Resist composition, resist pattern formation method, and compound

Abstract

To provide a resist composition that achieves enhanced sensitivity when forming a resist pattern, while offering superior resolution, a resist pattern forming method using the resist composition, and a compound suitable as raw material for base components for use in the resist composition.SOLUTION: A resist composition comprises a resin component (A1) having a constitutional unit (a0) derived from a compound represented by general formula (a0-1) (where R is a hydrogen atom, a C1 to 5 alkyl group or a C1 to 5 halogenated alkyl group; La01 and La02 independently represent a single bond or a divalent linking group; Ar is an aromatic ring; Ra01 is a substituent other than a hydroxy group).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resist composition, a resist pattern formation method, and a compound. [Background technology]

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

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

[0004] For example, Patent Document 1 discloses a resist composition containing a resin component having a styrene carboxylic acid skeleton and a structural unit in which an acid-dissociable group is bonded to the side chain terminal. This resist composition is disclosed to enable high sensitivity and improve lithography characteristics such as resolution and LWR. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2019-219469 [Overview of the project] [Problems that the invention aims to solve]

[0006] Further advancements in lithography technology and the expansion of its application fields are leading to rapid miniaturization of patterns. Consequently, when manufacturing semiconductor devices and other components, there is a demand for technologies that can form fine patterns with good shape. For example, in EUV and EB lithography, the goal is to form fine patterns of several tens of nanometers.

[0007] The present invention has been made in view of the above circumstances, and aims to provide a resist composition that can be made highly sensitive and has good resolution when forming a resist pattern, a method for forming a resist pattern using the resist composition, and a compound useful as a raw material for a substrate component used in the resist composition. [Means for solving the problem]

[0008] To solve the above problems, the present invention employs the following configuration. In other words, a first aspect of the present invention is a resist composition that generates acid upon exposure and whose solubility in a developer changes due to the action of the acid, the resist composition 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 constituent unit (a0) derived from a compound represented by the following general formula (a0-1).

[0009] [ka] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halogen having 1 to 5 carbon atoms; La 01 and La 02 Each is independently a single bond or a divalent linking group; Ar is an aromatic ring; Ra 01 is a substituent other than a hydroxyl group; m1 is an integer greater than or equal to 0, as long as the valence allows; and Rpg is an acid-dissociable group represented by the following general formula (a0-pg).

[0010] [ka] [In the formula, * represents -La 02 is a bond that binds to -O- in -C(=O)-O-; Ra 02 is a hydrogen atom or a hydrocarbon group; C 1 is a secondary carbon atom or a tertiary carbon atom; A is an aliphatic ring having 6 or more carbon atoms; C 2 and C 3 are each independently a carbon atom constituting a carbon-carbon unsaturated bond that forms a part of the ring skeleton of the aliphatic ring having 6 or more carbon atoms in A; Ra 03 and Ra 04 are each independently a hydrogen atom or a hydrocarbon group; Ra 05 is a hydrocarbon group; n1 is an integer of 0 or more as long as the valence permits; provided that C 1 does not constitute a part of the crosslinked structure; Ra 02 , Ra 03 and Ra 04 are all hydrogen atoms, n1 is an integer of 1 or more.]

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

[0012] A third aspect of the present invention is a compound represented by the following general formula (a0-1).

[0013] [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; La 01 and La 02 are each independently a single bond or a divalent linking group; Ar is an aromatic ring; Ra 01 is a substituent other than a hydroxy group; m1 is an integer of 0 or more as long as the valence permits; Rpg is an acid dissociable group represented by the following general formula (a0-pg).]

[0014] [ka] [In the formula, * represents -La 02 It is a bond that connects to -O- in -C(=O)-O-; Ra 02 C is a hydrogen atom or a hydrocarbon group; 1 is a secondary or tertiary carbon atom; A is an aliphatic ring with 6 or more carbon atoms; C 2 and C 3 Each of these is an independent carbon atom that constitutes a carbon-carbon unsaturated bond that forms part of the ring skeleton of an aliphatic ring with 6 or more carbon atoms in A; Ra 03 and Ra 04 Each is independently a hydrogen atom or a hydrocarbon group; Ra 05 is a hydrocarbon group; n1 is a non-negative integer as long as the valence allows; however, C 1 It does not constitute part of the cross-linking structure; Ra 02 Ra 03 and Ra 04 If both are hydrogen atoms, then n1 is an integer greater than or equal to 1. [Effects of the Invention]

[0015] According to the present invention, it is possible to provide a resist composition that can be made highly sensitive and has good resolution when forming a resist pattern, a method for forming a resist pattern using the resist composition, and a compound useful as a raw material for a substrate component used in the resist composition. [Modes for carrying out the invention]

[0016] In this specification and in the claims, "aliphatic" is defined as a concept relative to aromatic, meaning a group, compound, etc., that does not possess aromaticity. Unless otherwise specified, "alkyl group" includes linear, branched, and cyclic monovalent saturated hydrocarbon groups. The same applies to alkyl groups within alkoxy groups. Unless otherwise specified, the term "alkylene group" includes linear, branched, and cyclic divalent saturated hydrocarbon groups. Examples of "halogen atoms" include fluorine, chlorine, bromine, and iodine atoms. "Constituent unit" refers to the monomer unit (monomer unit) that makes up a polymer compound (resin, polymer, copolymer). When it is stated that a group "may have substituents," this includes both cases where a hydrogen atom (-H) is substituted with a monovalent group and cases where a methylene group (-CH2-) is substituted with a divalent group. "Exposure" is a concept that includes all forms of radiation exposure.

[0017] An "acid-degradable group" is a group that has acid-degradability, meaning that at least some of the bonds in its structure can be cleaved by the action of an acid. Examples of acid-degradable groups whose polarity increases upon the action of an acid include groups that decompose upon the action of an acid to produce polar groups. Examples of polar groups include carboxyl groups, hydroxyl groups, amino groups, and sulfo groups (-SO3H). More specifically, examples of acid-degradable groups include groups in which the aforementioned polar group is protected by an acid-dissociable group (for example, a group in which the hydrogen atom of an OH-containing polar group is protected by an acid-dissociable group).

[0018] The term "acid-dissociable group" refers to both (i) a group that has acid-dissociability, in which the bond between the acid-dissociable group and an adjacent atom can be cleaved by the action of an acid, and (ii) a group in which, after some of the bonds are cleaved by the action of an acid, a decarboxylation reaction occurs, further causing the bond between the acid-dissociable group and an adjacent atom to be cleaved. The acid-dissociable group constituting the acid-degradable group must be less polar than the polar group generated by its dissociation. This means that when the acid-dissociable group dissociates due to the action of acid, a polar group with higher polarity is generated, increasing the polarity. As a result, the overall polarity of component (A1) increases. This increase in polarity relatively changes the solubility in the developer; solubility increases when the developer is an alkaline developer, and decreases when the developer is an organic developer.

[0019] "Base material components" are organic compounds that have film-forming ability. Organic compounds used as base material components are broadly classified into nonpolymers and polymers. Nonpolymers typically have a molecular weight of 500 or more and less than 4000 (hereinafter referred to as "low molecular weight compounds"). Hereinafter, when "resins," "high molecular weight compounds," or "polymers" are used, polymers with a molecular weight of 1000 or more are referred to. For polymers, the weight-average molecular weight in terms of polystyrene obtained by GPC (gel permeation chromatography) shall be used as the molecular weight.

[0020] "Induced structural units" refer to structural units formed by the cleavage of multiple bonds between carbon atoms, such as ethylenic double bonds. "Acrylic acid ester" may have a substituent that replaces the hydrogen atom bonded to the α-carbon atom. αx ) is an atom or group other than a hydrogen atom. Also, substituents (R αx Itaconic acid diesters in which ) are substituted with substituents containing an ester bond, or substituents (R αx This also includes α-hydroxyacrylic esters in which the α group is substituted with a hydroxyalkyl group or a group that modifies the hydroxyl group thereof. Unless otherwise specified, the α-carbon atom of the acrylic acid ester refers to the carbon atom to which the carbonyl group of acrylic acid is bonded. Hereafter, acrylic acid esters in which the hydrogen atom bonded to the α-carbon atom is replaced by a substituent are sometimes called α-substituted acrylic acid esters.

[0021] The term "derivative" refers to a compound in which the α-position hydrogen atom of the target compound is substituted with another substituent such as an alkyl group or alkyl halide, as well as derivatives thereof. Examples of such derivatives include those in which the hydrogen atom of the hydroxyl group of the target compound (which may have the α-position hydrogen atom substituted with a substituent) is substituted with an organic group; and those in which a substituent other than a hydroxyl group is bonded to the target compound (which may have the α-position hydrogen atom substituted with a substituent). Unless otherwise specified, the α-position refers to the first carbon atom adjacent to the functional group. As substituents that substitute the hydrogen atom at the α-position of hydroxystyrene, R αx Similar examples include the above.

[0022] In this specification and in the claims, depending on the structure represented by the chemical formula, an asymmetric carbon may be present, and enantioisomers or diastereomers may exist. In such cases, a single chemical formula will represent all of these isomers. These isomers may be used individually or as a mixture.

[0023] (Resist composition) The resist composition of this embodiment generates acid upon exposure, and its solubility in the developer changes due to the action of the acid. Such a resist composition contains a base component (A) (hereinafter also referred to as "component (A)") whose solubility in the developer changes due to the action of an acid. Component (A1) has a constituent unit (a0) derived from a compound represented by the general formula (a0) described later. Furthermore, the resist composition of this embodiment may further contain other components in addition to component (A). Examples of other components include components (B), (D), (E), (F), and (S), which will be described later.

[0024] In the resist composition of this embodiment, component (A) may generate acid upon exposure, or an additive component formulated separately from component (A) may generate acid upon exposure. The resist composition of this embodiment may specifically (1) further contain an acid generating agent component (B) (hereinafter referred to as "component (B)") that generates acid upon exposure; (2) component (A) may be a component that generates acid upon exposure; or (3) component (A) may be a component that generates acid upon exposure and also contains component (B). In other words, in the cases of (2) and (3) above, component (A) is a "base component that generates acid upon exposure and whose solubility in the developer changes due to the action of the acid." When component (A) is a base component that generates acid upon exposure and whose solubility in the developer changes due to the action of the acid, it is preferable that component (A1), described later, is a resin that generates acid upon exposure and whose solubility in the developer changes due to the action of the acid. As such a resin, a polymer compound having a constituent unit that generates acid upon exposure can be used. Known constituent units that generate acid upon exposure can be used.

[0025] In this embodiment, the resist composition is preferably the one described in (1) above. That is, the resist composition of this embodiment preferably contains component (A) and component (B).

[0026] When a resist film is formed using the resist composition of this embodiment and selective exposure is performed on the resist film, for example, acid is generated from component (B) in the exposed areas of the resist film, and the solubility of component (A) in the developer changes due to the action of this acid, while the solubility of component (A) in the developer does not change in the unexposed areas of the resist film. As a result, a difference in solubility in the developer occurs between the exposed and unexposed areas. Therefore, when the resist film is developed, if the resist composition is positive type, the exposed areas of the resist film are dissolved and removed to form a positive type resist pattern, and if the resist composition is negative type, the unexposed areas of the resist film are 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. Furthermore, the resist composition of this embodiment may be for an alkaline development process that uses an alkaline developer for the development process during resist pattern formation, or for a solvent development process that uses a developer containing an organic solvent (organic developer) for the development process.

[0028] <(A) component> In the resist composition of this embodiment, component (A) includes a resin component (A1) (hereinafter also referred to as "component (A1)") whose solubility in the developer solution changes due to the action of an acid. By using component (A1), the polarity of the substrate component changes before and after exposure, so good development contrast can be obtained not only in the alkaline development process but also in the solvent development process. (A) Component (A1) may be used in combination with other high-molecular-weight compounds and / or low-molecular-weight compounds. Component (A) may be a "base component that generates acid upon exposure and whose solubility in the developer changes due to the action of the acid." If component (A) is a base component that generates acid upon exposure and whose solubility in the developer changes due to the action of the acid, it is preferable that component (A1) is a resin that generates acid upon exposure and whose solubility in the developer changes due to the action of the acid. As such a resin, a polymer compound having a constituent unit that generates acid upon exposure can be used. Known constituent units that generate acid upon exposure can be used.

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

[0030] (A1) About the ingredients Component (A1) is a resin component whose solubility in the developer changes due to the action of acid. Component (A1) has a constituent unit (a0) derived from a compound represented by the following general formula (a0-1). Component (A1) may have other constituent units in addition to the constituent unit (a0) as needed.

[0031] [ka] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halogen having 1 to 5 carbon atoms; La 01 and La 02Each is independently a single bond or a divalent linking group; Ar is an aromatic ring; Ra 01 is a substituent other than a hydroxyl group; m1 is an integer greater than or equal to 0, as long as the valence allows; and Rpg is an acid-dissociable group represented by the following general formula (a0-pg).

[0032] [ka] [In the formula, * represents -La 02 It is a bond that connects to -O- in -C(=O)-O-; Ra 02 C is a hydrogen atom or a hydrocarbon group; 1 is a secondary or tertiary carbon atom; A is an aliphatic ring with 6 or more carbon atoms; C 2 and C 3 Each of these is an independent carbon atom that constitutes a carbon-carbon unsaturated bond that forms part of the ring skeleton of an aliphatic ring with 6 or more carbon atoms in A; Ra 03 and Ra 04 Each is independently a hydrogen atom or a hydrocarbon group; Ra 05 is a hydrocarbon group; n1 is a non-negative integer as long as the valence allows; however, C 1 It does not constitute part of the cross-linking structure; Ra 02 Ra 03 and Ra 04 If both are hydrogen atoms, then n1 is an integer greater than or equal to 1.

[0033] In the above formula (a0-1), R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms. From the standpoint of industrial availability, a hydrogen atom, a methyl group, or a trifluoromethyl group is more preferred, a hydrogen atom or a methyl group is even more preferred, and a hydrogen atom is particularly preferred.

[0034] In the above formula (a0-1), La 01 and La 02 The divalent linking group in this is not particularly limited, but suitable examples include divalent hydrocarbon groups which may have substituents, and divalent linking groups which contain heteroatoms.

[0035] La 01 Preferably, the group is a single bond, an ester bond [-C(=O)-O-, -OC(=O)-], an ether bond (-O-), a linear or branched alkylene group, or a combination thereof, with single bonds and ester bonds [-C(=O)-O-, -OC(=O)-] being more preferred. In particular, from the viewpoint of increasing sensitivity and improving resolution, La 01 In this regard, single bonds are particularly preferred.

[0036] La 02 Preferably, the group consists of a single bond, an ester bond [-C(=O)-O-, -OC(=O)-], an ether bond (-O-), a linear or branched alkylene group, or a combination thereof. 021 -, -OC(=O)-La 021 -] is preferable. 021 It is an alkylene group having 1 to 5 carbon atoms. In particular, from the viewpoint of increasing sensitivity and improving resolution, La 02 In this regard, single bonds are particularly preferred.

[0037] In formula (a0-1) above, the aromatic ring in Ar is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene. Among these, Ar is preferably a benzene ring, a naphthalene ring, or an anthracene ring, more preferably a benzene ring or a naphthalene ring, and even more preferably a benzene ring.

[0038] In the above formula (a0-1), Ra 01Examples of substituents in include C1-C5 alkyl groups, carboxyl groups, halogen atoms, C1-C5 halogenated alkyl groups, C1-C5 alkoxy groups, and C1-C5 alkyloxycarbonyl groups. 01 Preferably, the substituents in are alkyl groups having 1 to 5 carbon atoms, more preferably alkyl groups having 1 to 3 carbon atoms, and even more preferably methyl groups.

[0039] In the above formula (a0-1), m1 is preferably an integer between 0 and 2, preferably 0 or 1, and more preferably 0.

[0040] In the above formula (a0-pg), Ra 02 The hydrocarbon group in this compound may be linear or branched, and may be saturated or unsaturated. Ra 02 Examples of saturated hydrocarbon groups in this context include linear alkyl groups having 1 to 12 carbon atoms and branched alkyl groups having 1 to 12 carbon atoms. Ra 02 Examples of unsaturated hydrocarbon groups in this context include linear alkenyl groups with 2 to 12 carbon atoms, branched alkenyl groups with 2 to 12 carbon atoms, and linear or branched alkynyl groups with 2 to 12 carbon atoms.

[0041] Ra 02 Examples of linear alkyl groups having 1 to 12 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. Linear alkyl groups having 1 to 5 carbon atoms are preferred, methyl, ethyl, or butyl groups are more preferred, and methyl or ethyl groups are even more preferred.

[0042] Ra 02 Examples of branched alkyl groups having 1 to 12 carbon atoms include isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 1,1-diethylpropyl group, and 2,2-dimethylbutyl group, with branched alkyl groups having 3 to 5 carbon atoms being preferred, and isopropyl group being more preferred.

[0043] Ra 02 Examples of unsaturated hydrocarbon groups in this context include -CH=CH2, -CH=CHCH3, -CH2-CH=CH2, -CH2-CH=CHCH3, -CH2-(CH3)C=CH2, -CH2CH2-CH=CH2, -CH2CH2-(CH3)C=CH2, -C≡CH, -C≡CCH3, -CH2-C≡CH, and -CH2-C≡CCH3.

[0044] In the above formula (a0-pg), Ra 02 Preferably, it is a hydrogen atom or a saturated hydrocarbon group.

[0045] In the above formula (a0-pg), Ra 02 If C is a hydrogen atom, 1 It is a secondary carbon atom, Ra 02 If C is an alkyl group, 1 It is a tertiary carbon atom.

[0046] In the above formula (a0-pg), the aliphatic ring in A may be either a polycyclic or monocyclic group. As the aliphatic ring, which is a monocyclic group, a group obtained by removing one hydrogen atom from a monocycloalkene is preferred. The monocycloalkene is preferably one having 6 to 10 carbon atoms, and specific examples include cyclohexene, cycloheptene, cyclooctene, cyclononene, and cyclodecene. As for the cyclic alkene, which is a polycyclic group, a group obtained by removing one hydrogen atom from a polycycloalkene is preferred, and as the polycycloalkene, those having 7 to 12 carbon atoms are preferred, and specifically, examples include bicyclo[3.1.1]hepta-2-ene, tricyclodecene, tetracyclododecene, and the like. Among the aliphatic rings with 6 or more carbon atoms in A, a group obtained by removing one hydrogen atom from a monocycloalkene or polycycloalkene is more preferred, a group obtained by removing one hydrogen atom from cyclohexene, cycloheptene, or bicyclo[3.1.1]hepta-2-ene is even more preferred, and a group obtained by removing one hydrogen atom from cyclohexene is particularly preferred.

[0047] In the above formula (a0-pg), Ra 03 and Ra 04 Examples of saturated hydrocarbon groups in this context include linear or branched alkyl groups. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15, and most preferably 1 to 10. Specifically, examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15, and most preferably 3 to 10. Specifically, examples include isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 1,1-diethylpropyl group, and 2,2-dimethylbutyl group.

[0048] Ra 03 and Ra 04 Examples of unsaturated hydrocarbon groups in this context include -CH=CH2, -CH=CHCH3, -CH2-CH=CH2, -CH2-CH=CHCH3, -CH2-(CH3)C=CH2, -CH2CH2-CH=CH2, -CH2CH2-(CH3)C=CH2, -C≡CH, -C≡CCH3, -CH2-C≡CH, and -CH2-C≡CCH3.

[0049] Among them, Ra 03 and Ra 04 Preferably, one of the atoms is a hydrogen atom, and the other is a chain-like alkyl group having 1 to 20 carbon atoms. 03 and Ra 04 One of the atoms is a hydrogen atom, and the other is more preferably a chain-like alkyl group having 1 to 10 carbon atoms, Ra 03 and Ra 04 It is even more preferable that one of the atoms is a hydrogen atom and the other is a chain-like alkyl group having 1 to 5 carbon atoms.

[0050] In the above formula (a0-pg), Ra 05The hydrocarbon group in this compound may be linear or branched, and may be saturated or unsaturated. Ra 05 Examples of saturated hydrocarbon groups in this context include linear alkyl groups having 1 to 12 carbon atoms and branched alkyl groups having 1 to 12 carbon atoms. Ra 05 Examples of unsaturated hydrocarbon groups in this context include linear alkenyl groups with 2 to 12 carbon atoms, branched alkenyl groups with 2 to 12 carbon atoms, and linear or branched alkynyl groups with 2 to 12 carbon atoms.

[0051] Ra 05 Examples of linear alkyl groups having 1 to 12 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. Linear alkyl groups having 1 to 5 carbon atoms are preferred, methyl, ethyl, or butyl groups are more preferred, and methyl or ethyl groups are even more preferred.

[0052] Ra 05 Examples of branched alkyl groups having 1 to 12 carbon atoms include isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 1,1-diethylpropyl group, and 2,2-dimethylbutyl group, with branched alkyl groups having 3 to 5 carbon atoms being preferred, and isopropyl group being more preferred.

[0053] Ra 05 Examples of unsaturated hydrocarbon groups in this context include -CH=CH2, -CH=CHCH3, -CH2-CH=CH2, -CH2-CH=CHCH3, -CH2-(CH3)C=CH2, -CH2CH2-CH=CH2, -CH2CH2-(CH3)C=CH2, -C≡CH, -C≡CCH3, -CH2-C≡CH, and -CH2-C≡CCH3.

[0054] In the above formula (a0-pg), Ra 05As for this, an alkyl group is preferable, an alkyl group having 1 to 5 carbon atoms is more preferable, an alkyl group having 1 to 3 carbon atoms is still more preferable, and a methyl group is particularly preferable.

[0055] In the formula (a0-pg), n1 is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.

[0056] In the formula (a0-pg), C 1 does not form a part of the crosslinked structure. Also, in the formula (a0-pg), Ra 02 , Ra 03 and Ra 04 are all hydrogen atoms, and n1 is an integer of 1 or more. That is, the aliphatic ring having 6 or more carbon atoms in A has at least one alkyl group as a substituent.

[0057] The structural unit (a0) may be a structural unit derived from a compound represented by the following general formula (a0-s1).

[0058] [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; La 01 and La 02 are each independently a single bond or a divalent linking group; Ar is an aromatic ring; Ra 01 is a substituent other than a hydroxy group; m1 is an integer of 0 or more as long as the valence allows; Cs is a secondary carbon atom; A is an aliphatic ring having 6 or more carbon atoms; C 2 and C 3 are each independently a carbon atom constituting a carbon-carbon unsaturated bond forming a part of the ring skeleton of the aliphatic ring having 6 or more carbon atoms in A; Ra 031 and Ra 041 are each independently a hydrogen atom or a hydrocarbon group; Ra 051 is a hydrocarbon group; n11 is an integer of 0 or more as long as the valence allows; provided that Ra 031 and Ra 041When all of them are hydrogen atoms, n11 is an integer of 1 or more.

[0059] In the formula (a0-s1), R, La 01 , La 02 , Ar, Ra 01 and m1 are the same as R, La 01 , La 02 , Ar, Ra 01 and m1 in the formula (a0-1) respectively. In the formula (a0-s1), A, C 2 and C 3 are the same as A, C 2 and C 3 in the formula (a0-pg) respectively. In the formula (a0-s1), Ra 031 , Ra 041 , Ra 051 and n11 are the same as Ra 03 , Ra 04 , Ra 05 and n1 in the formula (a0-pg) respectively.

[0060] The structural unit (a0) may be a structural unit derived from a compound represented by the following general formula (a0-t1).

[0061] [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; La 01 and La 02 are each independently a single bond or a divalent linking group; Ar is an aromatic ring; Ra 01 is a substituent other than a hydroxy group; m1 is an integer of 0 or more as long as the valence allows; Ra 022 is a hydrocarbon group; Ct is a tertiary carbon atom; A is an aliphatic ring having 6 or more carbon atoms; C 2 and C 3 are each independently a carbon atom constituting a carbon-carbon unsaturated bond forming a part of the ring skeleton of the aliphatic ring having 6 or more carbon atoms in A; Ra032 and Ra 042 Each is independently a hydrogen atom or a hydrocarbon group; Ra 052 n12 is a hydrocarbon group; n12 is a non-negative integer, as long as the valence allows.

[0062] In the above equation (a0-t1), R, La 01 La 02 , Ar, Ra 01 And m1 are R, La in the above formula (a0-1). 01 La 02 , Ar, Ra 01 And are the same as m1, respectively. In the above equation (a0-t1), A, C 2 and C 3 A and C in the above formula (a0-pg) are 2 and C 3 These are similar in each case. In the above formula (a0-t1), Ra 022 Ra 032 Ra 042 Ra 052 And n12 is Ra in the above formula (a0-pg). 02 Ra 03 Ra 04 Ra 05 And are the same as n1, respectively.

[0063] The following are specific examples of constituent units (a0). In each of the following equations, R α This represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0064] [ka]

[0065] [ka]

[0066] The constituent units (a0) of component (A1) may be one type or two or more types. The proportion of constituent units (a0) in component (A1) is preferably 40 to 80 mol%, more preferably 45 to 75 mol%, even more preferably 50 to 70 mol%, and particularly preferably 55 to 65 mol%, relative to the total amount (100 mol%) of all constituent units that make up component (A1). When the content of constituent unit (a0) is above the lower limit of the preferred range described above, sensitivity tends to be higher. On the other hand, keeping it below the upper limit makes it easier to balance with other constituent units, resulting in better resolution.

[0067] <<Other constituent units>> Component (A1) may have other constituent units in addition to the constituent unit (a0) described above, as needed. Other constituent units include, for example, constituent units (a1) containing acid-degradable groups whose polarity increases with the action of an acid (excluding those corresponding to constituent unit (a0)); constituent units (a10) represented by the general formula (a10-1) described later; constituent units (a2) containing lactone-containing cyclic groups; and constituent units (a8) derived from compounds represented by the general formula (a8-1) described later.

[0068] Regarding the constituent unit (a1): Constituent unit (a1) is a constituent unit that contains an acid-degradable group whose polarity increases upon the action of an acid. However, constituent units corresponding to constituent unit (a0) are excluded from constituent unit (a1).

[0069] Examples of acid-dissociable groups include those previously proposed as acid-dissociable groups for base resins used in chemically amplified resist compositions. Specifically, proposed acid-dissociable groups for base resins used in chemically amplified resist compositions include the following: "acetal-type acid-dissociable groups," "tertiary alkyl ester-type acid-dissociable groups," and "tertiary alkyloxycarbonyl acid-dissociable groups."

[0070] Acetal type acid dissociable group: As the acid-dissociable group that protects a carboxy group or a hydroxy group among the polar groups, for example, an acid-dissociable group represented by the following general formula (a1-r-1) (hereinafter sometimes referred to as an "acetal-type acid-dissociable group") can be mentioned.

[0071] [Chemical formula] [In the formula, Ra’ 1 , Ra’ 2 is a hydrogen atom or an alkyl group. Ra’ 3 is a hydrocarbon group, and Ra’ 3 may be bonded to either Ra’ 1 , Ra’ 2 to form a ring.]

[0072] 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 mentioned as the substituents that may be bonded to the carbon atom at the α-position in the description of the above α-substituted acrylic acid ester, and an alkyl group having 1 to 5 carbon atoms is 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. can be mentioned, a methyl group or an ethyl group is more preferable, and a methyl group is particularly preferable.

[0073] 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 methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, etc. Among these, methyl group, ethyl group, or n-butyl group is preferred, and methyl group or ethyl group is more preferred.

[0074] The branched alkyl group preferably has 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specifically, examples include isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 1,1-diethylpropyl group, 2,2-dimethylbutyl group, etc., with isopropyl group being preferred.

[0075] Ra' 3 When the hydrocarbon group is a cyclic hydrocarbon group, the hydrocarbon group may be an alicyclic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group. As a monocyclic alicyclic hydrocarbon group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferred. The monocycloalkane is preferably one having 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. As a polycyclic group, a alicyclic hydrocarbon group is preferred, which is a group obtained by removing one hydrogen atom from a polycycloalkane, and as a polycycloalkane, those having 7 to 12 carbon atoms are preferred, and specific examples include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.

[0076] Ra' 3 When the cyclic hydrocarbon group becomes an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. Examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced by heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of aromatic heterocycles include pyridine rings and thiophene rings. Ra' 3 Specific examples of aromatic hydrocarbon groups in this context include: a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group); a group obtained by removing one hydrogen atom from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and a group in which one of the hydrogen atoms of the aromatic hydrocarbon ring or aromatic heterocycle is substituted with an alkylene group (e.g., arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms in the alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocycle is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0077] Ra' 3 The cyclic hydrocarbon group in may have substituents. Examples of substituents include -R P1 , -R P2 -OR P1 , -R P2 -CO-R P1 , -R P2 -CO-OR P1 , -R P2 -O-CO-R P1 , -R P2 -OH, -R P2 -CN or -R P2 -COOH (These substituents are collectively referred to as "Ra" below) x5 It is also called "[...]." Examples include [...]. Here, R P1This is a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms, a monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms. Also, R P2 R is a single bond, a divalent chain saturated hydrocarbon group having 1 to 10 carbon atoms, a divalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms. However, R P1 and R P2 Some or all of the hydrogen atoms in the chain-like saturated hydrocarbon group, aliphatic cyclic saturated hydrocarbon group, and aromatic hydrocarbon group may be substituted with fluorine atoms. The aliphatic cyclic hydrocarbon group may have one or more of the substituents individually, or it may have one or more of each of the substituents. Examples of monovalent, chain-like saturated hydrocarbon groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl groups. Examples of monovalent aliphatic cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms include monocyclic aliphatic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and cyclododecyl groups; and polycyclic aliphatic saturated hydrocarbon groups such as bicyclo[2.2.2]octanyl, tricyclo[5.2.1.02,6]decanyl, tricyclo[3.3.1.13,7]decanyl, tetracyclo[6.2.1.13,6.02,7]dodecanyl, and adamantyl groups. Examples of monovalent aromatic hydrocarbon groups with 6 to 30 carbon atoms include groups obtained by removing one hydrogen atom from an aromatic hydrocarbon ring, such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene.

[0078] Ra' 3 However, Ra' 1 , Ra' 2 When the cyclic group is bonded to any of the above to form a ring, the cyclic group is preferably a 4- to 7-membered ring, and more preferably a 4- to 6-membered ring. Specific examples of the cyclic group include a tetrahydropyranyl group and a tetrahydrofuranyl group.

[0079] Tertiary alkyl ester type acid-dissociating group: Among the polar groups mentioned above, an example of an acid-dissociating group that protects a carboxyl group is the acid-dissociating group represented by the following general formula (a1-r-2). Furthermore, among the acid-dissociable groups represented by the following formula (a1-r-2), those composed of alkyl groups may, for convenience, be referred to below as "tertiary alkyl ester type acid-dissociable groups."

[0080] [ka] [In the formula, Ra' 4 ~Ra' 6 Each of these is a hydrocarbon group, Ra' 5 , Ra' 6 They may be joined to each other to form a ring.

[0081] Ra' 4 Examples of hydrocarbon groups include linear or branched alkyl groups, linear or cyclic alkenyl groups, linear alkynyl groups, or cyclic hydrocarbon groups. Ra' 4 In the above, linear or branched alkyl groups, cyclic hydrocarbon groups (monocyclic alicyclic hydrocarbon groups, polycyclic alicyclic hydrocarbon groups, aromatic hydrocarbon groups) are defined as the Ra' 3 Similar examples include the above. Ra' 4 The linear or cyclic alkenyl group in this is preferably an alkenyl group having 2 to 10 carbon atoms. Ra' 5 , Ra' 6 The hydrocarbon group is the aforementioned Ra' 3 Similar examples include the above.

[0082] Ra' 5 and Ra' 6When these groups bond to each other to form a ring, the following groups are preferred: the group represented by the general formula (a1-r2-1), the group represented by the general formula (a1-r2-2), and the group represented by the general formula (a1-r2-3). Meanwhile, Ra' 4 ~Ra' 6 When these are independent hydrocarbon groups that are not bonded to each other, the groups represented by the following general formula (a1-r2-4) are preferred.

[0083] [ka] [In formula (a1-r2-1), Ra' 10 This represents a linear or branched alkyl group having 1 to 12 carbon atoms, which may be partially substituted with halogen atoms or heteroatom-containing groups. 11 Ra' 10 This indicates a group that forms an aliphatic cyclic group with a bonded carbon atom. In formula (a1-r2-2), Ya is a carbon atom. Xa is a group that forms a cyclic hydrocarbon group with Ya. Some or all of the hydrogen atoms in this cyclic hydrocarbon group may be substituted. 101 ~Ra 103 Each of these is independently a hydrogen atom, a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms, or a monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms. Some or all of the hydrogen atoms in these linear saturated hydrocarbon groups and aliphatic cyclic saturated hydrocarbon groups may be substituted. 101 ~Ra 103 Two or more of these may be bonded to each other to form a cyclic structure. In formula (a1-r2-3), Yaa is a carbon atom. Xaa is a group that forms an aliphatic cyclic group together with Yaa. Ra 104 is an aromatic hydrocarbon group which may have substituents. In formula (a1-r2-4), Ra' 12 and Ra' 13 Each of these is independently a monovalent, chain-like saturated hydrocarbon group having 1 to 10 carbon atoms. Some or all of the hydrogen atoms in this chain-like saturated hydrocarbon group may be substituted. 14 is a hydrocarbon group that may have substituents. * indicates a bond (the same applies hereafter).

[0084] In the above equation (a1-r2-1), Ra' 10 This is a linear or branched alkyl group having 1 to 12 carbon atoms, which may be partially substituted with halogen atoms or heteroatom-containing groups.

[0085] Ra' 10 In this context, the linear alkyl group has 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, and particularly preferably 1 to 5 carbon atoms. Ra' 10 In this, the branched alkyl group is the Ra' 3 Similar examples include the above.

[0086] Ra' 10 In this case, the alkyl group may be partially substituted with a halogen atom or a heteroatom-containing group. For example, some of the hydrogen atoms constituting the alkyl group may be substituted with a halogen atom or a heteroatom-containing group. Also, some of the carbon atoms constituting the alkyl group (such as a methylene group) may be substituted with a heteroatom-containing group. Examples of heteroatoms used here include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of heteroatom-containing groups include (-O-), -C(=O)-O-, -OC(=O)-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -S-, -S(=O)2-, -S(=O)2-O-, etc.

[0087] In formula (a1-r2-1), Ra' 11 (Ra' 10 The aliphatic cyclic group formed with the bonded carbon atom is Ra' in formula (a1-r-1). 3 The groups listed as monocyclic or polycyclic alicyclic hydrocarbon groups are preferred. Among these, monocyclic alicyclic hydrocarbon groups are preferred, and specifically, cyclopentyl groups and cyclohexyl groups are more preferred.

[0088] In formula (a1-r2-2), the cyclic hydrocarbon group formed by Xa together with Ya is Ra' in formula (a1-r-1). 3 Examples include groups obtained by further removing one or more hydrogen atoms from a cyclic monovalent hydrocarbon group (alicyclic hydrocarbon group). The cyclic hydrocarbon group formed by Xa and Ya may have substituents. Examples of such substituents include the above-mentioned Ra' 3 Examples include substituents similar to those that may be present on the cyclic hydrocarbon group in the above. In formula (a1-r2-2), Ra 101 ~Ra 103 Examples of monovalent chain-like saturated hydrocarbon groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl groups. Ra 101 ~Ra 103 Examples of monovalent aliphatic cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms include monocyclic aliphatic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and cyclododecyl groups; and polycyclic aliphatic saturated hydrocarbon groups such as bicyclo[2.2.2]octanyl, tricyclo[5.2.1.02,6]decanyl, tricyclo[3.3.1.13,7]decanyl, tetracyclo[6.2.1.13,6.02,7]dodecanyl, and adamantyl groups. Ra 101 ~Ra 103 Of these, from the viewpoint of ease of synthesis, hydrogen atoms and monovalent chain saturated hydrocarbon groups having 1 to 10 carbon atoms are preferred, and among these, hydrogen atoms, methyl groups, and ethyl groups are more preferred, with hydrogen atoms being particularly preferred.

[0089] The above Ra 101 ~Ra 103 Examples of substituents on a chain-like saturated hydrocarbon group or an aliphatic cyclic saturated hydrocarbon group represented by the above-mentioned Ra x5 Similar bases can be cited.

[0090] Ra 101~Ra 103 Groups containing a carbon-carbon double bond formed by two or more of these groups bonding to each other to form a cyclic structure include, for example, cyclopentenyl group, cyclohexenyl group, methylcyclopentenyl group, methylcyclohexenyl group, cyclopentylideneethenyl group, and cyclohexyllideneethenyl group. Among these, cyclopentenyl group, cyclohexenyl group, and cyclopentylideneethenyl group are preferred from the viewpoint of ease of synthesis.

[0091] In formula (a1-r2-3), the aliphatic cyclic group formed by Xaa together with Yaa is Ra' in formula (a1-r-1). 3 The groups listed as monocyclic or polycyclic alicyclic hydrocarbon groups are preferred. In formula (a1-r2-3), Ra 104 Aromatic hydrocarbon groups in this context include groups obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring with 5 to 30 carbon atoms. Among them, Ra 104 The group is preferably an aromatic hydrocarbon ring having 6 to 15 carbon atoms with one or more hydrogen atoms removed; more preferably a group from benzene, naphthalene, anthracene, or phenanthrene with one or more hydrogen atoms removed; even more preferably a group from benzene, naphthalene, or anthracene with one or more hydrogen atoms removed; particularly preferably a group from benzene or naphthalene with one or more hydrogen atoms removed; and most preferably a group from benzene with one or more hydrogen atoms removed.

[0092] Ra in equation (a1-r2-3) 104 Examples of substituents that may be present include methyl groups, ethyl groups, propyl groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups (such as methoxy groups, ethoxy groups, propoxy groups, butoxy groups, etc.), and alkyloxycarbonyl groups.

[0093] In formula (a1-r2-4), Ra' 12 and Ra' 13 Each of these is independently a monovalent, chain-like saturated hydrocarbon group having 1 to 10 carbon atoms. 12 and Ra' 13In this context, the monovalent chain-like saturated hydrocarbon group having 1 to 10 carbon atoms is the above-mentioned Ra 101 ~Ra 103 Examples include monovalent chain-like saturated hydrocarbon groups having 1 to 10 carbon atoms. Some or all of the hydrogen atoms in this chain-like saturated hydrocarbon group may be substituted. Ra' 12 and Ra' 13 Among these, hydrogen atoms and alkyl groups having 1 to 5 carbon atoms are preferred, alkyl groups having 1 to 5 carbon atoms are more preferred, methyl groups and ethyl groups are even more preferred, and methyl groups are particularly preferred. The above Ra' 12 and Ra' 13 When a chain-like saturated hydrocarbon group represented by is substituted, the substituent may be, for example, the above-mentioned Ra x5 Similar bases can be cited.

[0094] In formula (a1-r2-4), Ra' 14 Ra' is a hydrocarbon group that may have substituents. 14 Examples of hydrocarbon groups in this context include linear or branched alkyl groups, or cyclic hydrocarbon groups.

[0095] Ra' 14 The linear alkyl group in this compound preferably has 1 to 5 carbon atoms, more preferably 1 to 4, and even more preferably 1 or 2. Specifically, examples include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, etc. Among these, methyl group, ethyl group, or n-butyl group is preferred, and methyl group or ethyl group is more preferred.

[0096] Ra' 14 The branched alkyl group in this compound preferably has 3 to 10 carbon atoms, and more preferably 3 to 5. Specifically, examples include isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 1,1-diethylpropyl group, 2,2-dimethylbutyl group, etc., with isopropyl group being preferred.

[0097] Ra'14 When the hydrocarbon group is a cyclic hydrocarbon group, the hydrocarbon group may be an alicyclic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group. As a monocyclic alicyclic hydrocarbon group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferred. The monocycloalkane is preferably one having 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. As a polycyclic group, a alicyclic hydrocarbon group is preferred, which is a group obtained by removing one hydrogen atom from a polycycloalkane, and as a polycycloalkane, those having 7 to 12 carbon atoms are preferred, and specific examples include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.

[0098] Ra' 14 As for aromatic hydrocarbon groups in this context, Ra 104 Examples include those similar to aromatic hydrocarbon groups in [the text]. Among them, Ra' 14 The group is preferably an aromatic hydrocarbon ring having 6 to 15 carbon atoms with one or more hydrogen atoms removed; more preferably a group from benzene, naphthalene, anthracene, or phenanthrene with one or more hydrogen atoms removed; even more preferably a group from benzene, naphthalene, or anthracene with one or more hydrogen atoms removed; particularly preferably a group from naphthalene or anthracene with one or more hydrogen atoms removed; and most preferably a group from naphthalene with one or more hydrogen atoms removed. Ra' 14 A substituent that may be present is Ra 104 Examples of substituents that may be present include those similar to those that the molecule may have.

[0099] Ra' in equation (a1-r2-4) 14 If is a naphthyl group, the position where it bonds with the tertiary carbon atom in formula (a1-r2-4) may be either position 1 or position 2 of the naphthyl group. Ra' in equation (a1-r2-4) 14If is an anthyl group, the position where it bonds with the tertiary carbon atom in formula (a1-r2-4) may be position 1, 2, or 9 of the anthyl group.

[0100] Specific examples of the group represented by the above formula (a1-r2-1) are given below.

[0101] [ka]

[0102] [ka]

[0103] [ka]

[0104] Specific examples of the group represented by the above formula (a1-r2-2) are given below.

[0105] [ka]

[0106] [ka]

[0107] [ka]

[0108] Specific examples of the group represented by the above formula (a1-r2-3) are given below.

[0109] [ka]

[0110] Specific examples of the group represented by the above formula (a1-r2-4) are given below.

[0111] [ka]

[0112] Tertiary alkyloxycarbonyl acid dissociable group: Among the aforementioned polar groups, an example of an acid-dissociating group that protects a hydroxyl group is the acid-dissociating group represented by the following general formula (a1-r-3) (hereinafter, for convenience, this may be referred to as a "tertiary alkyloxycarbonyl acid dissociating group").

[0113] [ka] [In the formula, Ra' 7 ~Ra' 9 These are each alkyl groups.

[0114] In formula (a1-r-3), Ra' 7 ~Ra' 9 Each of these is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. Furthermore, the total number of carbon atoms in each alkyl group is preferably 3 to 7, more preferably 3 to 5, and most preferably 3 to 4.

[0115] Secondary alkyl ester type acid-dissociating group: Among the polar groups mentioned above, an example of an acid-dissociating group that protects a carboxyl group is the acid-dissociating group represented by the following general formula (a1-r-4).

[0116] [ka] [In the formula, Ra' 10 Ra' is a hydrocarbon group. 11a and Ra' 11b Each of these is independently a hydrogen atom, a halogen atom, or an alkyl group. 12is a hydrogen atom or a hydrocarbon group. 10 and Ra' 11a Or Ra' 11b These elements may be joined together to form a ring. 11a Or Ra' 11b And, Ra' 12 These elements may be joined together to form a ring.

[0117] In the formula, Ra' 10 and Ra' 12 The hydrocarbon group in this is the Ra' 3 Similar examples include the above. In the formula, Ra' 11a and Ra' 11b The alkyl group in is the aforementioned Ra' 1 Examples include alkyl groups similar to those in the above. In the formula, Ra' 10 and Ra' 12 The hydrocarbon group in, and Ra' 11a and Ra' 11b The alkyl group in may have substituents. For example, the above-mentioned Ra is an example of such substituent. x5 These are some examples.

[0118] Ra' 10 and Ra' 11a Or Ra' 11b These elements may be bonded to each other to form a ring. This ring may be polycyclic or monocyclic, and may be an alicyclic or aromatic ring. The alicyclic and aromatic rings may also contain heteroatoms.

[0119] Ra' 10 and Ra' 11a Or Ra' 11b The rings formed by the bonding of these elements are preferably monocycloalkenes, rings in which some of the carbon atoms of a monocycloalkene are substituted with heteroatoms (oxygen atoms, sulfur atoms, etc.), monocycloalkadienes, cycloalkenes having 3 to 6 carbon atoms, and cyclopentene or cyclohexene.

[0120] Ra' 10 and Ra' 11a Or Ra' 11b The ring formed by the bonding of these elements may be a fused ring. Specific examples of such fused rings include indane.

[0121] Ra' 10 and Ra' 11a Or Ra' 11b The ring formed by the bonding of these elements may have substituents. For example, the above-mentioned Ra x5 These are some examples.

[0122] Ra' 11a Or Ra' 11b And, Ra' 12 These elements may be bonded together to form a ring, and the ring may be Ra' 10 and Ra' 11a Or Ra' 11b Examples include rings formed by the bonding of these elements together.

[0123] Specific examples of the group represented by the above formula (a1-r-4) are given below.

[0124] [ka]

[0125] Examples of constituent units (a1) include constituent units derived from acrylic acid esters in which the hydrogen atom bonded to the α-carbon atom may be substituted with a substituent, constituent units derived from acrylamide, constituent units derived from hydroxystyrene or hydroxystyrene derivatives in which at least a portion of the hydrogen atoms in the hydroxyl group of a constituent unit are protected by a substituent containing the acid-degradable group, and constituent units derived from vinyl benzoic acid or vinyl benzoic acid derivatives in which at least a portion of the hydrogen atoms in the -C(=O)-OH group are protected by a substituent containing the acid-degradable group.

[0126] As for the constituent unit (a1), among the above, a constituent unit derived from an acrylic acid ester in which the hydrogen atom bonded to the α-carbon atom may be substituted with a substituent is preferred. A preferred specific example of such a constituent unit (a1) is a constituent unit represented by the following general formula (a1-1) or (a1-2).

[0127] [ka] [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 n is a divalent hydrocarbon group which may have an ether bond. a1 is an integer between 0 and 2. 1 This is an acid-dissociable group represented by the general formula (a1-r-1) or (a1-r-2) above. 1 is n a2 It is a +1 valent hydrocarbon group, n a2 is an integer between 1 and 3, and Ra 2 This is an acid-dissociable group represented by the general formula (a1-r-1) or (a1-r-3) above.

[0128] In formula (a1-1), the C1-C5 alkyl group of R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, specifically including methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl groups. The C1-C5 halogenated alkyl group is a group in which some or all of the hydrogen atoms of the C1-C5 alkyl group are substituted with halogen atoms. Fluorine atoms are particularly preferred as the halogen atoms. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, with a hydrogen atom or a methyl group being the most preferred due to their industrial availability.

[0129] In the above formula (a1-1), Va 1The divalent hydrocarbon group in this expression may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0130] Va 1 The aliphatic hydrocarbon group as a divalent hydrocarbon group in this compound may be saturated or unsaturated, but is usually preferred to be saturated. More specifically, examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups containing a ring in their structure.

[0131] The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As for the linear aliphatic hydrocarbon group, linear alkylene groups are preferred, specifically the methylene group [-CH2-], ethylene group [-(CH2)2-], trimethylene group [-(CH2)3-], tetramethylene group [-(CH2)4-], pentamethylene group [-(CH2)5-], etc. The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. Preferred branched aliphatic hydrocarbon groups include branched alkylene groups, specifically alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkylalkylene groups such as alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. In the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0132] Examples of aliphatic hydrocarbon groups containing a ring in the aforementioned structure include alicyclic hydrocarbon groups (groups obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include those similar to the linear or branched aliphatic hydrocarbon group described above. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be polycyclic or monocyclic. A preferred monocyclic alicyclic hydrocarbon group is a monocycloalkane with two hydrogen atoms removed. The monocycloalkane is preferably one having 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. A preferred polycyclic alicyclic hydrocarbon group is a polycycloalkane with two hydrogen atoms removed, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.

[0133] Va 1 In this context, an aromatic hydrocarbon group as a divalent hydrocarbon group is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 12. However, this number of carbon atoms does not include the number of carbon atoms in substituents. Specific examples of aromatic rings in aromatic hydrocarbon groups include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced by heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of the aromatic hydrocarbon group include a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring (arylene group); and a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring (aryl group) in which one hydrogen atom is replaced by an alkylene group (for example, a group obtained by removing one more hydrogen atom from the aryl group in an arylalkyl group such as a benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms in the alkylene group (alkyl chain in an arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0134] In the above formula (a1-1), Ra 1 This is an acid-dissociable group represented by the above formula (a1-r-1) or (a1-r-2).

[0135] In the above formula (a1-2), Wa 1 n in a2The +1 valent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity, and may be saturated or unsaturated, but is usually preferred to be saturated. Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in its structure, or a group that is a combination of a linear or branched aliphatic hydrocarbon group and an aliphatic hydrocarbon group containing a ring in its structure. The aforementioned n a2 The +1 valent is preferably 2 to 4 valent, and more preferably 2 or 3 valent.

[0136] In the above formula (a1-2), Ra 2 This is an acid-dissociable group represented by the general formula (a1-r-1) or (a1-r-3) above.

[0137] The following are specific examples of constituent units (a1). In each of the following equations, R α This represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0138] [ka]

[0139] [ka]

[0140] [ka]

[0141] [ka]

[0142] [ka]

[0143] [ka]

[0144] [ka]

[0145] [ka]

[0146] The constituent units (a1) of component (A1) may be one type or two or more types. As for the constituent unit (a1), the constituent unit represented by formula (a1-1) is more preferable because it is easier to improve the properties (CDU, etc.) in lithography using electron beams or EUV.

[0147] [ka] [In the formula, Ra 1 " is an acid-dissociable group represented by the general formula (a1-r2-1), (a1-r2-3), or (a1-r2-4). * indicates a bond.

[0148] In the above formula (a1-1-1), R, Va 1 and n a1 R, Va in the above formula (a1-1) 1 and n a1 It is similar to that. The acid-dissociable groups represented by general formulas (a1-r2-1), (a1-r2-3), or (a1-r2-4) are described above. In particular, it is preferable to select acid-dissociable groups that are cyclic groups, as they are suitable for EB or EUV applications because they enhance reactivity, and the acid-dissociable group represented by general formula (a1-r2-1) is more preferable.

[0149] If component (A1) contains constituent unit (a1), the proportion of constituent unit (a1) in component (A1) is preferably 5 to 95 mol%, more preferably 10 to 90 mol%, even more preferably 30 to 70 mol%, and particularly preferably 40 to 60 mol%, relative to the total amount (100 mol%) of all constituent units that make up component (A1). By setting the proportion of the constituent unit (a1) to be above the lower limit of the preferred range described above, lithography characteristics such as sensitivity, CDU, resolution, and roughness improvement are enhanced. On the other hand, if it is below the upper limit of the preferred range described above, a balance can be achieved with other constituent units, resulting in good lithography characteristics across various fields.

[0150] Regarding the constituent unit (a10): A constituent unit (a10) is a constituent unit represented by the following general formula (a10-1) (excluding those corresponding to constituent unit (a1)).

[0151] [ka] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halogen having 1 to 5 carbon atoms. x1 Wa is a single bond or a divalent linking group. x1 n is an aromatic hydrocarbon group which may have substituents. ax1 [ is an integer greater than or equal to 1.]

[0152] In the above formula (a10-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide having 1 to 5 carbon atoms. For R, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms is preferred, and due to their industrial availability, a hydrogen atom, a methyl group, or a trifluoromethyl group is more preferred, a hydrogen atom or a methyl group is even more preferred, and a hydrogen atom is particularly preferred.

[0153] In the above formula (a10-1), Ya x1 It is a single bond or a divalent linking group. In the above chemical formula, Yax1 The divalent linking group in this is not particularly limited, but suitable examples include divalent hydrocarbon groups which may have substituents, and divalent linking groups which contain heteroatoms.

[0154] Ya x1 Preferably, the group is a single bond, an ester bond [-C(=O)-O-, -OC(=O)-], an ether bond (-O-), a linear or branched alkylene group, or a combination thereof, with single bonds and ester bonds [-C(=O)-O-, -OC(=O)-] being more preferred.

[0155] In the above formula (a10-1), Wa x1 This is an aromatic hydrocarbon group which may have substituents. Wa x1 The aromatic hydrocarbon group in this context may be an aromatic ring that may have substituents (n ax1 A group with 1+1 hydrogen atoms removed is an example. The aromatic ring here is not particularly limited as long as it is a cyclic conjugated system with 4n+2 π electrons. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced by heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of aromatic heterocycles include pyridine rings and thiophene rings. Also, Wa x1 The aromatic hydrocarbon group in this context is an aromatic compound containing an aromatic ring which may have two or more substituents (e.g., biphenyl, fluorene, etc.) (n ax1 Another example is a group with (+1) hydrogen atoms removed. Among the above, Wa x1 Examples include benzene, naphthalene, anthracene, or biphenyl (n ax1 A group with (+1) hydrogen atoms removed is preferred, and (n ax1A group with (+1) hydrogen atoms removed is more preferable, and from benzene (n ax1 A group with (+1) hydrogen atoms removed is even more preferable.

[0156] Wa x1 The aromatic hydrocarbon group in may or may not have substituents. Examples of substituents include alkyl groups, alkoxy groups, halogen atoms, and alkyl halides. Examples of alkyl groups, alkoxy groups, halogen atoms, and alkyl halides as substituents include Ya x1 Examples of substituents include those similar to those listed for the cyclic alicyclic hydrocarbon group in [the relevant section]. 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, even more preferably an ethyl group or a methyl group, and particularly preferably a methyl group. x1 In this context, it is preferable that the aromatic hydrocarbon group does not have substituents.

[0157] In the above formula (a10-1), n ax1 is an integer greater than or equal to 1, preferably an integer between 1 and 10, more preferably an integer between 1 and 5, even more preferably 1, 2, or 3, and particularly preferably 1 or 2.

[0158] The following are specific examples of the constituent unit (a10) represented by the above formula (a10-1). In each of the following equations, R α This represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0159] [ka]

[0160] [ka]

[0161] [ka]

[0162] The constituent units (a10) of component (A1) may be one type or two or more types. If component (A1) has constituent units (a10), the proportion of constituent units (a10) in component (A1) is preferably 20 to 60 mol%, more preferably 25 to 55 mol%, even more preferably 30 to 50 mol%, and particularly preferably 35 to 45 mol%, relative to the total amount (100 mol%) of all constituent units that make up component (A1). By setting the proportion of constituent unit (a10) above the lower limit, sensitivity can be more easily increased. On the other hand, by setting it below the upper limit, it becomes easier to balance it with other constituent units.

[0163] Regarding the constituent unit (a2): Component (A1) may further have a constituent unit (a2) containing a lactone-containing cyclic group (excluding those corresponding to constituent unit (a1)). The lactone-containing cyclic group of component (a2) is effective in improving the adhesion of the resist film to the substrate when component (A1) is used to form a resist film. Furthermore, the presence of component (a2) improves lithography characteristics, for example, by appropriately adjusting the acid diffusion length, improving the adhesion of the resist film to the substrate, and appropriately adjusting the solubility during development.

[0164] A "lactone-containing cyclic group" refers to a cyclic group that contains a ring (lactone ring) containing -OC(=O)- within its cyclic skeleton. The lactone ring is counted as the first ring. If it consists only of a lactone ring, it is called a monocyclic group. If it also has other ring structures, it is called a polycyclic group regardless of those structures. A lactone-containing cyclic group may be a monocyclic group or a polycyclic group. Any lactone-containing cyclic group can be used in the constituent unit (a2) without any particular limitations. Specifically, examples include the groups represented by the following general formulas (a2-r-1) to (a2-r-7).

[0165] [ka] [In the formula, Ra' 21 Each of these is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR'', -OC(=O)R'', a hydroxyalkyl group, or a cyano group; R'' is a hydrogen atom, an alkyl group, or a lactone-containing cyclic group; A'' is an alkylene group having 1 to 5 carbon atoms, which may contain an oxygen atom (-O-) or a sulfur atom (-S-), an oxygen atom, or a sulfur atom, where n' is an integer from 0 to 2, and m' is 0 or 1. * indicates a bond (the same applies below).

[0166] In the general formulas (a2-r-1) to (a2-r-7), Ra' 21 The alkyl group in is preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group is preferably linear or branched. Specifically, examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, etc. Among these, the methyl group or ethyl group is preferred, and the methyl group is particularly preferred. Ra' 21 The alkoxy group in is preferably an alkoxy group having 1 to 6 carbon atoms. The alkoxy group is preferably linear or branched. Specifically, the Ra' 21 Examples of alkyl groups in this context include groups formed by linking an alkyl group with an oxygen atom (-O-). Ra' 21 In this mixture, a fluorine atom is preferred as the halogen atom. Ra' 21 The halogenated alkyl group in is the Ra' 21 Examples include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with the halogen atoms. Fluorinated alkyl groups are preferred as the halogenated alkyl group, and perfluoroalkyl groups are particularly preferred.

[0167] Ra' 21In -COOR'' and -OC(=O)R'', R'' is either a hydrogen atom, an alkyl group, or a lactone-containing cyclic group. The alkyl group in R'' can be linear, branched, or cyclic, and preferably has 1 to 15 carbon atoms. When R'' is a linear or branched alkyl group, it is preferably 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 is preferably 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, examples include groups obtained by removing one or more hydrogen atoms from monocycloalkanes which may or may not be substituted with a fluorine atom or a fluorinated alkyl group; and groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as bicycloalkanes, tricycloalkanes, and tetracycloalkanes. More specifically, examples include groups obtained by removing one or more hydrogen atoms from monocycloalkanes such as cyclopentane and cyclohexane; and groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Examples of lactone-containing cyclic groups in R'' include those similar to those represented by the general formulas (a2-r-1) to (a2-r-7) mentioned above. Ra' 21 The hydroxyalkyl group in is preferably one having 1 to 6 carbon atoms, specifically the Ra' 21 Examples include groups in which at least one hydrogen atom of the alkyl group is substituted with a hydroxyl group.

[0168] Ra' 21 Among the above, it is preferable that each is independently a hydrogen atom or a cyano group.

[0169] In the general formulas (a2-r-2), (a2-r-3), and (a2-r-5) above, the alkylene group having 1 to 5 carbon atoms in A'' is preferably a linear or branched alkylene group, such as a methylene group, ethylene group, n-propylene group, or isopropylene group. When the alkylene group contains an oxygen atom or a sulfur atom, specific examples include a group in which -O- or -S- is interposed at the end or between carbon atoms of the alkylene group, such as -O-CH2-, -CH2-O-CH2-, -S-CH2-, or -CH2-S-CH2-. A'' is preferably an alkylene group having 1 to 5 carbon atoms or -O-, more preferably an alkylene group having 1 to 5 carbon atoms, and most preferably a methylene group.

[0170] The following are specific examples of the groups represented by the general formulas (a²-r-1) to (a²-r-7).

[0171] [ka]

[0172] [ka]

[0173] Among the constituent units (a2), those derived from acrylic acid esters in which the hydrogen atom bonded to the α-carbon atom may be substituted with a substituent are preferred. The constituent unit (a2) is preferably a constituent unit represented by the following general formula (a2-1).

[0174] [ka] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halogen having 1 to 5 carbon atoms. 21 It is a single bond or a divalent linking group. 21The R' is -O-, -COO-, -CON(R')-, -OCO-, -CONHCO-, or -CONHCS-, where R' represents a hydrogen atom or a methyl group. However, La 21 If -O-, Ya 21 It does not become -CO-. 21 It is a lactone-containing cyclic group.

[0175] In formula (a2-1) above, R is the same as above. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and a hydrogen atom or a methyl group is particularly preferred due to their industrial availability.

[0176] In the above formula (a2-1), Ya 21 The divalent linking group in this is not particularly limited, but preferred examples include divalent hydrocarbon groups which may have substituents, and divalent linking groups which contain heteroatoms.

[0177] Ya 21 Preferably, the group is a single bond, an ester bond [-C(=O)-O-], an ether bond (-O-), a linear or branched alkylene group, or a combination thereof.

[0178] In the above formula (a2-1), Ya 21 It is a single bond, La 21 It is preferable that it be -COO- or -OCO-.

[0179] In the above formula (a2-1), Ra 21 It is a lactone-containing cyclic group. Ra 21 Suitable lactone-containing cyclic groups in this compound include those represented by the general formulas (a2-r-1) to (a2-r-7) mentioned above.

[0180] The constituent units (a2) of component (A1) may be one type or two or more types. If component (A1) has constituent units (a2), the proportion of constituent units (a2) is preferably 1 to 20 mol%, more preferably 1 to 15 mol%, and even more preferably 1 to 10 mol%, relative to the total amount (100 mol%) of all constituent units that make up component (A1). If the proportion of constituent unit (a2) is set above a preferred lower limit, the effects of including constituent unit (a2) are fully obtained due to the effects described above, and if it is below the upper limit, a balance can be achieved with other constituent units, resulting in good lithography characteristics.

[0181] Regarding the constituent unit (a8): The constituent unit (a8) is a constituent unit derived from the compound represented by the following general formula (a8-1). However, those corresponding to constituent unit (a0) are excluded.

[0182] [ka] [In the formula, W 2 This is a polymerizable group-containing group. x2 is a single bond or (n ax2 It is a linking group with a +1 valence. x2 and W 2 It may form a fused ring with R. 1 R is a fluorinated alkyl group having 1 to 12 carbon atoms. 2 R is an organic group having 1 to 12 carbon atoms, which may contain a fluorine atom, or a hydrogen atom. 2 and Ya x2 These may be bonded to each other to form a ring structure. ax2 [This is an integer between 1 and 3.]

[0183] W 2 In the context of polymerizable group-containing groups, "polymerizable group" refers to a group that enables a compound containing a polymerizable group to polymerize by radical polymerization or the like, and includes, for example, a group containing multiple bonds between carbon atoms, such as an ethylenic double bond.

[0184] The polymerizable group-containing group may be a group composed solely of a polymerizable group, or a group composed of a polymerizable group and other groups other than the polymerizable group. Examples of other groups other than the polymerizable group include divalent hydrocarbon groups which may have substituents, and divalent linking groups which contain heteroatoms. Examples of polymerizable groups include those with the chemical formula: C(R X11 )(R X12 )=C(R X13 )-Ya x0 The group represented by - is preferably mentioned. In this chemical formula, R X11 , R X12 and R X13 These are, respectively, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, and Ya x0 It is a single bond or a divalent linking group.

[0185] Ya x2 and W 2 The condensed ring formed by these is W 2 Polymerizable groups of the site and Ya x2 The condensed ring formed by and W 2 Other groups besides the polymerizable group of the site and Ya x2 A condensed ring formed by these is one example. Ya x2 and W 2 The fused ring formed by these two components may have substituents.

[0186] The following are specific examples of constituent units (a8). In the following formula, R α This represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0187] [ka]

[0188] Among the examples above, the constituent unit (a8) is preferably at least one selected from the group consisting of constituent units represented by the 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 constituent units represented by the chemical formulas (a8-1-01) to (a8-1-04) and (a8-1-09).

[0189] The constituent units (a8) of component (A1) may be one type or two or more types. The proportion of constituent unit (a8) in component (A1) is preferably 50 mol% or less, and more preferably 0 to 30 mol%, relative to the total amount (100 mol%) of all constituent units that make up component (A1).

[0190] The (A1) component contained in the resist composition may be used alone or in combination of two or more types. In the resist composition of this embodiment, component (A1) is a polymer compound having a repeating structure of the constituent unit (a0). (A1) Among the above, polymer compounds containing a repeating structure of constituent unit (a0) and constituent unit (a10) are preferred as component (A1).

[0191] In a polymer compound having a repeating structure of constituent units (a0) and constituent units (a10), the proportion of constituent units (a0) is preferably 40 to 80 mol%, more preferably 45 to 75 mol%, even more preferably 50 to 70 mol%, and particularly preferably 55 to 65 mol%, relative to the total amount (100 mol%) of all constituent units that make up the polymer compound. Furthermore, the proportion of constituent units (a10) in the polymer compound is preferably 20 to 60 mol%, more preferably 25 to 55 mol%, even more preferably 30 to 50 mol%, and particularly preferably 35 to 45 mol%, relative to the total amount (100 mol%) of all constituent units that make up the polymer compound.

[0192] Such component (A1) can be produced by dissolving monomers that induce each constituent unit in a polymerization solvent and then adding a radical polymerization initiator such as azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyrate (e.g., V-601) to the mixture and polymerizing it. Alternatively, such component (A1) can be produced by dissolving a monomer that induces the constituent unit (a0) and, if necessary, a monomer that induces a constituent unit other than the constituent unit (a0) (for example, the constituent unit (a10)) in a polymerization solvent, adding the above-mentioned radical polymerization initiator to this solution and polymerizing it, and then carrying out a deprotection reaction. Furthermore, during polymerization, a chain transfer agent such as HS-CH2-CH2-CH2-C(CF3)2-OH may be used in combination to introduce a -C(CF3)2-OH group at the terminal. Copolymers in which a hydroxyalkyl group, in which some of the hydrogen atoms of the alkyl group are replaced with fluorine atoms, are introduced are effective in reducing development defects and LER (line edge roughness: uneven unevenness of the line sidewall).

[0193] The weight-average molecular weight (Mw) of component (A1) (based on polystyrene conversion by gel permeation chromatography (GPC)) is not particularly limited, but is preferably 1,000 to 50,000, more preferably 2,000 to 30,000, and even more preferably 3,000 to 20,000. If the Mw of component (A1) is below the preferred upper limit of this range, it has sufficient solubility in the resist solvent for use as a resist, and if it is above the preferred lower limit of this range, it has good dry etching resistance and a good cross-sectional shape of the resist pattern. (A1) The degree of dispersion of component (Mw / Mn) is not particularly limited, but is preferably 1.0 to 4.0, more preferably 1.0 to 3.0, and particularly preferably 1.0 to 2.0. Mn represents the number-average molecular weight.

[0194] (A2) About the ingredients The resist composition of this embodiment may also include, as component (A), a base component (hereinafter referred to as "component (A2)") that does not correspond to component (A1) and whose solubility in the developer solution changes due to the action of an acid. (A2) The component is not particularly limited and can be arbitrarily selected from a large number of components that have been conventionally known as base components for chemically amplified resist compositions. (A2) Component may be a single high-molecular-weight compound or a low-molecular-weight compound, or two or more may be used in combination.

[0195] The proportion of component (A1) in component (A) is preferably 25% by mass or more, more preferably 50% by mass or more, even more preferably 75% by mass or more, and may also be 100% by mass, based on the total mass of component (A). When the proportion is 25% by mass or more, it becomes easier to form a resist pattern that is excellent in various lithography characteristics such as high sensitivity, resolution, and roughness improvement.

[0196] In the resist composition of this embodiment, the content of component (A) may be adjusted according to the resist film thickness to be formed.

[0197] <Other ingredients> The resist composition of this embodiment may further contain other components in addition to the above-described components (A) and (B). Examples of other components include components (B), (D), (E), (F), and (S) shown below.

[0198] ≪Acid Generating Agent Component (B)≫ The resist composition of this embodiment preferably further contains an acid-generating component (B) that generates acid upon exposure. (B) The component is not particularly limited, and any acid generators previously proposed 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; oximesulfonate-based acid generators; diazomethane-based acid generators such as bisalkyl or bisarylsulfonyl diazomethanes and poly(bissulfonyl) diazomethanes; nitrobenzyl sulfonate-based acid generators, iminosulfonate-based acid generators, and disulfone-based acid generators, among many others.

[0199] Examples of onium salt-based acid generators include the compound represented by the following general formula (b-1) (hereinafter also referred to as "component (b-1)"), the compound represented by the general formula (b-2) (hereinafter also referred to as "component (b-2)"), or the compound represented by the general formula (b-3) (hereinafter also referred to as "component (b-3)").

[0200] Examples of onium salt-based acid generators include the compound represented by the following general formula (b-1) (hereinafter also referred to as "component (b-1)"), the compound represented by the general formula (b-2) (hereinafter also referred to as "component (b-2)"), or the compound represented by the general formula (b-3) (hereinafter also referred to as "component (b-3)").

[0201] [ka] [In the formula, R 101 and R 104 ~R 108 Each of these is independently a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents. 104 and R 105 These may be bonded to each other to form a ring structure. 102 This is a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom. 101 This is a divalent linking group or single bond containing an oxygen atom. 101 ~V 103 These are, independently, a single bond, an alkylene group, or a fluorinated alkylene group. 101 ~L 102 Each of these is independently either a single bond or an oxygen atom. 103 ~L105 These are, independently, single bonds, -CO-, or -SO2-. m is an integer greater than or equal to 1, and M' m+ This is an onium cation with a valence of m.

[0202] {Anion Division} • Anion in component (b-1) In formula (b-1), R 101 This is a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents.

[0203] Cyclic groups that may have substituents: The cyclic group is preferably a cyclic hydrocarbon group, which may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity. Furthermore, the aliphatic hydrocarbon group is preferably saturated.

[0204] R 101 The aromatic hydrocarbon group in this formula is a hydrocarbon group having an aromatic ring. The number of carbon atoms in the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, this number of carbon atoms does not include the number of carbon atoms in substituents. R 101 Specific examples of aromatic rings in aromatic hydrocarbon groups include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic heterocycles in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, nitrogen atoms, etc. R 101Specific examples of aromatic hydrocarbon groups in this context include groups obtained by removing one hydrogen atom from the aromatic ring (aryl groups: for example, phenyl groups, naphthyl groups, etc.), and groups in which one of the hydrogen atoms of the aromatic ring is replaced by an alkylene group (for example, benzyl groups, phenethyl groups, 1-naphthylmethyl groups, etc.). The number of carbon atoms in the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0205] R 101 In this context, cyclic aliphatic hydrocarbon groups include aliphatic hydrocarbon groups that contain a ring in their structure. Examples of aliphatic hydrocarbon groups containing a ring in this structure include alicyclic hydrocarbon groups (groups from which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. A preferred monocyclic alicyclic hydrocarbon group is a group obtained by removing one or more hydrogen atoms from a monocycloalkane. The monocycloalkane is preferably one having 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. A preferred polycyclic alicyclic hydrocarbon group is a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 30 carbon atoms. Among these, polycycloalkanes having a bridging ring polycyclic skeleton such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; and polycycloalkanes having a fused ring polycyclic skeleton such as a cyclic group having a steroid skeleton are more preferred.

[0206] Among them, R 101The cyclic aliphatic hydrocarbon group in is preferably a monocycloalkane or polycycloalkane from which one or more hydrogen atoms have been removed, more preferably a polycycloalkane from which one hydrogen atom has been removed, even more preferably an adamantyl group or a norbornyl group, and particularly preferably an adamantyl group.

[0207] The linear aliphatic hydrocarbon group, which may be bonded to the alicyclic hydrocarbon group, preferably has 1 to 10 carbon atoms, more preferably 1 to 6, even more preferably 1 to 4, and most preferably 1 to 3. Examples of linear aliphatic hydrocarbon groups include linear alkylene groups, specifically methylene groups [-CH2-], ethylene groups [-(CH2)2-], trimethylene groups [-(CH2)3-], tetramethylene groups [-(CH2)4-], pentamethylene groups [-(CH2)5-], and the like. The branched aliphatic hydrocarbon group, which may be bonded to the alicyclic hydrocarbon group, preferably has 2 to 10 carbon atoms, more preferably 3 to 6, even more preferably 3 or 4, and most preferably 3. Preferred branched aliphatic hydrocarbon groups include branched alkylene groups, specifically alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkylalkylene groups such as alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. In the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0208] Also, R 101The cyclic hydrocarbon group in the formula may contain heteroatoms, such as heterocycles. Specifically, examples include lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-7), the -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). In the formulas, * represents Y in formula (b-1). 101 This represents a coupling that connects to something.

[0209] [ka] [In the formula, Rb' 51 Each of the following is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR'', -OC(=O)R'', a hydroxyalkyl group, or a cyano group; R'' is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, or a -SO2--containing cyclic group; B'' is an alkylene group having 1 to 5 carbon atoms, which may contain an oxygen atom or a sulfur atom, an oxygen atom, or a sulfur atom, and n' is an integer from 0 to 2. * indicates a bond.

[0210] In the above general formulas (b5-r-1) to (b5-r-2), B'' is an alkylene group having 1 to 5 carbon atoms, which may contain an oxygen atom or a sulfur atom, or an oxygen atom or a sulfur atom. For B'', an alkylene group or -O- having 1 to 5 carbon atoms is preferred, an alkylene group having 1 to 5 carbon atoms is more preferred, and a methylene group is even more preferred.

[0211] In the above general formulas (b5-r-1) to (b5-r-4), Rb' 51 Each of these is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR'', -OC(=O)R'', a hydroxyalkyl group, or a cyano group, and among these, each is preferably independently a hydrogen atom or a cyano group.

[0212] Specific examples of the groups represented by the general formulas (b5-r-1) to (b5-r-4) are given below. In the formulas, "Ac" indicates an acetyl group.

[0213] [ka]

[0214] [ka]

[0215] [ka]

[0216] [ka]

[0217] R 101 Examples of substituents on the cyclic group include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, and nitro groups. As the alkyl group used as a substituent, an alkyl group having 1 to 5 carbon atoms is preferred. As the substituent, an alkoxy group having 1 to 5 carbon atoms is preferred, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group are more preferred, and a methoxy group and an ethoxy group are most preferred. Preferred halogen atoms as substituents are fluorine, bromine, and iodine atoms. Examples of alkyl halides used as substituents include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, and tert-butyl groups, in which some or all of the hydrogen atoms are substituted with the halogen atoms. A carbonyl group as a substituent is a group that substitutes for a methylene group (-CH2-) that constitutes a cyclic hydrocarbon group.

[0218] R 101 The cyclic hydrocarbon group in may be a fused ring group containing a fused ring formed by the fusion of an aliphatic hydrocarbon ring and an aromatic ring. Examples of the fused ring include a polycycloalkane having a bridging ring system with one or more aromatic rings fused to it. Specific examples of the bridging ring system polycycloalkane include bicycloalkanes such as bicyclo[2.2.1]heptane (norbornane) and bicyclo[2.2.2]octane. The fused ring group is preferably a group containing a fused ring formed by the fusion of two or three aromatic rings to a bicycloalkane, and more preferably a group containing a fused ring formed by the fusion of two or three aromatic rings to bicyclo[2.2.2]octane. 101 Specific examples of fused ring groups in this context include those represented by the following formulas (r-br-1) to (r-br-2). In the formulas, * represents Y in formula (b-1). 101 This represents a coupling that connects to something.

[0219] [ka]

[0220] R 101 Examples of substituents that the fused ring group in the compound may have include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, nitro groups, aromatic hydrocarbon groups, and alicyclic hydrocarbon groups. The alkyl group, alkoxy group, halogen atom, and halogenated alkyl group as substituents of the fused cyclic group are as described above in R 101 Examples of substituents on cyclic groups in the above are similar to those listed. Examples of aromatic hydrocarbon groups as substituents on the fused ring group include groups obtained by removing one hydrogen atom from an aromatic ring (aryl groups: for example, phenyl groups, naphthyl groups, etc.), groups in which one of the hydrogen atoms of the aromatic ring is replaced by an alkylene group (for example, arylalkyl groups such as benzyl groups, phenethyl groups, 1-naphthylmethyl groups, 2-naphthylmethyl groups, 1-naphthylethyl groups, 2-naphthylethyl groups, etc.), and heterocyclic groups represented by the above formulas (r-hr-1) to (r-hr-6). Examples of alicyclic hydrocarbon groups as substituents on the fused cyclic group include: groups obtained by removing one hydrogen atom from monocycloalkanes such as cyclopentane and cyclohexane; groups obtained by removing one hydrogen atom from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; 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 heterocyclic groups represented by the formulas (r-hr-7) to (r-hr-16).

[0221] Chain-like alkyl groups that may have substituents: R 101 The chain-like alkyl group may be either linear or branched. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15, and most preferably 1 to 10. The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15, and most preferably 3 to 10. Specifically, examples include 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, and 4-methylpentyl group.

[0222] A chain-like alkenyl group which may have substituents: R 101The linear alkenyl group may be linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5, even more preferably 2 to 4, and particularly preferably 3. Examples of linear alkenyl groups include vinyl groups, propenyl groups (allyl groups), and butynyl groups. Examples of branched alkenyl groups include 1-methylvinyl groups, 2-methylvinyl groups, 1-methylpropenyl groups, and 2-methylpropenyl groups. Among the above, linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred.

[0223] R 101 Examples of substituents in the chain-like alkyl or alkenyl group include alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, nitro groups, amino groups, and the above R 101 Examples include cyclic groups in this context.

[0224] In formula (b-1), Y 101 It is a single bond or a divalent linking group containing an oxygen atom. Y 101 If Y is a divalent linking group containing an oxygen atom, 101 It may contain atoms other than oxygen atoms. Examples of atoms other than oxygen atoms include carbon atoms, hydrogen atoms, sulfur atoms, nitrogen atoms, etc. Examples of divalent linking groups containing an oxygen atom include the linking groups represented by the following general formulas (y-al-1) to (y-al-7). Note that in the following general formulas (y-al-1) to (y-al-7), R in formula (b-1) above 101 The V' in the following general formulas (y-al-1)~(y-al-7) is what combines with it. 101 That is the case.

[0225] [ka] [In the formula, V' 101 V' is a single bond or an alkylene group with 1 to 5 carbon atoms. 102It is a divalent saturated hydrocarbon group with 1 to 30 carbon atoms.

[0226] V' 102 The divalent saturated hydrocarbon group in 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.

[0227] V' 101 and V' 102 The alkylene group in this product may be a linear alkylene group or a branched alkylene group, but a linear alkylene group is preferred. V' 101 and V' 102 Specifically, the alkylene groups in these include: methylene group [-CH2-]; alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-; ethylene group [-CH2CH2-]; -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2 Examples include alkylethylene groups such as -CH2CH2CH2-; trimethylene groups (n-propylene groups) [-CH2CH2CH2-]; alkyltrimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; tetramethylene groups [-CH2CH2CH2CH2-]; alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-; and pentamethylene groups [-CH2CH2CH2CH2CH2-]. Also, oshiV' 101 or V' 102 Some of the methylene groups in the alkylene group may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms. The aliphatic cyclic group is Ra' in formula (a1-r-1). 3A divalent group is preferred, which is obtained by removing one more hydrogen atom from a cyclic aliphatic hydrocarbon group (monocyclic aliphatic hydrocarbon group, polycyclic aliphatic hydrocarbon group), and a cyclohexylene group, a 1,5-adamantilene group, or a 2,6-adamantilene group is more preferred.

[0228] In formula (b-1), V 101 These are single bonds, alkylene groups, or fluorinated alkylene groups. Among them, V 101 It is preferable that the fluorinated alkylene group is a single bond or a linear chain having 1 to 4 carbon atoms.

[0229] In formula (b-1), R 102 R is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. 102 It is preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and more preferably a fluorine atom.

[0230] A specific example of the anion part represented by the above formula (b-1) is, for example, Y 101 When it is a single bond, examples include fluorinated alkyl sulfonate anions such as trifluoromethanesulfonate anions and perfluorobutanesulfonate anions; Y 101 When is a divalent linking group containing an oxygen atom, the anions can be represented by any of the following formulas (an-1) to (an-3).

[0231] [ka] [In the formula, R” 101 R” is an optionally substituted aliphatic cyclic group, a monovalent heterocyclic group represented by the above chemical formulas (r-hr-1) to (r-hr-6), a fused cyclic group represented by the above formula (r-br-1) or (r-br-2), an optionally substituted linear alkyl group, or an optionally substituted aromatic cyclic group. 102R” is an aliphatic cyclic group which may have substituents, a fused cyclic group represented by formula (r-br-1) or (r-br-2), a lactone-containing cyclic group represented by the general formulas (a2-r-1), (a2-r-3) to (a2-r-7), respectively, or a -SO2-containing cyclic group represented by the general formulas (b5-r-1) to (b5-r-4), respectively. 103 V” is an optionally substituted aromatic cyclic group, an optionally substituted aliphatic cyclic group, or an optionally substituted linear alkenyl group. 101 This is a single bond, an alkylene group having 1 to 4 carbon atoms, or a fluorinated alkylene group having 1 to 4 carbon atoms. 102 [wherein 'v' is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms; where 'v' is an independent integer from 0 to 3, where 'q' is an independent integer from 0 to 20, and where 'n' is 0 or 1.]

[0232] R" 101 , R” 102 and R” 103 The aliphatic cyclic group which may have substituents is R in formula (b-1) above. 101 It is preferable that the substituent is the group exemplified as a cyclic aliphatic hydrocarbon group in formula (b-1). 101 Examples include substituents similar to those that may be substituted for the cyclic aliphatic hydrocarbon group in the above.

[0233] R" 101 and R” 103 The aromatic cyclic group which may have substituents in formula (b-1) is R 101 It is preferable that the substituent is the aromatic hydrocarbon group exemplified in the cyclic hydrocarbon group in formula (b-1). 101 Examples include substituents similar to those that may be substituted for the aromatic hydrocarbon group in the above.

[0234] R" 101 The chain-like alkyl group which may have substituents in formula (b-1) is R 101 It is preferable that the group is one of the examples given as a chain-like alkyl group in the compound. R" 103 The chain-like alkenyl group which may have substituents in formula (b-1) is R 101 It is preferable that the group is one of the examples given as a chain-like alkenyl group in the formula.

[0235] • Anion in component (b-2) In formula (b-2), R 104 , R 105 Each of these is independently a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents, and each of them is R in formula (b-1). 101 Similar examples can be given. However, R 104 , R 105 These may be bonded to each other to form a ring. R 104 , R 105 The alkyl group is preferably a linear alkyl group which may have substituents, and more preferably a linear or branched alkyl group, or a linear or branched fluorinated alkyl group. The number of carbon atoms in the chain-like alkyl group is preferably 1 to 10, more preferably 1 to 7, and even more preferably 1 to 3. 104 , R 105 The number of carbon atoms in the chain-like alkyl group is preferably small within the above range of carbon atoms, for reasons such as good solubility in the resist solvent. 104 , R 105 In the chain-like alkyl group, a larger number of hydrogen atoms substituted with fluorine atoms is preferable because it increases the acid strength and improves transparency to high-energy light and electron beams below 250 nm. The proportion of fluorine atoms in the chain-like alkyl group, i.e., the fluorination rate, is preferably 70-100%, more preferably 90-100%, and most preferably a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms. In formula (b-2), V 102 , V 103 These are, independently, a single bond, an alkylene group, or a fluorinated alkylene group, and each is V in formula (b-1).101 Similar examples include the above. In formula (b-2), L 101 , L 102 Each of these is either a single bond or an oxygen atom, independently of the others.

[0236] • Anion in component (b-3) In formula (b-3), R 106 ~R 108 Each of these is independently a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents, and each of them is R in formula (b-1). 101 Similar examples include the above. In formula (b-3), L 103 ~L 105 These are, independently, single bonds, -CO-, or -SO2-.

[0237] Among the above, the anion in component (b-1) is preferred as the anion portion of component (B).

[0238] {cation part} In the above equations (b-1), (b-2), and (b-3), M' m+ This represents an onium cation with an m-valence. Among these, sulfonium cations and iodonium cations are preferred. m is an integer greater than or equal to 1.

[0239] Preferred cation portion ((M' m+ ) 1 / m Examples of these include organic cations represented by the following general formulas (ca-1) to (ca-3).

[0240] [ka] [In the formula, R 201 ~R 207 Each of these independently represents an aryl group, alkyl group, or alkenyl group, which may have substituents. 201 ~R 203 , R 206 ~R 207These atoms may bond to each other to form a ring with the sulfur atom in the formula. 208 ~R 209 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 210 This is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted -SO2- containing cyclic group. 201 This represents -C(=O)- or -C(=O)-O-.

[0241] In the above general formulas (ca-1) to (ca-3), R 201 ~R 207 Examples of aryl groups in this context include unsubstituted aryl groups having 6 to 20 carbon atoms, with phenyl and naphthyl groups being preferred. R 201 ~R 207 The alkyl group in this is preferably a linear or cyclic alkyl group having 1 to 30 carbon atoms. R 201 ~R 207 The alkenyl group in this compound preferably has 2 to 10 carbon atoms. R 201 ~R 207 , and R 210 Examples of substituents that may be present include alkyl groups, halogen atoms, alkyl halides, carbonyl groups, cyano groups, amino groups, aryl groups, and groups represented by the following general formulas (ca-r-1) to (ca-r-7).

[0242] [ka] [In the formula, R' 201 Each of these is independently a hydrogen atom, an optionally substituted cyclic group, an optionally substituted linear alkyl group, or an optionally substituted linear alkenyl group.

[0243] Cyclic groups that may have substituents: The cyclic group is preferably a cyclic hydrocarbon group, which may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity. Furthermore, the aliphatic hydrocarbon group may be saturated or unsaturated, but is usually preferred to be saturated.

[0244] R' 201 The aromatic hydrocarbon group in this context is a hydrocarbon group having an aromatic ring. The number of carbon atoms in the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, this number of carbon atoms does not include the number of carbon atoms in substituents. R' 201 Specific examples of aromatic rings in aromatic hydrocarbon groups include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic heterocycles in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, nitrogen atoms, etc. R' 201 Specific examples of aromatic hydrocarbon groups in this context include groups obtained by removing one hydrogen atom from the aromatic ring (aryl groups: e.g., phenyl group, naphthyl group, etc.), and groups in which one of the hydrogen atoms of the aromatic ring is replaced by an alkylene group (e.g., arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms in the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0245] R' 201 In this context, cyclic aliphatic hydrocarbon groups include aliphatic hydrocarbon groups that contain a ring in their structure. Examples of aliphatic hydrocarbon groups containing a ring in this structure include alicyclic hydrocarbon groups (groups from which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. A preferred monocyclic alicyclic hydrocarbon group is a group obtained by removing one or more hydrogen atoms from a monocycloalkane. The monocycloalkane is preferably one having 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. A preferred polycyclic alicyclic hydrocarbon group is a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 30 carbon atoms. Among these, polycycloalkanes having a bridging ring polycyclic skeleton such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; and polycycloalkanes having a fused ring polycyclic skeleton such as a cyclic group having a steroid skeleton are more preferred.

[0246] Among them, R' 201 The cyclic aliphatic hydrocarbon group in is preferably a monocycloalkane or polycycloalkane from which one or more hydrogen atoms have been removed, more preferably a polycycloalkane from which one hydrogen atom has been removed, with adamantyl and norbornyl groups being particularly preferred, and the adamantyl group being the most preferred.

[0247] The linear or branched aliphatic hydrocarbon group, which may be bonded to the alicyclic hydrocarbon group, preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms. As for the linear aliphatic hydrocarbon group, linear alkylene groups are preferred, specifically the methylene group [-CH2-], ethylene group [-(CH2)2-], trimethylene group [-(CH2)3-], tetramethylene group [-(CH2)4-], pentamethylene group [-(CH2)5-], etc. Preferred branched aliphatic hydrocarbon groups include branched alkylene groups, specifically alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkylalkylene groups such as alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. In the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0248] Also, R' 201 The cyclic hydrocarbon group in the above formula may contain heteroatoms, such as heterocycles. Specifically, examples include 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 above chemical formulas (r-hr-1) to (r-hr-16).

[0249] R' 201 Examples of substituents in the cyclic group include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, and nitro groups. As alkyl groups used as substituents, alkyl groups having 1 to 5 carbon atoms are preferred, with methyl, ethyl, propyl, n-butyl, and tert-butyl groups being the most preferred. As the substituent, an alkoxy group having 1 to 5 carbon atoms is preferred, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group are more preferred, and a methoxy group and an ethoxy group are most preferred. As the halogen atom used as a substituent, a fluorine atom is preferred. Examples of alkyl halides used as substituents include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, and tert-butyl groups, in which some or all of the hydrogen atoms are substituted with the halogen atoms. A carbonyl group as a substituent is a group that substitutes for a methylene group (-CH2-) that constitutes a cyclic hydrocarbon group.

[0250] Chain-like alkyl groups that may have substituents: R' 201 The chain-like alkyl group may be either linear or branched. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specifically, examples include 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, and 4-methylpentyl group.

[0251] A chain-like alkenyl group which may have substituents: R' 201The linear alkenyl group may be linear or branched, preferably having 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, even more preferably 2 to 4 carbon atoms, and particularly preferably 3 carbon atoms. Examples of linear alkenyl groups include vinyl groups, propenyl groups (allyl groups), and butynyl groups. Examples of branched alkenyl groups include 1-methylvinyl groups, 2-methylvinyl groups, 1-methylpropenyl groups, and 2-methylpropenyl groups. Among the above, linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred.

[0252] R' 201 Substituents in the chain-like alkyl or alkenyl group include, for example, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, nitro groups, amino groups, and the above R' 201 Examples include cyclic groups in this context.

[0253] R' 201 In addition to those mentioned above, the optionally substituted cyclic groups, optionally substituted linear alkyl groups, or optionally substituted linear alkenyl groups may also include those similar to the acid-dissociable group represented by formula (a1-r-2) above, as optionally substituted cyclic groups or optionally substituted linear alkyl groups.

[0254] Among them, R' 201 The cyclic group is preferably a cyclic group which may have substituents, and more preferably a cyclic hydrocarbon group which may have substituents. More specifically, preferred groups include, for example, a phenyl group, a naphthyl group, a polycycloalkane from which one or more hydrogen atoms have been removed; lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-7); and -SO2--containing cyclic groups represented by the general formulas (b5-r-1) to (b5-r-4).

[0255] In the above general formulas (ca-1) to (ca-3), R 201 ~R203 , R 206 ~R 207 When these atoms bond to each other and form a ring with the sulfur atom in the formula, they may be heteroatoms such as sulfur, oxygen, or nitrogen atoms, or carbonyl groups, -SO-, -SO2-, -SO3-, -COO-, -CONH-, or -N(R N )-(the R N is an alkyl group having 1 to 5 carbon atoms. ) may be bonded via functional groups such as ). The formed ring preferably has 3 to 10 members, and particularly preferably 5 to 7 members, including the sulfur atom in its ring skeleton. Specific examples of the formed ring include, for example, a thiophene ring, a thiazole ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthlene ring, a phenoxatiyne ring, a tetrahydrothiophenium ring, and a tetrahydrothiopyranium ring.

[0256] R 208 ~R 209 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. If an alkyl group is formed, it may bond with other elements to form a ring.

[0257] R 210 This is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted -SO2- containing cyclic group. R 210 Examples of aryl groups in this context include unsubstituted aryl groups having 6 to 20 carbon atoms, with phenyl and naphthyl groups being preferred. R 210 The alkyl group in this is preferably a linear or cyclic alkyl group having 1 to 30 carbon atoms. R 210 The alkenyl group in this compound preferably has 2 to 10 carbon atoms. R 210In this context, the optionally substituent-containing -SO2- cyclic group is preferably a "-SO2- containing polycyclic group," and more preferably a group represented by the general formula (b5-r-1).

[0258] Specific examples of the cation represented by the above formula (ca-1) are shown below.

[0259] Specific examples of suitable cations represented by the above formula (ca-1) include the cations represented by the following chemical formulas.

[0260] [ka]

[0261] [ka]

[0262] [ka] [In the formula, g1, g2, and g3 represent the number of repetitions, where g1 is an integer from 1 to 5, g2 is an integer from 0 to 20, and g3 is an integer from 0 to 20.]

[0263] [ka]

[0264] [ka]

[0265] [ka] [In the formula, R” 201 is a hydrogen atom or a substituent, and the substituent is the aforementioned R 201 ~R 207 , and R 210 ~R 212 These are the same as those listed as substituents that may be present.

[0266] [ka]

[0267] Suitable cations represented by the formula (ca-2) include, specifically, diphenyliodonium cation and bis(4-tert-butylphenyl)iodonium cation.

[0268] Specific examples of suitable cations represented by the above formula (ca-3) include the cations represented by the following formulas (ca-3-1) to (ca-3-6).

[0269] [ka]

[0270] In the resist composition of this embodiment, component (B) may be used alone or in combination of two or more types. If the resist composition contains component (B), the content of component (B) in the resist composition is preferably less than 50 parts by mass, and more preferably 10 to 40 parts by mass, per 100 parts by mass of component (A). (B) By setting the content of component (B) within the preferred range described above, pattern formation is sufficiently achieved. Furthermore, when each component of the resist composition is dissolved in an organic solvent, a uniform solution is easily obtained, which is preferable because it results in good storage stability for the resist composition.

[0271] ≪Basic component (D)≫ The resist composition of this embodiment may further contain, in addition to component (A), a basic component (component (D)) that traps (i.e., controls the diffusion of) the acid generated by exposure. Component (D) acts as a quencher (acid diffusion control agent) that traps the acid generated by exposure in the resist composition. Examples of component (D) include a photo-disintegrating base (D1) (hereinafter referred to as "component (D1)") that decomposes upon exposure and loses its ability to control acid diffusion, and a nitrogen-containing organic compound (D2) (hereinafter referred to as "component (D2)") that does not fall under component (D1). Among these, a photo-disintegrating base (component (D1)) is preferred because it is easier to improve the characteristics of high sensitivity, roughness reduction, and suppression of coating defects.

[0272] • About the (D1) component By using a resist composition containing component (D1), the contrast between the exposed and unexposed areas of the resist film can be further improved when forming a resist pattern. The (D1) component is not particularly limited as long as it decomposes upon exposure and loses its acid diffusion controllability, and is preferably one or more compounds selected from the group consisting of the compound represented by the following general formula (d1-1) (hereinafter referred to as "(d1-1) component"), the compound represented by the following general formula (d1-2) (hereinafter referred to as "(d1-2) component"), and the compound represented by the following general formula (d1-3) (hereinafter referred to as "(d1-3) component"). Components (d1-1) to (d1-3) decompose in the exposed areas of the resist film and lose their acid diffusion control properties (basicity), so they do not act as quenchers, but they act as quenchers in the unexposed areas of the resist film.

[0273] [ka] [In the formula, Rd 1 ~Rd 4 Rd in formula (d1-2) is a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents. 2 In this example, assume that no fluorine atoms are bonded to the carbon atoms adjacent to the sulfur atoms. 1 is a single bond or a divalent linking group. m is an integer greater than or equal to M m+ These are each independently m-valent organic cations.

[0274] {(d1-1) component} ··Anion Club In formula (d1-1), Rd 1 R' is a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents, and each of the above R' is... 201 Similar examples include the above. Among these, Rd 1 Preferred substituents are optionally substituted aromatic hydrocarbon groups, optionally substituted aliphatic cyclic groups, or optionally substituted linear alkyl groups. Examples of substituents these groups may have include hydroxyl groups, oxo groups, alkyl groups, aryl groups, fluorine atoms, fluorinated alkyl groups, lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-7), ether bonds, ester bonds, or combinations thereof. When ether bonds or ester bonds are included as substituents, they may be mediated via alkylene groups, and in this case, preferred substituents are the linking groups represented by the general formulas (y-al-1) to (y-al-5). Note that Rd 1 If the aromatic hydrocarbon group, aliphatic cyclic group, or linear alkyl group in has a linking group represented by the general formulas (y-al-1) to (y-al-7) as a substituent, then in the general formulas (y-al-1) to (y-al-7), Rd in formula (d3-1) 1 The carbon atom constituting the aromatic hydrocarbon group, aliphatic cyclic group, or linear alkyl group in the above general formula (y-al-1) to (y-al-7) is V'. 101 That is the case. Suitable examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and a polycyclic structure containing a bicyclooctane skeleton (a polycyclic structure consisting of a bicyclooctane skeleton and other ring structures). The aliphatic cyclic group is more preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane. The linear alkyl group is preferably one with 1 to 10 carbon atoms, and specifically includes linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups; and branched alkyl groups such as 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, and 4-methylpentyl groups.

[0275] When the chain-like alkyl group is a fluorinated alkyl group having a fluorinated alkyl group as a substituent, the number of carbon atoms in the fluorinated alkyl group is preferably 1 to 11, more preferably 1 to 8, and even more preferably 1 to 4. The fluorinated alkyl group may contain atoms other than fluorine. Examples of atoms other than fluorine include oxygen atoms, sulfur atoms, nitrogen atoms, and the like.

[0276] The following are some preferred specific examples of the anionic portion of component (d1-1).

[0277] [ka]

[0278] ··Cation section In formula (d1-1), M m+ This is an m-valent organic cation. M m+ Suitable organic cations include those similar to the cations represented by the general formulas (ca-1) to (ca-5), with the cation represented by the general formula (ca-1) being more preferred, and the cations represented by the formulas (ca-1-1) to (ca-1-70) being even more preferred. (d1-1) Component may be used alone or in combination of two or more types.

[0279] {(d1-2) component} ··Anion Club In formula (d1-2), Rd 2 R' is a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents. 201 Similar examples include the above. However, Rd 2 In this mixture, we assume that the carbon atom adjacent to the S atom is not bonded to a fluorine atom (i.e., not fluorine-substituted). This results in the anions of components (d1-2) becoming appropriately weak acid anions, improving the quenching ability of component (D). Rd 2 The preferred group is a chain-like alkyl group which may have substituents, or an aliphatic cyclic group which may have substituents. The chain-like alkyl group is preferably one with 1 to 10 carbon atoms, and more preferably three to 10. The preferred aliphatic cyclic group is a group obtained by removing one or more hydrogen atoms from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. (which may have substituents); more preferably a group obtained by removing one or more hydrogen atoms from camphor, etc. Rd 2 The hydrocarbon group may have substituents, and such substituents may be Rd of formula (d1-1). 1 Examples include substituents similar to those that may be present on hydrocarbon groups (aromatic hydrocarbon groups, aliphatic cyclic groups, and linear alkyl groups) in the above.

[0280] The following are preferred specific examples of the anionic portion of component (d1-2).

[0281] [ka]

[0282] ··Cation section In formula (d1-2), M m+ is an m-valent organic cation, and M in formula (d1-1) above. m+ It is similar to that. (d1-2) Components may be used individually or in combination of two or more.

[0283] {(d1-3) components} ··Anion Club In formula (d1-3), Rd 3 R' is a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents, and the R' 201 Similar to the above, it is preferable that the group is a cyclic group containing a fluorine atom, a linear alkyl group, or a linear alkenyl group. Among these, a fluorinated alkyl group is preferred, and the above Rd 1 A fluorinated alkyl group similar to the one shown is more preferable.

[0284] In formula (d1-3), Rd 4 R' is a cyclic group which may have substituents, a linear alkyl group which may have substituents, or a linear alkenyl group which may have substituents. 201 Similar examples include the above. In particular, alkyl groups, alkoxy groups, alkenyl groups, and cyclic groups, which may have substituents, are preferred. Rd 4 The alkyl group in is preferably a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc. 4 Some of the hydrogen atoms in the alkyl group may be substituted with hydroxyl groups, cyano groups, etc. Rd 4 The alkoxy group in is preferably an alkoxy group having 1 to 5 carbon atoms. Specifically, examples of alkoxy groups having 1 to 5 carbon atoms include the methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, and tert-butoxy group. Among these, the methoxy group and ethoxy group are preferred.

[0285] Rd 4 The alkenyl group in R' 201Examples of alkenyl groups similar to those in the above include vinyl groups, propenyl groups (allyl groups), 1-methylpropenyl groups, and 2-methylpropenyl groups, which are preferred. These groups may further have substituents of an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms.

[0286] Rd 4 The cyclic group in is R' 201 Examples of cyclic groups similar to those in the above include alicyclic groups obtained by removing one or more hydrogen atoms from cycloalkanes such as cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane, or aromatic groups such as phenyl groups and naphthyl groups. 4 When Rd is an alicyclic group, the resist composition dissolves well in organic solvents, resulting in good lithography properties. 4 When the group is an aromatic group, the resist composition exhibits excellent light absorption efficiency and good sensitivity and lithographic characteristics in lithography using EUV or the like as the exposure light source.

[0287] In formula (d1-3), Yd 1 It is a single bond or a divalent linking group. Yd 1 The divalent linking group in formula (a2-1) is not particularly limited, but may include divalent hydrocarbon groups (aliphatic hydrocarbon groups, aromatic hydrocarbon groups) which may have substituents, and divalent linking groups containing heteroatoms. 21 Examples include divalent hydrocarbon groups that may have substituents, and divalent linking groups containing heteroatoms, as mentioned in the explanation of divalent linking groups in [reference]. Yd 1 The preferred members are carbonyl groups, ester bonds, amide bonds, alkylene groups, or combinations thereof. The alkylene group is more preferably a linear or branched alkylene group, and even more preferably a methylene group or an ethylene group.

[0288] The following are preferred specific examples of the anionic parts of components (d1-3).

[0289] [ka]

[0290] [ka]

[0291] ··Cation section In formula (d1-3), M m+ is an m-valent organic cation, and M in formula (d1-1) above. m+ It is similar to that. (d1-3) Components may be used individually or in combination of two or more.

[0292] Component (D1) may consist of only one of the above components (d1-1) to (d1-3), or it may consist of a combination of two or more components. If the resist composition contains component (D1), the content of component (D1) in the resist composition is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, and even more preferably 2 to 8 parts by mass, per 100 parts by mass of component (A1). When the content of component (D1) is above the preferred lower limit, particularly good lithography characteristics and resist pattern shape are easily obtained. On the other hand, when it is below the upper limit, good sensitivity can be maintained and throughput is also excellent.

[0293] (D1) Method for producing component: The methods for producing the aforementioned components (d1-1) and (d1-2) are not particularly limited and can be produced by known methods. Furthermore, the method for producing components (d1-3) is not particularly limited and may be, for example, similar to the method described in US2012-0149916.

[0294] • About the (D2) component Component (D) may include nitrogen-containing organic compounds that do not fall under component (D1) above (hereinafter referred to as "component (D2)"). Component (D2) is not particularly limited as long as it acts as an acid diffusion control agent and does not fall under component (D1), and any known component may be used. Among these, aliphatic amines are preferred, and among these, secondary aliphatic amines and tertiary aliphatic amines are more preferred. An aliphatic amine is an amine having one or more aliphatic groups, and it is preferable that the aliphatic group has 1 to 12 carbon atoms. Examples of aliphatic amines include amines (alkylamines or alkyl alcoholamines) or cyclic amines in which at least one hydrogen atom of ammonia (NH3) is substituted with an alkyl group or hydroxyalkyl group having 12 or fewer carbon atoms. Specific examples of alkylamines and alkyl alcoholamines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-decylamine; dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine, and dicyclohexylamine; trialkylamines such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, and tri-n-dodecylamine; and alkyl alcoholamines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, and tri-n-octanolamine. Among these, trialkylamines having 5 to 10 carbon atoms are more preferred, and tri-n-pentylamine or tri-n-octylamine are particularly preferred.

[0295] Examples of cyclic amines include heterocyclic compounds containing a nitrogen atom as a heteroatom. These heterocyclic compounds may be monocyclic (aliphatic monocyclic amines) or polycyclic (aliphatic polycyclic amines). Examples of aliphatic monocyclic amines include piperidine and piperazine. As aliphatic polycyclic amines, those having 6 to 10 carbon atoms are preferred, and specifically, examples include 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, hexamethylenetetramine, and 1,4-diazabicyclo[2.2.2]octane.

[0296] Other aliphatic amines include tris(2-methoxymethoxyethyl)amine, tris{2-(2-methoxyethoxy)ethyl}amine, tris{2-(2-methoxyethoxymethoxy)ethyl}amine, tris{2-(1-methoxyethoxy)ethyl}amine, tris{2-(1-ethoxyethoxy)ethyl}amine, tris{2-(1-ethoxypropoxy)ethyl}amine, tris[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]amine, triethanolamine triacetate, etc., with triethanolamine triacetate being preferred.

[0297] Furthermore, an aromatic amine may be used as component (D2). Examples of aromatic amines include 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or their derivatives, trimenzylamine, 2,6-diisopropylaniline, N-tert-butoxycarbonylpyrrolidine, and 2,6-di-tert-butylpyridine.

[0298] (D2) Component may be used alone or in combination of two or more types. When the resist composition contains component (D2), the content of component (D2) in the resist composition is usually in the range of 0.01 to 5 parts by mass per 100 parts by mass of component (A1). By using this range, the resist pattern shape, settling stability over time, etc., are improved.

[0299] <<At least one compound (E) selected from the group consisting of organic carboxylic acids, phosphorus oxoacids and their derivatives>> The resist composition of this embodiment may contain, as an optional component, at least one compound (E) selected from the group consisting of organic carboxylic acids and phosphorus oxoacids and their derivatives (hereinafter referred to as "component (E)"). Examples of organic carboxylic acids include acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, and salicylic acid, among which salicylic acid is preferred. Examples of phosphorus oxoacids include phosphoric acid, phosphonic acid, and phosphinic acid, with phosphonic acid being particularly preferred among these. Examples of derivatives of phosphorus oxoacids include esters obtained by substituting the hydrogen atoms of the above oxoacid with hydrocarbon groups, and examples of hydrocarbon groups include alkyl groups having 1 to 5 carbon atoms and aryl groups having 6 to 15 carbon atoms. Examples of phosphoric acid derivatives include phosphate esters such as di-n-butyl phosphate and diphenyl phosphate. Examples of phosphonic acid derivatives include phosphonic acid esters such as dimethyl phosphonate, di-n-butyl phosphonate, phenylphosphonic acid, diphenyl phosphonate, and dibenzyl phosphonate. Examples of phosphinic acid derivatives include phosphinic acid esters and phenylphosphinic acid. In the resist composition of this embodiment, component (E) may be used alone or in combination of two or more types. If the resist composition contains component (E), the content of component (E) is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 3 parts by mass, per 100 parts by mass of component (A). By setting the content within the above range, sensitivity and lithography characteristics are improved.

[0300] ≪Fluorine additive component (F)≫ The resist composition of this embodiment may contain a fluorine additive component (hereinafter referred to as "component (F)") as a hydrophobic resin. Component (F) is used to impart water repellency to the resist film and, when used as a resin separate from component (A), can improve lithography properties. As component (F), for example, fluorine-containing polymer compounds described in Japanese Patent Publication No. 2010-002870, Japanese Patent Publication No. 2010-032994, Japanese Patent Publication No. 2010-277043, Japanese Patent Publication No. 2011-13569, and Japanese Patent Publication No. 2011-128226 can be used. More specifically, component (F) includes polymers having a constituent unit (f1) represented by the following general formula (f1-1). This polymer is preferably a polymer (homopolymer) consisting only of the constituent unit (f1) represented by the following formula (f1-1); a copolymer of the constituent unit (f1) and the constituent unit (a1); and more preferably a copolymer of the constituent unit (f1) and a constituent unit derived from acrylic acid or methacrylic acid and the constituent unit (a1). Here, the constituent unit (a1) copolymerized with the constituent unit (f1) is preferably a constituent unit derived from 1-ethyl-1-cyclooctyl (meth)acrylate, and more preferably a constituent unit derived from 1-methyl-1-adamantyl (meth)acrylate.

[0301] [ka] [In the formula, R is the same as above, and Rf 102 and Rf 103Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, and Rf 102 and Rf 103 They may be the same or different. 1 Rf is an integer between 0 and 5. 101 It is an organic group containing a fluorine atom.

[0302] In formula (f1-1), R bonded to the α-carbon atom is the same as described above. R is preferably a hydrogen atom or a methyl group. In formula (f1-1), Rf 102 and Rf 103 A fluorine atom is preferred as the halogen atom. Rf 102 and Rf 103 Examples of alkyl groups having 1 to 5 carbon atoms in R include those similar to the alkyl groups having 1 to 5 carbon atoms in R above, with methyl or ethyl groups being preferred. 102 and Rf 103 Specifically, examples of halogenated alkyl groups having 1 to 5 carbon atoms include groups in which some or all of the hydrogen atoms of an alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. Fluorine atoms are preferred as the halogen atoms, particularly Rf. 102 and Rf 103 Preferably, the element is a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms; more preferably, a hydrogen atom, a fluorine atom, a methyl group, or an ethyl group; and even more preferably, a hydrogen atom. In formula (f1-1), nf 1 is an integer between 0 and 5, preferably between 0 and 3, and more preferably 1 or 2.

[0303] In formula (f1-1), Rf 101 This is an organic group containing a fluorine atom, and preferably a hydrocarbon group containing a fluorine atom. The hydrocarbon group containing fluorine atoms may be linear, branched, or cyclic, and preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and particularly preferably 1 to 10 carbon atoms. Furthermore, in hydrocarbon groups containing fluorine atoms, 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 preferable that 60% or more are fluorinated, as this increases the hydrophobicity of the resist film during immersion exposure. Among them, Rf 101 More preferably, fluorinated hydrocarbon groups having 1 to 6 carbon atoms are used, with trifluoromethyl groups, -CH2-CF3, -CH2-CF2-CF3, -CH(CF3)2, -CH2-CH2-CF3, and -CH2-CH2-CF2-CF2-CF2-CF3 being particularly preferred.

[0304] The weight-average molecular weight (Mw) of component (F) (based on polystyrene conversion by gel permeation chromatography) is preferably 1,000 to 50,000, more preferably 5,000 to 40,000, and most preferably 10,000 to 30,000. If it is below the upper limit of this range, it has sufficient solubility in resist solvents for use as a resist, and if it is above the lower limit of this range, the water repellency of the resist film is good. The degree of dispersion of component (F) (Mw / Mn) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.0 to 2.5.

[0305] In the resist composition of this embodiment, component (F) may be used alone or in combination of two or more types. If the resist composition contains component (F), the content of component (F) is preferably 0.5 to 10 parts by mass, and more preferably 1 to 10 parts by mass, per 100 parts by mass of component (A).

[0306] ≪Organic solvent component (S)≫ The resist composition of this embodiment can be manufactured by dissolving the resist material in an organic solvent component (hereinafter referred to as "component (S)"). The (S) component can be any solvent that can dissolve each component used to form a homogeneous solution, and any solvent that is conventionally known as a solvent for chemically amplified resist compositions can be appropriately selected and used. In the resist composition of this embodiment, component (S) may be used alone or as a mixture of two or more solvents. Among these, PGMEA, PGME, γ-butyrolactone, EL, and cyclohexanone are preferred.

[0307] Furthermore, a mixed solvent obtained by mixing PGMEA and a polar solvent is also preferred as component (S). The mixing ratio (mass ratio) can be appropriately determined considering the compatibility between PGMEA and the polar solvent. Furthermore, 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 mass ratio of the former to the latter is preferably 70:30 to 95:5. The amount of component (S) used is not particularly limited and is set appropriately according to the coating thickness, at a concentration that can be applied to a substrate or the like. Generally, component (S) is used so that the solid content concentration of the resist composition is in the range of 0.1 to 20% by mass, preferably 0.2 to 15% by mass.

[0308] The resist composition of this embodiment may further contain, if desired, miscible additives such as additional resins to improve the performance of the resist film, dissolution inhibitors, plasticizers, stabilizers, colorants, anti-halation agents, dyes, etc.

[0309] The resist composition of this embodiment may be subjected to removal of impurities after dissolving the resist material in component (S), using a polyimide porous membrane, a polyamide-imide 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 polyamide-imide porous membrane, or a filter made of a polyimide porous membrane and a polyamide-imide porous membrane. Examples of the polyimide porous membrane and the polyamide-imide porous membrane include those described in Japanese Patent Application Publication No. 2016-155121.

[0310] The resist composition of this embodiment described above includes a resin component (A1) having a constituent unit (a0) derived from a compound represented by the general formula (a0-1). The constituent unit (a0) has an acid-dissociable group represented by the general formula (a0-pg) (hereinafter also referred to as "acid-dissociable group (a0-pg)") bonded to the aromatic ring Ar. The acid-dissociable group (a0-pg) is a secondary or tertiary carbon atom C bonded to a carbonyloxy group (C(=O)-O-). 1 Adjacent carbon atom C 2 And the carbon atom C 2 Adjacent carbon atom C 2 This forms an unsaturated double bond. Therefore, the carbocation generated when the acid-dissociable group (a0-pg) dissociates is the carbon C 2 and the carbon C 3 Compared to carbocations formed when acid-dissociable groups that do not form unsaturated double bonds dissociate, it has higher stability. Therefore, the constituent unit (a0) has improved acid-dissociability. Furthermore, in the constituent unit (a0), the carboxylic acid produced by the dissociation of the acid-dissociable group (a0-pg) contains the aromatic ring Ar, and is therefore more hydrophobic than methacrylic acid or acrylic acid. It is therefore presumed that this can suppress film peeling and pattern collapse of the resist pattern.

[0311] (Method for forming resist patterns) A resist pattern formation method according to a second aspect of the present invention is a method comprising the steps of forming a resist film on a support using the resist composition according to the first aspect of the present invention described above, exposing the resist film, and developing the exposed resist film to form a resist pattern. One embodiment of such a resist pattern formation method is, for example, a resist pattern formation method carried out as follows.

[0312] First, the resist composition of the above embodiment is applied onto a support using a spinner or the like, and a bake (post-application bake (PAB)) treatment is performed for 40 to 120 seconds, preferably 60 to 90 seconds, at a temperature of, for example, 80 to 150°C, to form a resist film. Next, the resist film is subjected to selective exposure using an exposure apparatus such as an electron beam lithography apparatus or an ArF exposure apparatus, either through exposure via a mask (mask pattern) on which a predetermined pattern has been formed, or by direct irradiation with an electron beam without going through a mask pattern. After this, a bake (post-exposure bake (PEB)) treatment is performed for 40 to 120 seconds, preferably 60 to 90 seconds, at a temperature of, for example, 80 to 150°C. Next, the resist film is subjected to a developing process. In the case of an alkaline developing process, an alkaline developer is used, and in the case of a solvent developing process, a developer containing an organic solvent (organic developer) is used.

[0313] After the developing process, a rinsing process is preferably performed. In the case of an alkaline developing process, a water rinse using pure water is preferred, and in the case of a solvent developing process, a rinsing solution containing an organic solvent is preferred. In the case of a solvent development process, after the development or rinsing process, a process may be performed to remove the developer or rinse solution adhering to the pattern using a supercritical fluid. After development or rinsing, the film is dried. In some cases, a bake (post-bake) process may be performed after the development process.

[0314] The support material is not particularly limited and can be any conventionally known material, such as a substrate for electronic components or a substrate on which a predetermined wiring pattern has been formed. More specifically, examples include silicon wafers, metal substrates such as copper, chromium, iron, and aluminum, and glass substrates. As for the wiring pattern material, for example, copper, aluminum, nickel, and gold can be used.

[0315] The wavelength used for exposure is not particularly limited, and can be used with radiation such as ArF excimer lasers, KrF excimer lasers, F2 excimer lasers, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-rays, and soft X-rays.

[0316] The method for exposing the resist film may be conventional exposure (dry exposure) performed in an inert gas such as air or nitrogen, or it may be liquid immersion lithography. Immersion lithography is an exposure method in which the space between the resist film and the lens at the lowest position of the exposure apparatus is first filled with a solvent (immersion medium) that has a refractive index greater than that of air, and then exposure (immersion exposure) is performed in that state. As the immersion medium, a solvent having a refractive index greater than that of air and less than that of the resist film being exposed is preferred. Examples include water, fluorinated inert liquids, silicon-based solvents, and hydrocarbon-based solvents. Water is preferably used as the immersion medium.

[0317] Examples of alkaline developers used in the alkaline development process include 0.1 to 10% by mass of tetramethylammonium hydroxide (TMAH) aqueous solution. The organic solvent contained in the organic developer solution used in the solvent development process can be any solvent capable of dissolving component (A) (component (A) before exposure), and can be appropriately selected from known organic solvents. Specifically, examples include polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, as well as hydrocarbon solvents.

[0318] 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.

[0319] Examples of nitrile solvents include acetonitrile, propionitrile, valeronitrile, and butyronitrile.

[0320] Organic developers may contain known additives as needed. Examples of such additives include surfactants.

[0321] The development process can be carried out by known development methods, such as immersing the support in a developer solution for a certain period of time (dip method), piling the developer solution onto the surface of the support using surface tension and leaving it still for a certain period of time (paddle method), spraying the developer solution onto the surface of the support (spray method), or continuously dispensing the developer solution onto a support rotating at a constant speed while scanning the developer dispensing nozzle at a constant speed (dynamic dispensing method).

[0322] In the solvent-based development process, the rinsing solution used for rinsing after development can contain an organic solvent that is less likely to dissolve the resist pattern, selected from among the organic solvents listed above for use in the organic developer. Typically, 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 individually or in combination of two or more. They may also be used in mixtures with other organic solvents or water.

[0323] Rinsing (cleaning) using a rinsing solution can be carried out by known rinsing methods. Examples of such rinsing methods include continuously applying the rinsing solution onto a support rotating at a constant speed (rotary coating method), immersing the support in the rinsing solution for a certain period of time (dip method), and spraying the rinsing solution onto the surface of the support (spray method).

[0324] It is preferable that the resist composition of the above-described embodiment and the various materials used in the resist pattern formation method of the above-described embodiment (for example, resist solvent, developer, rinse solution, anti-reflective film forming composition, top coat forming composition, etc.) do not contain impurities such as metals, metal salts containing halogens, acids, alkalis, sulfur atoms, or phosphorus atoms. 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 amount of impurities contained in these materials is preferably 200 ppb or less, more preferably 1 ppb or less, even more preferably 100 ppt (parts per trillion) or less, particularly preferably 10 ppt or less, and most preferably substantially absent (below the detection limit of the measuring device).

[0325] As described above, the resist pattern formation method of this embodiment uses the resist composition described above, making it possible to form a resist pattern with high sensitivity and good resolution.

[0326] (compound) The compound of this embodiment is represented by the following general formula (a0-1).

[0327] [ka] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halogen having 1 to 5 carbon atoms; La 01 and La 02 Each is independently a single bond or a divalent linking group; Ar is an aromatic ring; Ra 01 is a substituent other than a hydroxyl group; m1 is an integer greater than or equal to 0, as long as the valence allows; and Rpg is an acid-dissociable group represented by the following general formula (a0-pg).

[0328] [ka] [In the formula, * represents -La 02 It is a bond that connects to -O- in -C(=O)-O-; Ra 02 C is a hydrogen atom or a hydrocarbon group; 1 is a secondary or tertiary carbon atom; A is an aliphatic ring with 6 or more carbon atoms; C 2 and C 3 Each of these is an independent carbon atom that constitutes a carbon-carbon unsaturated bond that forms part of the ring skeleton of an aliphatic ring with 6 or more carbon atoms in A; Ra 03 and Ra 04 Each is independently a hydrogen atom or a hydrocarbon group; Ra 05 is a hydrocarbon group; n1 is a non-negative integer as long as the valence allows; however, C 1 It does not constitute part of the cross-linking structure; Ra 02 Ra 03 and Ra 04 If both are hydrogen atoms, then n1 is an integer greater than or equal to 1.

[0329] The compound of this embodiment is similar to the compound that derives the constituent unit (a0) of component (A1) of the resist composition according to the first embodiment. The compound of this embodiment is preferably at least one selected from the group consisting of compounds represented by the general formula (a0-t1) and compounds represented by the general formula (a0-s1).

[0330] (Method of producing compounds) The method for producing the compound of this embodiment is not particularly limited and can be produced by appropriately combining known methods.

[0331] The compound of this embodiment is useful for producing a polymer compound having the constituent unit (a0) (the resin component (A1) in the first embodiment).

[0332] <Polymer compounds> The polymer compound of this embodiment has a constituent unit (a0) derived from the compound represented by formula (a0-1). That is, the polymer compound of this embodiment is the same as the resin component (A1) in the first embodiment. [Examples]

[0333] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0334] <Synthesis of Compounds> [Synthesis Example 1: Synthesis of monomer (m01)] 5.9 g of styrene carboxylic acid was dissolved in 40.0 g of tetrahydrofuran. A mixed solution of 7.6 g of diazabicycloundensene (DBU), 5.8 g of 3-methylcyclohexenol, 9.0 g of carbonyldiimidazole (CDI), and 40.0 g of tetrahydrofuran was added dropwise to this solution under ice cooling. After stirring at 60°C for 4 hours, the solvent was removed by distillation, and 80.0 g of heptane was added to the residue. Impurities were removed by filtration. Subsequently, the monomer (m01) was obtained by purification by column chromatography.

[0335] [ka]

[0336] monomer (m01) 1 The 1H NMR measurement results are shown below. 1H NMR(400MHz,DMSO-d6)δ(ppm)=1.63(4H,m),1.93(2H,m),2.19(2H,m),5.13(1H,q) ,5.25(1H,dd),5.37(1H,m),5.76(1H,dd),6.72(1H,dd),7.45(2H,d),7.67(2H,d)

[0337] [Synthesis Examples 2-10: Synthesis of monomers (m02)-(m06)] Except for changing the combination of starting materials, monomers (m02) to (m06) were obtained in the same manner as in "Synthesis Example 1: Synthesis of monomer (m01)" described above.

[0338] monomer (m02) 1 The 1H NMR measurement results are shown below. 1 H NMR(400MHz,DMSO-d6)δ(ppm)=1.50(2H,m),1.73(5H,m),2.09(4H,m),5.20(1H,m ),5.25(1H,m),5.29(1H,m),5.76(1H,dd),6.72(1H,dd),7.45(2H,d),7.67(2H,d)

[0339] [ka]

[0340] monomer (m03) 1 The 1H NMR measurement results are shown below. 1 H NMR(400MHz,DMSO-d6)δ(ppm)=1.63(4H,m),1.93(2H,m),2.19(2H,m),5.13(1H,q) ,5.25(1H,dd),5.37(1H,m),5.76(1H,dd),6.72(1H,dd),7.37(2H,m),7.84(2H,m)

[0341] [ka]

[0342] monomer (m04) 1 The 1H NMR measurement results are shown below. 1 H NMR(400MHz,DMSO-d6)δ(ppm)=1.70(4H,m),2.01(4H,m),5.13(1H,m),5.27(1H,m),5.76(1H,dd),6.72(1H,dd),7.45(2H,d),7.67(2H,d)

[0343] [ka]

[0344] monomer (m05) 1 The 1H NMR measurement results are shown below. 1 H NMR(400MHz,DMSO-d6)δ(ppm)=1.24(3H,m),1.65(2H,m),1.88(2H,m),2.06(2H,m),5.25 (1H,dd),5.59(1H,m),5.68(1H,m),5.76(1H,dd),6.72(1H,dd),7.45(2H,d),7.69(2H,d)

[0345] [ka]

[0346] monomer (m06) 1 The 1H NMR measurement results are shown below. 1 H NMR(400MHz,DMSO-d6)δ(ppm)=1.47(4H,m),1.66(3H,m),2.76(1H,m),2.90(1H,m),5.03 (1H,m),5.25(1H,dd),5.37(1H,m),5.76(1H,dd),6.72(1H,dd),7.45(2H,d)7.67(2H,d)

[0347] [ka]

[0348] [Synthesis Example 7: Synthesis of monomer (m07)] 20.0 g of 4-hydroxybenzoic acid and 16.9 g of triethylamine were dissolved in 100 g of dichloromethane. A mixed solution of 18.2 g of methacrylate chloride and 36.4 g of dichloromethane was added dropwise to this solution under ice bath. After stirring at 25°C for 2 hours, the solvent was removed by distillation, and methacryloyloxybenzoic acid was obtained by purification by column chromatography.

[0349] [ka]

[0350] 10.0 g of methacryloyloxybenzoic acid was dissolved in 60.0 g of tetrahydrofuran. A mixed solution of 9.2 g of diazabicycloundensene (DBU), 7.1 g of 3-methylcyclohexenol, 11.0 g of carbonyldiimidazole (CDI), and 60.0 g of tetrahydrofuran was added dropwise to this solution under ice cooling. After stirring at 60°C for 4 hours, the solvent was removed by distillation, and 120 g of heptane was added to the residue. Impurities were removed by filtration. Subsequently, the monomer (m07) was obtained by purification by column chromatography.

[0351] [ka]

[0352] monomer (m07) 1 The 1H NMR measurement results are shown below. 1 H NMR(400MHz,DMSO-d6)δ(ppm)=1.65(4H,m),1.94(2H,m),2.01(3H,m),2.19(2H, m),5.13(1H,m),5.37(1H,m),6.18(1H,d),6.43(1H,d),7.44(2H,d),8.06(2H,d)

[0353] [Synthesis Example 8: Synthesis of monomer (m08)] 10.0 g of hydroxyacetic acid and 15.3 g of triethylamine were dissolved in 100 g of dichloromethane, and a mixed solution of 26.3 g of benzoyl chloride and 52.6 g of dichloromethane was added dropwise to the solution under ice bath. After stirring at 25°C for 2 hours, the solvent was removed by distillation, and intermediate A was obtained by purification by column chromatography.

[0354] [ka]

[0355] 10 g of intermediate A was dissolved in 60.0 g of tetrahydrofuran, and a mixed solution of 9.2 g of diazabicycloundensene (DBU), 7.1 g of 3-methylcyclohexenol, 11.0 g of carbonyldiimidazole (CDI), and 60.0 g of tetrahydrofuran was added dropwise to the solution under ice cooling. After stirring at 60°C for 4 hours, the solvent was removed by distillation, and 120 g of heptane was added to the residue. Impurities were removed by filtration. Subsequently, the monomer (m08) was obtained by purification by column chromatography.

[0356] [ka]

[0357] Monomer (m08) 1 The 1H NMR measurement results are shown below. 1 H NMR(400MHz,DMSO-d6)δ(ppm)=1.65(3H,m),1.70(2H,m),1.98(4H,m),5.13(1H,m),5.21 (2H,m),5.25(1H,m),5.37(1H,m),5.76(1H,dd),6.72(1H,dd),7.45(2H,d),7.67(2H,d)

[0358] [Synthesis Examples 9-10: Synthesis of monomers (m09)-(m010)] Except for changing the combination of starting materials, monomers (m09) to (m010) were obtained in the same manner as in "Synthesis Example 1: Synthesis of monomer (m01)" described above.

[0359] monomer (m09) 1 The 1H NMR measurement results are shown below. 1 H NMR(400MHz,DMSO-d6)δ(ppm)=0.95(3H,d),1.64(1H,m),1.65(3H,m),1.85(2H,m),2.03(2H,m) ,5.13(1H,m),5.25(1H,dd),5.37(1H,m),5.76(1H,dd),6.72(1H,dd),7.45(2H,d),7.67(2H,d)

[0360] [ka]

[0361] monomer (m010) 1 The 1H NMR measurement results are shown below. 1 H NMR(400MHz,DMSO-d6)δ(ppm)=1.65(3H,m),1.70(2H,m),1.94(2H,m),2.09(2H,m),2.48(3H,s),5.13 (1H,m),5.37(1H,m),5.60(1H,dd),5.72(1H,dd),7.37(1H,m),7.40(1H,m),7.57(1H,m),7.78(1H,m)

[0362] [ka]

[0363] <Synthesis of polymer compounds> The polymer compounds (A0-1) to (A0-10) and (A1-1) to (A1-5) used in this example were obtained by radical polymerization using monomers that induce the constituent units of each polymer compound in a predetermined molar ratio. For each obtained polymer compound, the weight-average molecular weight (Mw) and molecular weight dispersion (Mw / Mn) were determined by GPC measurement (converted to standard polystyrene). The results are shown in Table 1. Furthermore, for each obtained polymer compound, the copolymerization composition ratio (the proportion (molar ratio) of each constituent unit in the structural formula) was determined by the carbon-13 nuclear magnetic resonance spectrum (600 MHz, 13 The results were determined by 13C-NMR. The results are shown in Table 1.

[0364] [ka]

[0365] [ka]

[0366] [Table 1]

[0367] The structures of the polymer compounds (A0-1) to (A0-10) and (A1-1) to (A1-5) are shown below. In each formula, l and m represent the composition ratio of each constituent unit, where l / m = 60 / 40.

[0368] [ka]

[0369] [ka]

[0370] <Preparation of the resist composition> (Examples 1-16, Comparative Examples 1-5) Each of the components shown in Tables 2 and 3 was mixed and dissolved to prepare the resist compositions for each example.

[0371] [Table 2]

[0372] [Table 3]

[0373] In Tables 2 and 3, each abbreviation has the following meaning. The numbers in brackets [ ] represent the amount (parts by mass) of the ingredients.

[0374] (A0)-1~(A0)-10: The aforementioned polymer compounds (A0-1)~(A0-10). (A1)-1 to (A1)-5: The aforementioned polymer compounds (A1-1) to (A1-5).

[0375] (B)-1: An acid generator consisting of the following compound (B1-1). (B)-2: An acid generator consisting of the following compounds (B1-2). (B)-3: An acid generator consisting of the following compounds (B1-3). (B)-4: An acid generator consisting of the following compounds (B1-4). (B)-5: An acid generator consisting of the following compounds (B1-5). (B)-6: An acid generator consisting of the following compounds (B1-6). (B)-7: An acid generator consisting of the following compounds (B1-7). (D)-1: An acid diffusion control agent consisting of the following compound (D1-1). (S)-1: A mixed solvent of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 60 / 40 (mass ratio).

[0376] [ka]

[0377] <Resist pattern formation> Each example of the resist composition was applied to an 8-inch silicon substrate treated with hexamethyldisilazane (HMDS) using a spinner, and a 50 nm thick resist film was formed by pre-baking (PAB) on a hot plate at 110°C for 60 seconds and drying. Next, the resist film was subjected to a JEOL-JBX-9300FS electron beam lithography system (manufactured by JEOL Ltd.) at an acceleration voltage of 100kV to create a 1:1 line-and-space pattern (hereinafter referred to as an LS pattern) with a target size of 50nm line width. This was followed by a post-exposure heating (PEB) treatment at 100°C for 60 seconds. Next, alkaline development was performed at 23°C for 60 seconds using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) "NMD-3" (product name, manufactured by Tokyo Ohka Kogyo Co., Ltd.). Afterward, a 15-second rinse was performed using pure water. As a result, a 1:1 LS pattern with a line width of 50 nm was formed.

[0378] [Evaluation of optimal exposure (Eop)] The optimal exposure amount Eop(μC / cm²) for forming a target-sized LS pattern by the above-described resist pattern formation method is: 2 The result was calculated as "Eop(μC / cm²)". 2 )" is shown in Tables 2-3.

[0379] [Resolution evaluation] The optimal exposure amount Eop(μC / cm²) for forming the target-sized LS pattern through the above <resist pattern formation> method is to form the resist pattern. 2 When forming an LS pattern by gradually increasing the exposure amount from ), the minimum size at which the pattern is resolved was determined using a scanning electron microscope S-9380 (Hitachi High-Technologies Corporation). The results are shown in Tables 2-3 as "resolution (nm)".

[0380] The results shown in Tables 2-3 confirm that the resist compositions of Examples 1-10 exhibited higher sensitivity and better resolution in resist pattern formation compared to the resist compositions of Comparative Examples 1-5.

Claims

1. A resist composition that generates acid upon exposure and whose solubility in a developer changes due to the action of the acid, It contains a resin component (A1) whose solubility in the developer changes due to the action of acid, The resin component (A1) is a resist composition having a constituent unit (a0) derived from a compound represented by the following general formula (a0-s1). 【Chemistry 1】 [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halogen having 1 to 5 carbon atoms; La ０１ These are single bonds or ester bonds [-C(=O)-O-, -O-C(=O)-]; La ０２ is a single bond; Ar is a benzene ring; Ra ０１ C is an alkyl group having 1 to 5 carbon atoms; m1 is an integer greater than or equal to 0, as long as the valence allows; Cs is a secondary carbon atom; A is an aliphatic ring having 6 or more carbon atoms; C2 and C3 are carbon atoms that independently constitute a carbon-carbon unsaturated bond forming part of the ring skeleton of the aliphatic ring having 6 or more carbon atoms in A; Ra031 and Ra041 are one hydrogen atom and the other a chain-like alkyl group having 1 to 5 carbon atoms; Ra051 is an alkyl group having 1 to 5 carbon atoms; n11 is an integer greater than or equal to 0, as long as the valence allows.

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

3. The resist pattern forming method according to claim 2, wherein in the step of exposing the resist film, the resist film is exposed to EUV (extreme ultraviolet) or EB (electron beam).

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