopropylcarbodiimide, carbodiimidazole; and inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate (K2CO3), Cs2CO3, and the like.

[0427] <<Reaction (II)>> Compound (M0) is obtained by a salt exchange reaction of compound (Pre-0).

[0428]

Chemical formula

[0429] The temperature condition of reaction (II) is not particularly limited, for example, it is about 0 to 70 °C, preferably 5 to 60 °C, and more preferably 10 to 50 °C. The reaction time of reaction (II) is not particularly limited, for example, it is about 10 minutes to 24 hours, and preferably 20 minutes to 12 hours.

[0430] Examples of the reaction solvent for reaction (I) include dichloromethane, dichloroethane, chloroform, tetrahydrofuran, N,N-dimethylformamide, acetonitrile, propionitrile, N,N'-dimethylacetamide, dimethyl sulfoxide, etc.

[0431] Reaction (II) may be carried out under basic conditions. Examples of the base include organic bases such as triethylamine, 4-dimethylaminopyridine, pyridine, ethyl diisopropylaminocarbodiimide (EDCI) hydrochloride, dicyclohexylcarbodiimide (DCC), N,N'-diisopropylcarbodiimide, carbodiimidazole, etc.; inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate (K2CO3), Cs2CO3, etc.

[0432] As the compound (MCA-0) used in reaction (II), a known compound may be used, or it may be synthesized by appropriately combining known methods as in the <Compound Synthesis Example> shown in the following [Examples]. For example, the compound (MCA-0) can be obtained by reacting a phenolic compound having a polymerizable group with a bromo compound.

[0433] 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, etc. 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.

[0434] 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 in the production of the polymer compound according to the fourth aspect and the acid diffusion controller according to the fifth aspect described later.

[0435] (Polymer compound) The polymer compound according to the fourth aspect of the present invention has a structural unit derived from the compound according to the third aspect. The structural unit derived from the compound according to the third aspect is the same as the structural unit (a0). The polymer compound of the present embodiment is the same as the component (A1) described above. The polymer compound of the present embodiment can be used in the production of the resist composition according to the first aspect. By incorporating the polymer compound of the present embodiment into the resist composition, it is possible to reduce roughness and improve resolution while maintaining good sensitivity.

[0436] (Acid diffusion controller) The acid diffusion controller according to the fifth aspect of the present invention contains the compound (M0). By incorporating the acid diffusion controller of the present embodiment into the resist composition, it is possible to reduce roughness and improve resolution while maintaining good sensitivity.

Examples

[0437] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0438] (Synthesis example of compound) (Synthesis example of compound (M0-1)) ≪Synthesis of compound (Pre-01)≫ p-Styrenesulfonyl chloride (10.1 g, 50.0 mmol) and triethylamine (7.6 g, 75 mmol) were dissolved in 50 g of N,N-dimethylformamide (DMF). Subsequently, a solution of compound (SA-01) (14.1 g, 50.0 mmol) dissolved in 50 g of DMF was added dropwise to this solution. After stirring at room temperature for 3 hours, 200 g of tert-butyl methyl ether (TBME) and 50 g of MEK were added, and the mixture was washed three times with 200 g of ultrapure water. After distilling off the solvent, the resulting concentrate was dissolved in 60 g of acetone and then added dropwise to 600 g of heptane over 30 minutes. The precipitate was collected by filtration and dried under reduced pressure to obtain compound (Pre-01) (17.5 g, yield = 78.0%).

[0439]

Chemical formula

[0440] ≪Synthesis of compound (M0-1)≫ Compound (Pre-01) (9.0 g, 20.0 mmol) and compound (A) (7.6 g, 22.2 mmol) were dissolved in 200 g of dichloromethane, 50 g of 2% aqueous sodium hydroxide solution was added, and the mixture was reacted at room temperature for 30 minutes. After completion of the reaction, the aqueous phase was removed, and the organic phase was washed five times with 50 g of ultrapure water. The organic phase was concentrated to dryness using a rotary evaporator to obtain compound (M0-1) (13.8 g, yield = 97.0%).

[0441]

Chemical formula

[0442] (Synthesis examples of compounds (M0-2) to (M0-22)) ≪Synthesis of compound (MCA-01)≫ 4-Vinylphenol (PO-01) (12.0 g, 100.0 mmol) was dissolved in 50 g of DMF, and potassium carbonate (20.7 g, 150.0 mmol) was added to the solution. Subsequently, a solution of methyl bromoacetate (BR-01) (16.8 g, 110.0 mmol) dissolved in 50 g of DMF was added dropwise thereto. The resulting solution was stirred at room temperature for 3 hours, then 100 g of TBME was added, and the mixture was washed three times with 200 g of ultrapure water. After distilling off the solvent, the obtained concentrate was dissolved in 50 g of acetonitrile, 160 g of 5% aqueous sodium hydroxide solution was added to this solution, and the mixture was stirred at room temperature for 16 hours. Then, 630 g of 5% aqueous citric acid solution was added dropwise to this solution over 30 minutes, and the precipitate was collected by filtration. The obtained precipitate was washed with 200 g of ultrapure water and then dried under reduced pressure to obtain compound (MCA-01) (11.6 g, yield = 65.0%).

[0443] [Chemical formula]

[0444] <<Synthesis of Compound (MCA-02)>> Compound (MCA-02) was obtained in the same manner as in the above <<Synthesis of Compound (MCA-01)>>, except that compound (BR-02) was used in an equimolar amount instead of methyl bromoacetate (BR-01).

[0445] [Chemical formula]

[0446] <<Synthesis of Compounds (MCA-03) and (MCA-04)>> Compounds (MCA-03) and (MCA-04) were obtained in the same manner as in the above <<Synthesis of Compound (MCA-01)>>, except that either compound (PO-02) or (PO-03) was used in an equimolar amount instead of 4-vinylphenol.

[0447] [Chemical formula]

[0448] ≪Synthesis of Compound (MCA-05)≫ 3,5-Diiodosalicylic acid (15.6 g, 40.0 mmol) and triethylamine (7.6 g, 75 mmol) were dissolved in 100 g of acetonitrile. Subsequently, methacryloyl chloride (6.3 g, 55.0 mmol) was added dropwise at 10 °C or lower. After stirring at room temperature for 6 hours, 200 g of dichloromethane and 200 g of 1% aqueous NH3 solution were added to stop the reaction. The recovered organic layer was washed three times with 200 g of ultrapure water. Thereafter, the solvent was distilled off, and the obtained concentrate was dissolved in 80 g of tetrahydrofuran (THF) and added dropwise to 400 g of ultrapure water over 30 minutes. The precipitate was collected by filtration, washed with 200 g of ultrapure water, and then dried under reduced pressure to obtain Compound (MCA-05) (13.7 g, yield = 75.0%).

[0449]

Chem.

[0450] ≪Synthesis of Compounds (Pre-02) to (Pre-14), (Pre-19) to (Pre-22)≫ Compounds (Pre-02) to (Pre-22) were obtained in the same manner as in the above ≪Synthesis of Compound (pre-01)≫, except that equimolar amounts of p-styrenesulfonyl chloride or any one of Compounds (MCA-01) to (MCA-08) were used instead of p-styrenesulfonyl chloride, and any one of Compounds (SA-02) to (SA-07) was used instead of Compound (SA-01) or Compound (SA-01).

[0451]

Chem.

[0452]

Chem.

[0453]

Chem.

[0454] ≪Synthesis of Compounds (M0-2) to (M0-14), (M0-19) to (M0-22)≫ Compounds (M0-2) to (M0-14), (M0-19) to (M0-22) were obtained in the same manner as in the above ≪Synthesis of Compound (M0-1)≫, except that any one of Compounds (Pre-02) to (Pre-22) was used instead of Compound (Pre-01).

[0455]

Chem.

[0456]

Chem.

[0457] ≪Synthesis of Compounds (M0-15) to (M0-18)≫ Compounds (M0-15) to (M0-118) were obtained in the same manner as in the above ≪Synthesis of Compound (M0-1)≫, except that either Compound (Pre-8) or (Pre-13) was used instead of Compound (Pre-01), and either Compound (B) to (C) was used instead of Compound (A).

[0458]

Chem.

[0459]

Chem.

[0460] NMR measurements were performed on the obtained Compounds (M0-1) to (M0-22), and their structures were identified from the following analysis results.

[0461] Compound (M0-1): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 7.92 - 7.96 (m, ArH, 2H), 7.74 - 7.90 (m, ArH, 15H), 7.55 - 7.64 (m, ArH + I-ArH, 4H), 6.73 - 6.77 (m, I-ArH, 2H), 6.56 - 6.63 (dd, CH=CH2, 1H), 5.80 - 5.84 (d, CH=CH2, 1H), 5.23 - 5.25 (d, CH=CH2, 1H)

[0462] Compound (M0-2): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 7.92 - 7.96 (m, ArH, 2H), 7.74 - 7.90 (m, ArH, 15H), 7.60 - 7.64 (m, ArH, 2H), 7.55 - 7.57 (m, I-ArH, 1H), 6.84 (d, I-ArH, 1H), 6.73 - 6.77 (m, I-ArH, 2H), 6.56 - 6.63 (dd, CH=CH2, 1H), 5.80 - 5.84 (d, CH=CH2, 1H), 5.23 - 5.25 (d, CH=CH2, 1H)

[0463] Compound (M0-3): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 7.92 - 7.96 (m, ArH, 2H), 7.74 - 7.90 (m, ArH, 15H), 7.57 - 7.64 (m, ArH + I-ArH, 3H), 6.73 - 6.77 (m, I-ArH, 2H), 6.56 - 6.63 (dd, CH=CH2, 1H), 5.80 - 5.84 (d, CH=CH2, 1H), 5.23 - 5.25 (d, CH=CH2, 1H)

[0464] Compound (M0-4): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 7.74 - 7.92 (m, ArH, 17H), 7.55 - 7.60 (m, ArH + I-ArH, 4H), 6.73 - 6.77 (m, I-ArH, 2H), 6.56 - 6.63 (dd, CH=CH2, 1H), 5.80 - 5.84 (d, CH=CH2, 1H), 5.23 - 5.25 (d, CH=CH2, 1H)

[0465] Compound (M0-5): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 7.74 - 7.92 (m, ArH, 17H), 7.55 - 7.62 (m, ArH + I-ArH, 4H), 6.73 - 6.77 (m, I-ArH, 2H), 6.56 - 6.63 (dd, CH=CH2, 1H), 5.80 - 5.84 (d, CH=CH2, 1H), 5.23 - 5.25 (d, CH=CH2, 1H), 4.54 (s, CH2, 2H)

[0466] Compound (M0-6): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 7.74 - 7.94 (m, ArH, 17H), 7.55 - 7.62 (m, ArH + I-ArH, 4H), 6.73 - 6.77 (m, I-ArH, 2H), 6.56 - 6.63 (dd, CH=CH2, 1H), 5.80 - 5.84 (d, CH=CH2, 1H), 5.23 - 5.25 (d, CH=CH2, 1H)

[0467] Compound (M0-7): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 8.02 (d, I-ArH, 1H), 7.74 - 7.90 (m, ArH, 15H), 7.58 - 7.62 (m, I-ArH, 2H), 6.56 - 6.63 (dd, CH=CH2, 1H), 5.80 - 5.84 (d, CH=CH2, 1H), 5.23 - 5.25 (d, CH=CH2, 1H), 4.54 (s, CH2, 2H)

[0468] Compound (M0-8): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 8.05 (d, I-ArH, 1H), 7.92 - 7.96 (m, ArH, 2H), 7.74 - 7.90 (m, ArH + I-ArH, 17H), 7.60 - 7.64 (m, ArH, 2H), 6.56 - 6.63 (dd, CH=CH2, 1H), 5.80 - 5.84 (d, CH=CH2, 1H), 5.23 - 5.25 (d, CH=CH2, 1H)

[0469] Compound (M0-9): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 8.02 (d, I-ArH, 2H), 7.74 - 7.96 (m, ArH, 20H), 6.56 - 6.63 (dd, CH=CH2, 1H), 5.80 - 5.84 (d, CH=CH2, 1H), 5.23 - 5.25 (d, CH=CH2, 1H), 4.54 (s, CH2, 2H)

[0470] Compound (M0-10): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 8.02 (d, I-ArH, 2H), 7.74 - 7.90 (m, ArH, 15H), 6.56 - 6.63 (dd, CH=CH2, 1H), 5.80 - 5.84 (d, CH=CH2, 1H), 5.23 - 5.25 (d, CH=CH2, 1H), 4.54 (s, CH2, 2H)

[0471] Compound (M0-11): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 8.02 (d, I-ArH, 1H), 7.74 - 7.90 (m, ArH, 15H), 7.55 - 7.62 (m, I-ArH, 4H), 6.73 - 6.77 (m, I-ArH, 2H), 6.56 - 6.63 (dd, CH=CH2, 1H), 5.80 - 5.84 (d, CH=CH2, 1H), 5.23 - 5.25 (d, CH=CH2, 1H), 4.54 (s, CH2, 2H)

[0472] Compound (M0-12): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 7.74 - 7.94 (m, ArH, 17H), 7.67 - 7.68 (m, I-ArH, 2H), 7.58 - 7.62 (m, ArH, 2H), 6.56 - 6.63 (dd, CH=CH2, 1H), 5.80 - 5.84 (d, CH=CH2, 1H), 5.23 - 5.25 (d, CH=CH2, 1H)

[0473] Compound (M0-13): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 8.05 (d, I-ArH, 1H), 8.02 (d, I-ArH, 2H), 7.74 - 7.90 (m, ArH + I-ArH, 17H), 6.56 - 6.63 (dd, CH=CH2, 1H), 5.80 - 5.84 (d, CH=CH2, 1H), 5.23 - 5.25 (d, CH=CH2, 1H), 4.54 (s, CH2, 2H)

[0474] Compound (M0-14): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 8.02 (d, I-ArH, 2H), 7.74 - 7.90 (m, ArH, 15H), 7.67 - 7.68 (m, I-ArH, 2H), 6.56 - 6.63 (dd, CH=CH2, 1H), 5.80 - 5.84 (d, CH=CH2, 1H), 5.23 - 5.25 (d, CH=CH2, 1H), 4.54 (s, CH2, 2H)

[0475] Compound (M0-15): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 8.05 (d, I-ArH, 1H), 7.77 - 7.98 (m, ArH + I-ArH, 16H), 7.60 - 7.64 (m, ArH, 2H), 6.56 - 6.63 (dd, CH=CH2, 1H), 5.80 - 5.84 (d, CH=CH2, 1H), 5.23 - 5.25 (d, CH=CH2, 1H)

[0476] Compound (M0-16): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 8.02 (d, I-ArH, 2H), 7.77 - 7.98 (m, ArH, 17H), 6.56 - 6.63 (dd, CH=CH2, 1H), 5.80 - 5.84 (d, CH=CH2, 1H), 5.23 - 5.25 (d, CH=CH2, 1H), 4.54 (s, CH2, 2H)

[0477] Compound (M0-17): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 8.24 (d, ArH, 4H), 8.02 (d, I-ArH, 2H), 7.74 - 7.96 (m, ArH, 5H), 7.59 (t, ArH, 2H), 7.47 (t, ArH, 4H), 6.56 - 6.63 (dd, CH=CH2, 1H), 5.80 - 5.84 (d, CH=CH2, 1H), 5.23 - 5.25 (d, CH=CH2, 1H), 4.54 (s, CH2, 2H),

[0478] Compound (M0-18): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 8.02 (d, I-ArH, 2H), 7.74 - 7.96 (m, ArH, 5H), 7.50 - 7.60 (m, ArH, 5H), 6.56 - 6.63 (dd, CH=CH2, 1H), 5.80 - 5.84 (d, CH=CH2, 1H), 5.23 - 5.25 (d, CH=CH2, 1H), 4.54 (s, CH2, 2H), 4.50 (s, CH2, 2H), 3.02 (s, CH3, 9H)

[0479] Compound (M0-19): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 7.74 - 7.90 (m, ArH, 15H), 7.55 - 7.59 (m, I-ArH, 2H), 6.73 - 6.77 (m, I-ArH, 2H), 5.98 - 6.02 (d, CH2, 1H), 5.64 - 5.68 (d, CH2, 1H), 1.75 (s, CH3, 3H)

[0480] Compound (M0-20): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 8.05 (d, I-ArH, 1H), 7.74 - 7.90 (m, ArH + I-ArH, 17H), 5.98 - 6.02 (d, CH2, 1H), 5.64 - 5.68 (d, CH2, 1H), 1.75 (s, CH3, 3H)

[0481] Compound (M0-21): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 8.32 (d, I-ArH, 1H), 8.05 (d, I-ArH, 1H), 7.74 - 7.94 (m, ArH, 20H), 5.98 - 6.02 (d, CH2, 1H), 5.64 - 5.68 (d, CH2, 1H), 1.75 (s, CH3, 3H)

[0482] Compound (M0-22): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 8.32 (d, I-ArH, 1H), 8.05 (d, I-ArH, 1H), 7.74 - 7.90 (m, ArH, 15H), 7.55 - 7.59 (m, I-ArH, 2H), 6.63 - 6.67 (m, I-ArH, 2H), 5.98 - 6.02 (d, CH2, 1H), 5.64 - 5.68 (d, CH2, 1H), 1.75 (s, CH3, 3H)

[0483] (Synthesis of Compound (M-100)) 3,5-Diiodosalicylic acid (40.0 g) and THF (160.0 g) were charged and stirred to dissolve. To this, 1,1'-carbonyldiimidazole (CDI) (20.0 g) was added, and then the temperature was raised to 60 °C in a water bath and stirred for 1 hour. To this, Compound (K-1) (38.3 g) was added and aged for 1 hour. Then, ultrapure water (160.0 g) and methylene chloride (160.0 g) were charged and stirred. After stopping the stirring, the aqueous layer was removed, and the organic layer was washed with ultrapure water (160 g). The organic layer was concentrated under reduced pressure, and the concentrated residue was crystallized with acetonitrile / tert-butyl methyl ether to obtain 43.2 g of a white compound (Intermediate A).

[0484] 4-Vinylbenzoic acid (9.6 g), Intermediate (I-A) (40.0 g), 4-dimethylaminopyridine (0.7 g), and dichloromethane (400.0 g) were mixed and stirred at 0 °C, and 1,3-diisopropylcarbodiimide (8.9) was added thereto. After stirring at room temperature for 3 hours, it was concentrated under reduced pressure. The concentrated residue was crystallized with acetonitrile / tert-butyl methyl ether to obtain 31.5 g of a white compound (Intermediate (I-B)).

[0485] Intermediate B (30.0 g), Compound E (25.0 g), dichloromethane (150.0 g), and ultrapure water (60.0 g) were mixed and stirred at room temperature, followed by liquid separation. The organic layer was washed 5 times with ultrapure water (60.0 g) and then concentrated under reduced pressure to obtain 30.5 g of Compound (M-100).

[0486] For the obtained Compound (M-100), NMR measurement was performed, and its structure was identified based on the analysis results shown below. 1H-NMR (DMSO-d6, 400 MHz): δ (ppm) = 8.31 (d, 1H), 8.13 (d, 1H), 7.72 - 8.00 (m, 17H), 7.60 - 7.64 (m, 2H), 6.92 - 6.85 (m, 1H), 6.07 (d, 1H), 5.49 (d, 1H), 4.67 (m, 2H).

[0487]

Chemical formula

[0488] <Production of Polymer Compounds> Polymer compounds (A1-1) to (A1-27), (A2-100), and (A2-1) to (A2-6) were obtained by radical polymerization using monomers that induce the constituent units of each polymer compound in a predetermined molar ratio, and then performing a deprotection reaction if necessary. Polymer compounds (A1-1) to (A1-27), (A2-100), and (A2-1) to (A2-6) are shown below. In the following formulas, l, m, n, and o represent the composition ratios (molar ratios) of the respective constituent units.

[0489]

Chemical formula

[0490]

Chemical formula

[0491]

Chemical formula

[0492]

Chem.

[0493]

Chem.

[0494]

Chem.

[0495]

Chem.

[0496]

Chem.

[0497] For the high molecular compounds (A1-1) to (A1-27), the weight average molecular weight (Mw) and the molecular weight dispersity (Mw / Mn) were determined by GPC measurement (in terms of standard polystyrene). Also, for the high molecular compounds (A1-1) to (A1-27), 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 in Table 1.

[0498]

Table 1

[0499]

Table 2

[0500] <Preparation of Resist Composition> (Examples 1 to 30, Comparative Examples 1 to 7) The resist compositions of each example were respectively prepared by mixing and dissolving the components shown in Tables 3 to 5.

[0501] [Table 3]

[0502] [Table 4]

[0503] [Table 5]

[0504] In Tables 3 to 5, each abbreviation has the following meaning respectively. The numerical values in [ ] are the blending amounts (parts by mass). (A1)-1 to (A1)-27: The above-mentioned polymer compounds (A1-1) to (A1-27). (A2)-1 to (A2)-7: The above-mentioned polymer compounds (A2-1) to (A2-7).

[0505] (B1)-1: An acid generator composed of the following compound (B1-1).

[0506] [Chemical formula]

[0507] (D1)-1 to (D1)-2: An acid diffusion control agent composed of the compounds represented by the following chemical formulas (D1-1) to (D1-2).

[0508] [Chemical formula]

[0509] (S)-1: A mixed solvent of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 60 / 40 (mass ratio).

[0510] <Formation of Resist Pattern> Step of forming a resist film: On an 8-inch silicon substrate treated with hexamethyldisilazane (HMDS), each resist composition of each example was applied using a spinner, and pre-baked (PAB) at a temperature of 110 °C for 60 seconds on a hot plate and dried to form a resist film with a thickness of 50 nm.

[0511] Step of exposing the resist film: Next, using an electron beam lithography apparatus JEOL-JBX-9300FS (manufactured by JEOL Ltd.), a contact hole pattern (hereinafter referred to as "CH pattern") in which holes with a diameter of 32 nm were arranged at equal intervals (pitch 64 nm) was drawn (exposed) on the resist film at an acceleration voltage of 100 kV. Thereafter, post-exposure bake (PEB) treatment was performed at 100 °C for 60 seconds.

[0512] Step of developing the exposed resist film: Next, at 23 °C, alkali development was performed for 60 seconds using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) "NMD-3" (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.). Thereafter, water rinsing was performed for 15 seconds using pure water. As a result, a CH pattern in which holes with a diameter of 32 nm were arranged at equal intervals (pitch 64 nm) was formed.

[0513] [Evaluation of Optimum Exposure Dose (Eop)] The optimum exposure dose Eop (μC / cm 2 ) at which a CH pattern of the target size is formed by the above <Formation of Resist Pattern> was determined. This is shown in Tables 6 to 8 as "Eop (μC / cm 2 )".

[0514] [Evaluation of In-Plane Uniformity of Pattern Dimensions (CDU)] Regarding the CH pattern formed by the above <formation of resist pattern>, using a length-measuring SEM (scanning electron microscope, acceleration voltage 500 V, product name: CG5000, manufactured by Hitachi High-Technologies Corporation), it was observed 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 obtained. The results are shown in Tables 6 to 8 as "CDU (nm)". The smaller the value of 3σ obtained in this way, the higher the dimensional (CD) uniformity of the plurality of holes formed in the resist film.

[0515] [Evaluation of limit resolution] Regarding 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 that resolves was determined using a scanning electron microscope S-9380 (manufactured by Hitachi High-Technologies Corporation). The results are shown in Tables 3 to 8 as "resolution (nm)".

[0516] [Table 6]

[0517] [Table 7]

[0518] [Table 8]

[0519] As shown in Tables 5 to 8, it was confirmed that the resist compositions of Examples 1 to 30 maintained good sensitivity and improved both CDU and limit resolution compared to the resist compositions of Comparative Examples 1 to 7.

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 resin component (A1) whose solubility in a developer changes due to the action of the acid, wherein the resin component (A1) has a structural unit (a0) derived from a compound represented by the following general formula (a0-m), resist composition. 【Chemical 1】 [In the formula, W ０ represents a polymerizable group-containing group. Ar ０１ and Ar ０２ each independently represent an aromatic ring. L ０ represents a single bond or a divalent linking group. Ra ０１ and Ra ０２ each independently represent a substituent other than iodine. Rx ０ represents a hydrocarbon group which may have a substituent. m01 and m02 each independently represent an integer of 0 or more as long as the valence allows, and m01 + m02 ≧ 1. n01 and n02 each independently represent an integer of 0 or more as long as the valence allows. r01 and r02 each independently represent 0 or 1, and r01 + r02 ≧ 1. k0 represents 0 or 1, and r02 + k0 = 1. When n01 is an integer of 2 or more, two or more Ra ０１ may be the same as or different from each other. When n02 is an integer of 2 or more, two or more Ra ０１ may be the same as or different from each other. m is an integer of 1 or more, and M ｍ＋ is an m-valent cation. ]

2. The resist composition according to claim 1, wherein m01 and m02 in the general formula (a0-m) satisfy 1 ≦ m01 + m02 ≦ 5.

3. The resist composition according to claim 1 or 2, wherein the structural unit (a0) is a structural unit represented by the following general formula (a0-1). [Chemical Formula 2] [In the formula, R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. Ar ０１ and Ar ０２ each independently represents an aromatic ring. L ０ represents a single bond or a divalent linking group. Ra ０１ and Ra ０２ each independently represents a substituent other than iodine. Rx ０ represents a hydrocarbon group which may have a substituent. m01 and m02 each independently represent an integer of 0 or more as long as the valence allows, and m01 + m02 ≧ 1. n01 and n02 each independently represent an integer of 0 or more as long as the valence allows. r01 and r02 each independently represent 0 or 1, and r01 + r02 ≧ 1. k0 represents 0 or 1, and r02 + k0 = 1. When n01 is an integer of 2 or more, two or more Ra ０１ may be the same as or different from each other. When n02 is an integer of 2 or more, two or more Ra ０１ may be the same as or different from each other. m is an integer of 1 or more, and M ｍ＋ is an m-valent cation. ]

4. The resist composition according to claim 1 or 2, wherein the structural unit (a0) is a structural unit represented by the following general formula (a0-2). 【Chemical Formula 3】 [In the formula, R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. Ar ０１ and Ar ０２ each independently represents an aromatic ring. L ０ represents a single bond or a divalent linking group. Ra ０１ and Ra ０２ each independently represents a substituent other than iodine. Rx ０ represents a hydrocarbon group which may have a substituent. m01 and m02 each independently represent an integer of 0 or more as long as the valence allows, and m01 + m02 ≧ 1. n01 and n02 each independently represent an integer of 0 or more as long as the valence allows. r01 and r02 each independently represent 0 or 1, and r01 + r02 ≧ 1. k0 represents 0 or 1, and r02 + k0 = 1. When n01 is an integer of 2 or more, two or more Ra ０１ may be the same as or different from each other. When n02 is an integer of 2 or more, two or more Ra ０１ may be the same as or different from each other. A ０ represents an oxygen atom or -NH-. m is an integer of 1 or more, and M ｍ＋ is an m-valent cation. ]

5. The resist composition according to claim 1 or 2, wherein the structural unit (a0) is a structural unit represented by the following general formula (a0-3). 【Chemical 4】 [In the formula, R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. Ar ０２ represents an aromatic ring. Ra ０２ represents a substituent other than iodine. m03 represents an integer of 1 or more as long as the valence allows. n02 represents an integer of 0 or more as long as the valence allows. When n02 is an integer of 2 or more, two or more Ra ０１ may be the same as or different from each other. m is an integer of 1 or more, and M ｍ＋ is an m-valent cation. ]

6. A resist pattern forming method having a step of forming a resist film using the resist composition according to claim 1 or 2 on a support, a step of exposing the resist film, and a step of developing the exposed resist film to form a resist pattern.

7. A compound represented by the following general formula (a0-m). [Chemical Formula 5] [In the formula, W ０ represents a polymerizable group-containing group. Ar ０１ and Ar ０２ each independently represent an aromatic ring. L ０ represents a single bond or a divalent linking group. Ra ０１ and Ra ０２ each independently represent a substituent other than iodine. Rx ０ represents a hydrocarbon group which may have a substituent. m01 and m02 each independently represent an integer of 0 or more as long as the valence allows, and m01 + m02 ≧ 1. n01 and n02 each independently represent an integer of 0 or more as long as the valence allows. r01 and r02 each independently represent 0 or 1, and r01 + r02 ≧ 1. k0 represents 0 or 1, and r02 + k0 = 1. When n01 is an integer of 2 or more, two or more Ra ０１ may be the same as or different from each other. When n02 is an integer of 2 or more, two or more Ra ０１ may be the same as or different from each other. m is an integer of 1 or more, and M ｍ＋ is an m-valent cation. ]

8. The compound according to claim 7, wherein m01 and m02 in the general formula (a0-m) satisfy 1 ≦ m01 + m02 ≦ 5.

9. The compound according to claim 7 or 8, which is a compound represented by the following general formula (a0-m1). 【Chemical Formula 6】 [In the formula, R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. Ar ０１ and Ar ０２ each independently represents an aromatic ring. L ０ represents a single bond or a divalent linking group. Ra ０１ and Ra ０２ each independently represents a substituent other than iodine. Rx ０ represents a hydrocarbon group which may have a substituent. m01 and m02 each independently represent an integer of 0 or more as long as the valence allows, and m01 + m02 ≧ 1. n01 and n02 each independently represent an integer of 0 or more as long as the valence allows. r01 and r02 each independently represent 0 or 1, and r01 + r02 ≧ 1. k0 represents 0 or 1, and r02 + k0 = 1. When n01 is an integer of 2 or more, two or more Ra ０１ may be the same as or different from each other. When n02 is an integer of 2 or more, two or more Ra ０１ may be the same as or different from each other. m is an integer of 1 or more, and M ｍ＋ is an m-valent cation. ]

10. The compound according to claim 7 or 8, which is a compound represented by the following general formula (a0-m2). 【Chemical Formula 7】 [In the formula, R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. Ar ０１ and Ar ０２ each independently represents an aromatic ring. L ０ represents a single bond or a divalent linking group. Ra ０１ and Ra ０２ each independently represents a substituent other than iodine. Rx ０ represents a hydrocarbon group which may have a substituent. m01 and m02 each independently represent an integer of 0 or more as long as the valence allows, and m01 + m02 ≧ 1. n01 and n02 each independently represent an integer of 0 or more as long as the valence allows. r01 and r02 each independently represent 0 or 1, and r01 + r02 ≧ 1. k0 represents 0 or 1, and r02 + k0 = 1. When n01 is an integer of 2 or more, two or more Ra ０１ may be the same as or different from each other. When n02 is an integer of 2 or more, two or more Ra ０１ may be the same as or different from each other. A ０ represents an oxygen atom or -NH-. m is an integer of 1 or more, and M ｍ＋ is an m-valent cation. ]

11. The compound according to claim 7 or 8, which is a compound represented by the following general formula (a0-m3). [Chemical Formula 8] [In the formula, R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. Ar ０２ represents an aromatic ring. Ra ０２ represents a substituent other than iodine. m03 represents an integer of 1 or more as long as the valence permits. n02 represents an integer of 0 or more as long as the valence permits. When n02 is an integer of 2 or more, two or more Ra ０１ may be the same as or different from each other. m is an integer of 1 or more, and M ｍ＋ is an m-valent cation. ]

12. A polymer compound containing a structural unit derived from the compound according to claim 7 or 8.

13. An acid diffusion control agent containing the compound according to claim 7 or 8.

Images