Resist composition, resist pattern formation method, compound, and polymer compound

Abstract

Provided is a resist composition capable of improving lithography properties such as resolution, pattern roughness, and exposure margin. 【Solution Means】A resist composition that generates an acid upon exposure and has its solubility in a developer changed by the action of the acid, the resist composition containing a resin component having a structural unit derived from a compound represented by formula (a0-m0). In general formula (a0-m0), W 0 represents a polymerizable group-containing group. X 0 represents a hydrogen atom, an alkyl group, or a group represented by *-L 02 -COOR 02 . L 01 and L 02 each independently represent a linear or cyclic aliphatic hydrocarbon group which may have a substituent. R 01 and R 02 each independently represent an acid-dissociable group. TIFF2026168518000129.tif48170

Description

Technical Field

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

Background Art

[0002] In recent years, in the manufacture of semiconductor elements and liquid crystal display elements, pattern miniaturization has been rapidly progressing due to advances in lithography technology. As a method for miniaturization, shortening the wavelength (increasing the energy) of the exposure light source is generally carried out.

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

[0004] In chemically amplified resist compositions, a resin having a specific structural unit is generally used to improve lithographic properties and the like. For example, Patent Document 1 discloses a resist composition containing a resin component (A1) having a structural unit (a0) including an arylene group bonded to the nitrogen atom of an amide bond, and an acid-dissociable group bonded to the arylene group via a linking group.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of Invention

Problems to be Solved by the Invention

[0006] Along with ongoing miniaturization of resist patterns, for example, in lithography using EUV or EB, the formation of fine patterns on the order of several tens of nanometers is targeted. Along with such miniaturization of resist patterns, improvement in all lithography properties such as resolution, pattern roughness, and exposure latitude has become an issue.

[0007] The present invention has been made in view of the above circumstances, and an object thereof is to provide a resist composition capable of enhancing lithography properties such as resolution, pattern roughness, and exposure latitude, a method for forming a resist pattern using the resist composition, a polymer compound useful for the resist composition, and a compound usable for the synthesis of the polymer compound. [Means for Solving the Problems]

[0008] In order to solve the above problems, the present invention adopts the following configurations. That is, a first aspect of the present invention is a resist composition that generates an acid upon exposure, and whose solubility in a developing solution changes under the action of the acid, the resist composition containing a resin component (A1) whose solubility in a developing solution changes under the action of an acid, wherein the resin component (A1) has a structural unit (a0) derived from a compound represented by the following general formula (a0-m0).

[0009] [Chemical Formula] [In the formula, W 0 represents a polymerizable group-containing group. X 0 represents a hydrogen atom, an alkyl group, or *-L 02 -COOR 02 represents a group represented by. * represents a bond bonded to the adjacent nitrogen atom. L 01 and L 02 each independently represent a chain or cyclic aliphatic hydrocarbon group which may have a substituent. R 01 and R 02 each independently represent an acid dissociable group. n0 is 1 or 2. When n0 is 1, the X 0 is *-L 02-COOR 02 The group is represented by . When n0 is 2, the X 0 is a hydrogen atom or an alkyl group. When n0 is 2, two R 01 They may be the same or they may be different.

[0010] A second aspect of the present invention is a resist pattern forming method comprising the steps of forming a resist film on a support using a resist composition according to the first aspect, exposing the resist film, and developing the exposed resist film to form a resist pattern.

[0011] A third aspect of the present invention is a compound represented by the following general formula (a0-m0).

[0012] [ka] [In the formula, W 0 X represents a polymerizable group-containing group. 0 is a hydrogen atom, an alkyl group, or *-L 02 -COOR 02 This represents a group represented by *. * represents a bond to an adjacent nitrogen atom. 01 and L 02 Each of these independently represents a chain or cyclic aliphatic hydrocarbon group which may have substituents. 01 and R 02 Each of these independently represents an acid-dissociable group. n0 is either 1 or 2. When n0 is 1, the X 0 is, *-L 02 -COOR 02 The group is represented by . When n0 is 2, the X 0 is a hydrogen atom or an alkyl group. When n0 is 2, two R 01 They may be the same or they may be different.

[0013] A fourth aspect of the present invention is a polymer compound having a constituent unit (a0) derived from the compound of the third aspect. [Effects of the Invention]

[0014] According to the present invention, it is possible to provide a resist composition that can improve lithography characteristics such as resolution, pattern roughness, and exposure margin, a method for forming a resist pattern using the resist composition, a polymer compound useful for the resist composition, and a compound that can be used for the synthesis of the polymer compound. [Modes for carrying out the invention]

[0015] 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.

[0016] 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, the acid-decomposable group includes a group in which the polar group is protected by an acid-dissociable group (for example, a group in which a hydrogen atom of a hydroxyl group-containing polar group is protected by an acid-dissociable group).

[0017] The term "acid-dissociable group" refers to both (i) a group having acid dissociability that allows the bond between the acid-dissociable group and the atom adjacent to the acid-dissociable group to be cleaved under the action of an acid, and (ii) a group that allows the bond between the acid-dissociable group and the atom adjacent to the acid-dissociable group to be cleaved as a result of a further decarboxylation reaction after partial bonds are cleaved under the action of an acid. The acid-dissociable group constituting the acid-decomposable group needs to be a group having lower polarity than the polar group generated by dissociation of the acid-dissociable group, whereby when the acid-dissociable group is dissociated under the action of an acid, a polar group having higher polarity than the acid-dissociable group is generated to increase the polarity. As a result, the polarity of the entire component (A1) increases. The increase in polarity relatively changes the solubility in a developer; the solubility increases when the developer is an alkaline developer, and the solubility decreases when the developer is an organic developer.

[0018] The term "base component" refers to an organic compound having film-forming ability. The organic compounds used as the base component are roughly classified into non-polymers and polymers. As the non-polymer, those having a molecular weight of usually 500 or more and less than 4000 are used. Hereinafter, the term "low-molecular compound" refers to a non-polymer having a molecular weight of 500 or more and less than 4000. As the polymer, those having a molecular weight of usually 1000 or more are used. Hereinafter, the terms "resin", "high-molecular compound" or "polymer" refer to a polymer having a molecular weight of 1000 or more. As the molecular weight of the polymer, a polystyrene-equivalent weight average molecular weight measured by GPC (gel permeation chromatography) is used.

[0019] The term "derived structural unit" means a structural unit formed by cleavage of a multiple bond between carbon atoms, for example, an ethylenic double bond. In the "acrylate ester", the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent. The substituent (R that substitutes the hydrogen atom bonded to the carbon atom at the α-positionαx ) 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.

[0020] 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.

[0021] 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.

[0022] (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.

[0023] 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 "substrate 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 substrate 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. As the constituent unit that generates acid upon exposure, the constituent unit (a5), described later, may be used.

[0024] 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 of the resist film. 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.

[0025] 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.

[0026] <Base material component (A)> In the resist composition of this embodiment, it is preferable to use a component (A) that contains 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 that 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.

[0027] In the resist composition of this embodiment, component (A) may be used alone or in combination of two or more types.

[0028] (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 general formula (a0-m0) described below.

[0029] ≪Component Unit (a0)≫ Component (A1) has a constituent unit (a0) derived from a compound represented by the following general formula (a0-m0) (hereinafter also referred to as "compound (m0)").

[0030] [ka] [In the formula, W 0 X represents a polymerizable group-containing group. 0is a hydrogen atom, an alkyl group, or *-L 02 -COOR 02 This represents a group represented by *. * represents a bond to an adjacent nitrogen atom. 01 and L 02 Each of these independently represents a chain or cyclic aliphatic hydrocarbon group which may have substituents. 01 and R 02 Each of these independently represents an acid-dissociable group. n0 is either 1 or 2. When n0 is 1, the X 0 is, *-L 02 -COOR 02 The group is represented by . When n0 is 2, the X 0 is a hydrogen atom or an alkyl group. When n0 is 2, two R 01 They may be the same or they may be different.

[0031] In the above formula (a0-m0), W 0 This represents a polymerizable group. W 0 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.

[0032] 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 Each of these is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, or an alkyl halide having 1 to 5 carbon atoms, and Ya x0It is a single bond or a divalent linking group. Ya x0 Examples of divalent linking groups in this context include divalent hydrocarbon groups which may have substituents, and divalent linking groups which contain heteroatoms. x0 Examples of divalent linking groups in this include ester bonds (-C(=O)-O-), oxycarbonyl groups (-OC(=O)-), amide bonds (-C(=O)-NH-, -NH-C(=O)-), ether bonds (-O-), linear or branched alkylene groups, phenylene groups, or combinations thereof. x0 The phenylene group is preferably a single bond or may have a hydroxyl group as a substituent, and a single bond is more preferred.

[0033] In the above formula (a0-m0), L 01 This represents a linear or cyclic aliphatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated (e.g., an alkenylene group, an alkylylene group, etc.).

[0034] • Chain-like aliphatic hydrocarbon groups The chain-like aliphatic hydrocarbon group may be a linear aliphatic hydrocarbon group or a branched aliphatic hydrocarbon group. The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, particularly preferably 1 to 3 carbon atoms, and most preferably 1 or 2 carbon atoms. The linear aliphatic hydrocarbon group is preferably a linear alkylene group, specifically a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], a pentamethylene group [-(CH2)5-], and the like. 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, a linear alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group is even more preferred.

[0035] Examples of substituents that the linear or branched aliphatic hydrocarbon group may have include alkoxy groups (such as methoxy, ethoxy, propoxy, and butoxy groups), hydroxyl groups, carbonyl groups, and halogen atoms.

[0036] • Cyclic aliphatic hydrocarbon group A cyclic aliphatic hydrocarbon group is a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring. This cyclic aliphatic hydrocarbon group may be bonded to the chain-like aliphatic hydrocarbon group described above. Examples of the cyclic aliphatic hydrocarbon group include a group in which a cyclic aliphatic hydrocarbon group is bonded to the end of the chain-like aliphatic hydrocarbon group, and a group in which a cyclic aliphatic hydrocarbon group is interposed in the middle of the chain-like aliphatic hydrocarbon group. The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms, and even more preferably 3 to 6 carbon atoms. The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. A preferred monocyclic alicyclic hydrocarbon group is a group obtained by removing two 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 two hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.

[0037] Substituents that the cyclic aliphatic hydrocarbon group may have include alkyl groups, alkoxy groups (such as methoxy, ethoxy, propoxy, and butoxy groups), hydroxyl groups, carbonyl groups, halogen atoms, and alkyl halides. A cyclic aliphatic hydrocarbon group may have some of the carbon atoms constituting its ring structure replaced by substituents containing heteroatoms. Preferred substituents containing heteroatoms are -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0038] In the above formula (a0-m0), L 01 Among the above, it is preferable that the group is a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched hydrocarbon group having 3 carbon atoms, or a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, and more preferably a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, and more preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms.

[0039] In the above equation (a0-m0), R 01 This represents an acid-dissociable group. Examples of acid-dissociating groups include the "acetal-type acid-dissociating groups," "tertiary alkyl ester-type acid-dissociating groups," and "secondary-type acid-dissociating groups," which are described below.

[0040] Acetal type acid dissociable group: The acid-dissociable group (R) protects the carboxyl group as a polar group. 01 Examples of such groups include the acid-dissociating group represented by the following general formula (a0-r-1) (hereinafter sometimes referred to as the "acetal-type acid-dissociating group").

[0041] [ka] [In the formula, Ra' 1 , Ra' 2 is a hydrogen atom or an alkyl group. 3 Ra' is a hydrocarbon group. 3 Ra' 1 , Ra' 2 It may combine with any of the following to form a ring.

[0042] In formula (a0-r-1), Ra' 1 and Ra' 2 Preferably, at least one of them is a hydrogen atom, and more preferably, both are hydrogen atoms. Ra' 1 Or Ra' 2 If the alkyl group is an alkyl group, the alkyl group can be the same as those listed as substituents that may be bonded to the α-carbon in the description of the α-substituted acrylic acid ester above, and an alkyl group having 1 to 5 carbon atoms is preferred. Specifically, linear or branched alkyl groups are preferred. More 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., with methyl group or ethyl group being more preferred, and methyl group being particularly preferred.

[0043] In formula (a0-r-1), Ra' 3 Examples of hydrocarbon groups include linear or branched alkyl groups, or cyclic hydrocarbon groups. 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.

[0044] 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.

[0045] Ra' 3 When the hydrocarbon group is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic group, and may be a polycyclic group or a monocyclic group. As a monocyclic aliphatic 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 the polycyclic aliphatic hydrocarbon group, a group obtained by removing one hydrogen atom from a polycycloalkane is preferred, and as the polycycloalkane, those having 7 to 12 carbon atoms are preferred, specifically adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 Examples include decane and tetracyclododecane.

[0046] Ra' 3 When the cyclic hydrocarbon group becomes an aromatic group, the aromatic group is a group having at least one aromatic ring. This aromatic ring is not particularly limited as long as it is a cyclic conjugated system with 4n+2 π electrons, and can be monocyclic or polycyclic. Examples of aromatic rings include aromatic hydrocarbon rings and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced by heteroatoms. The number of carbon atoms in the aromatic hydrocarbon ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 5 to 15, and particularly preferably 6 to 12. Specific examples of aromatic hydrocarbon rings include benzene, naphthalene, anthracene, and phenanthrene. 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. Ra' 3 The aromatic group in this compound preferably has 4 to 30 carbon atoms, more preferably 4 to 20, even more preferably 4 to 15, and particularly preferably 4 to 12 carbon atoms. Ra' 3 Specific examples of aromatic 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.

[0047] 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 -RP2 -COOH (hereinafter, these substituents are collectively referred to as "Ra x5 ".) and the like. Here, R P1 is a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms, a monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or a monovalent aromatic group having 4 to 30 carbon atoms. Further, R P2 is a single bond, a divalent linear saturated hydrocarbon group having 1 to 10 carbon atoms, a divalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or a divalent aromatic group having 4 to 30 carbon atoms. Provided that part or all of the hydrogen atoms contained in the linear saturated hydrocarbon group, aliphatic cyclic saturated hydrocarbon group and aromatic group of R P1 and R P2 may be substituted with fluorine atoms. The aliphatic cyclic hydrocarbon group may have one or more of the above-mentioned substituents singly, or may have one or more of each of a plurality of the above-mentioned substituents. Examples of the monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group and the like. Examples of the monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms include monocyclic aliphatic saturated hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, cyclododecyl group; and polycyclic aliphatic saturated hydrocarbon groups such as bicyclo[2.2.2]octanyl group, tricyclo[5.2.1.02,6]decanyl group, tricyclo[3.3.1.13,7]decanyl group, tetracyclo[6.2.1.13,6.02,7]dodecanyl group, adamantyl group and the like. Examples of the monovalent aromatic group having 4 to 30 carbon atoms include groups obtained by removing one hydrogen atom from an aromatic hydrocarbon ring such as benzene, biphenyl, fluorene, naphthalene, anthracene, phenanthrene, and groups obtained by removing one hydrogen atom from an aromatic heterocycle such as pyridine ring, thiophene ring and the like.

[0048] Ra' 3 is, Ra' 1 , Ra'2 When any one of them bonds to form a ring, the cyclic group is preferably a 4- to 7-membered ring, more preferably a 4- to 6-membered ring. Specific examples of the cyclic group include a tetrahydropyranyl group, a tetrahydrofuranyl group and the like.

[0049] Tertiary alkyl ester type acid dissociable group: Examples of the aforementioned acid dissociable group (R that protects a carboxy group as a polar group 01 ) include the acid dissociable group represented by the following general formula (a0-r-2). Among the acid dissociable groups represented by the following formula (a0-r-2), those constituted by alkyl groups may hereinafter be referred to as "tertiary alkyl ester type acid dissociable group" for convenience.

[0050]

Chemical Formula

[0051] Examples of the hydrocarbon group for Ra' 4 include a linear or branched alkyl group, a chain or cyclic alkenyl group, or a cyclic hydrocarbon group. Examples of the linear or branched alkyl group, cyclic hydrocarbon group (monocyclic aliphatic hydrocarbon group, polycyclic aliphatic hydrocarbon group, aromatic group) for Ra' 4 include the same groups as the aforementioned Ra' 3 . The chain or cyclic alkenyl group for Ra' 4 is preferably an alkenyl group having 2 to 10 carbon atoms. Examples of the hydrocarbon group for Ra' 5 and Ra' 6 include the same groups as the aforementioned Ra' 3 .

[0052] Ra'5 and Ra' 6 When these groups bond to each other to form a ring, the following groups are preferred: the group represented by the general formula (a0-r2-1), the group represented by the general formula (a0-r2-2), and the group represented by the general formula (a0-r2-3). Meanwhile, Ra' 4 ~Ra' 6 When these are independent hydrocarbon groups that are not bonded to each other, the group represented by the following general formula (a0-r2-4) is preferred.

[0053] [ka] [In formula (a0-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 (a0-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 (a0-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 group which may have substituents. In formula (a0-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. 14is a hydrocarbon group that may have substituents. * indicates a bond (the same applies hereafter).

[0054] In the above equation (a0-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.

[0055] 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.

[0056] 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.

[0057] In formula (a0-r2-1), Ra' 11 (Ra' 10 The aliphatic cyclic group formed with the bonded carbon atom is Ra' in formula (a0-r-1). 3 The aliphatic hydrocarbon groups (alicyclic hydrocarbon groups) listed above, which are monocyclic or polycyclic groups, are preferred. Among these, monocyclic alicyclic hydrocarbon groups are preferred, and specifically, cyclopentyl groups and cyclohexyl groups are more preferred.

[0058] In formula (a0-r2-2), the cyclic hydrocarbon group formed by Xa together with Ya is Ra' in formula (a0-r-1). 3 Examples include groups obtained by further removing one or more hydrogen atoms from a cyclic monovalent hydrocarbon group (aliphatic 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 (a0-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; bicyclo[2.2.2]octanyl, tricyclo[5.2.1.0 2,6 ]decanyl group, tricyclo[3.3.1.1 3,7 ]decanyl group, tetracyclo[6.2.1.1 3,6 .0 2,7 Examples include polycyclic aliphatic saturated hydrocarbon groups such as dodecanyl groups 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.

[0059] 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.

[0060] 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.

[0061] In formula (a0-r2-3), the aliphatic cyclic group formed by Xaa together with Yaa is Ra' in formula (a0-r-1). 3 The aliphatic hydrocarbon groups listed above, which are monocyclic or polycyclic groups, are preferred. Some of the carbon atoms constituting the aliphatic cyclic group may be substituted with heteroatoms. Examples of heteroatoms include oxygen atoms, sulfur atoms, nitrogen atoms, etc. Some or all of the hydrogen atoms in the aliphatic cyclic group may be substituted with substituents. Examples of substituents include hydroxyl groups, carboxyl groups, halogen atoms, oxo groups (=O), alkoxy groups (methoxy groups, ethoxy groups, propoxy groups, butoxy groups, etc.), and the above-mentioned Ra x5 Similar groups can be mentioned. Preferred substituents that the aliphatic cyclic group may have include, for example, halogen atoms, oxo groups (=O), and methyl groups.

[0062] In formula (a0-r2-3), Ra 104 The aromatic group in this is the aforementioned Ra' 3 Examples include those similar to aromatic groups in [the text]. Among them, Ra 104Specifically, the aromatic groups in this are preferably groups obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring having 5 to 15 carbon atoms, or groups obtained by removing one or more hydrogen atoms from an aromatic heterocycle having 4 to 15 carbon atoms; more preferably groups obtained by removing one or more hydrogen atoms from benzene, naphthalene, anthracene, phenanthrene, pyridine, or thiophene; even more preferably groups obtained by removing one or more hydrogen atoms from benzene, naphthalene, anthracene, or thiophene; particularly preferably groups obtained by removing one or more hydrogen atoms from benzene, naphthalene, or thiophene; and most preferably groups obtained by removing one or more hydrogen atoms from benzene or thiophene.

[0063] Ra in equation (a0-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.

[0064] In formula (a0-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' 13 In 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, 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.

[0065] In formula (a0-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, linear or branched alkenyl groups, linear or branched alkynyl groups, or cyclic hydrocarbon groups.

[0066] 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.

[0067] 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.

[0068] Ra' 14 The linear alkenyl group in this compound preferably has 2 to 5 carbon atoms, more preferably 2 to 4, and even more preferably 2. Specifically, examples include vinyl groups, 1-propenyl groups, 1-butenyl groups, and 1-pentenyl groups. Ra' 14 The branched alkenyl group in this compound preferably has 3 to 5 carbon atoms, more preferably 3 to 4, and even more preferably 3. Specifically, examples include 1-methylvinyl group, 2-methylvinyl group, and 1-methylpropenyl group.

[0069] Ra' 14The linear alkynyl groups in this context include, specifically, ethynyl, 1-propynyl, 1-butynyl, and 1-pentynyl groups. Ra' 14 Examples of branched alkynyl groups in this context include, specifically, 3,3-dimethyl-1-butynyl groups.

[0070] Ra' 14 When the hydrocarbon group is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic group, and may be a polycyclic group or a monocyclic group. Examples of monocyclic aliphatic hydrocarbon groups include monocycloalkanes or monocycloalkenes from which one hydrogen atom has been removed. The monocycloalkanes are preferably those having 3 to 6 carbon atoms, specifically cyclopentane and cyclohexane. The monocycloalkenes are preferably those having 3 to 6 carbon atoms, specifically cyclopentenyl, cyclohexenyl, methylcyclopentenyl, and methylcyclohexenyl groups. As the polycyclic aliphatic hydrocarbon group, a group obtained by removing one hydrogen atom from a polycycloalkane is preferred, and as the polycycloalkane, those having 7 to 12 carbon atoms are preferred, specifically adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 Examples include decane and tetracyclododecane.

[0071] Ra' 14 As for aromatic groups in this context, Ra 104 Examples include those similar to aromatic groups in [the text]. Among them, Ra' 14 The group is preferably an aromatic hydrocarbon ring having 5 to 15 carbon atoms from which one or more hydrogen atoms have been removed, or an aromatic heterocycle having 4 to 15 carbon atoms from which one or more hydrogen atoms have been removed. A group obtained by removing one or more hydrogen atoms from benzene, naphthalene, anthracene, or phenanthrene is more preferably a group obtained by removing one or more hydrogen atoms from benzene, naphthalene, or anthracene is even more preferably a group obtained by removing one or more hydrogen atoms from benzene or naphthalene is particularly preferred, and a group obtained by removing one or more hydrogen atoms from benzene is most preferably a group obtained by removing one or more hydrogen atoms from benzene. 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.

[0072] Ra' in equation (a0-r2-4) 14 If is a naphthyl group, the position where it bonds with the tertiary carbon atom in formula (a0-r2-4) may be either position 1 or position 2 of the naphthyl group. Ra' in equation (a0-r2-4) 14 If is an anthyl group, the position where it bonds with the tertiary carbon atom in formula (a0-r2-4) may be position 1, 2, or 9 of the anthyl group.

[0073] Specific examples of the group represented by the formula (a0-r2-1) are given below.

[0074] [ka]

[0075] [ka]

[0076] [ka]

[0077] Specific examples of the group represented by the formula (a0-r2-2) are given below.

[0078] [ka]

[0079] [ka]

[0080] [ka]

[0081] Specific examples of the group represented by the formula (a0-r2-3) are given below.

[0082] [ka]

[0083] [ka]

[0084] Specific examples of the group represented by the formula (a0-r2-4) are given below.

[0085] [ka]

[0086] Secondary alkyl ester type acid-dissociating group: The above acid-dissociable group (R) protects the carboxyl group as a polar group. 01 Examples of such groups include the acid-dissociating group represented by the following general formula (a0-r-4).

[0087] [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. 12 is 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.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] 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.

[0094] Specific examples of the group represented by the formula (a0-r-4) are given below.

[0095] [ka]

[0096] In the above equation (a0-m0), R 01 Among the above, It is preferable that it be a "tertiary alkyl ester type acid dissociable group" or a "secondary type acid dissociable group," and among these, R 01 It is more preferable that the acid-dissociable group has a carbon atom (C*) bonded to an adjacent oxygen atom (-O-), and that the α-position and β-position of the carbon atom (C*) form a carbon-carbon bond other than a single bond. In this context, "carbon-carbon bonds other than single bonds formed between the α-position of the carbon atom (C*) and the β-position of the carbon atom (C*)" means carbon-carbon bonds having a pi bond, and includes double bonds between carbon atoms, triple bonds between carbon atoms, and bonds in which the pi bond in aromatic rings such as benzene rings is resonance-stabilized. Double bonds and triple bonds between carbon atoms are collectively referred to as "carbon-carbon unsaturated bonds" below.

[0097] R 01 The acid-dissociating group in this is the following general formula (R 0-1) or the following general formula (R 0 It is preferable that the acid-dissociable group is represented by (-2).

[0098] [ka] [Formula(R 0 -1) Medium, C* T This indicates that it is a tertiary carbon atom. X1 is the aforementioned tertiary carbon atom (C* T ) and the α position of the tertiary carbon atom (C* T The tertiary carbon atom (C* T ) and the α position of the tertiary carbon atom (C* T It is an aliphatic hydrocarbon group having a carbon-carbon unsaturated bond formed at the β position of (the aliphatic hydrocarbon group may have substituents). Y1 and R Z1 Each of these is independently a substituted linear saturated hydrocarbon group, or they are bonded to each other to form a substituted saturated aliphatic cyclic group. *1 indicates a bond to an adjacent oxygen atom (-O-).

[0099] The above formula (R 0 -1) Medium, R X1 In the tertiary carbon atom (C* T ) and the α position of the tertiary carbon atom (C* T Aromatic groups having carbon-carbon bonds other than the single bond formed by the β-position of ) are functional groups having at least one aromatic ring. The aromatic group is Ra' in formula (a0-r-1). 3 Examples include those similar to aromatic groups in [the context of the example].

[0100] R X1In the above, the aromatic groups having carbon-carbon bonds other than single bonds are preferably groups obtained by removing one or more hydrogen atoms from benzene, naphthalene, anthracene, phenanthrene, or thiophene, more preferably groups obtained by removing one or more hydrogen atoms from benzene, naphthalene, anthracene, or thiophene, even more preferably groups obtained by removing one or more hydrogen atoms from benzene, naphthalene, or thiophene, and particularly preferably groups obtained by removing one or more hydrogen atoms from benzene or thiophene.

[0101] R X1 In this, aromatic groups having carbon-carbon bonds other than single bonds may have substituents. Examples of such substituents include hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups (methoxy groups, ethoxy groups, propoxy groups, butoxy groups, etc.), and the above Ra x5 Examples of substituents represented by the above are available. Among the substituents mentioned above, halogen atoms are more preferred from the viewpoint of increasing sensitivity, and iodine atoms are particularly preferred.

[0102] The above formula (R 0 -1) Medium, R X1 In the tertiary carbon atom (C* T ) and the α position of the tertiary carbon atom (C* T Examples of aliphatic hydrocarbon groups having a carbon-carbon unsaturated bond formed at the β position of ) include linear or cyclic alkenyl groups and linear alkynyl groups.

[0103] Chain-like or cyclic alkenyl groups: R X1 In this context, the 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 2 carbon atoms. Examples of linear alkenyl groups include vinyl groups, 1-propenyl groups, and 1-butenyl groups. Examples of branched alkenyl groups include 1-methylvinyl groups, 2-methylvinyl groups, and 1-methylpropenyl groups. R X1Examples of cyclic alkenyl groups in this context include cyclopentenyl, cyclohexenyl, methylcyclopentenyl, and methylcyclohexenyl groups.

[0104] Chain-like alkynyl groups: R X1 In this context, the chain-like alkynyl group may be either linear or branched, and examples include linear alkynyl groups such as ethynyl, 1-propynyl, 1-butynyl, and 1-pentynyl groups; and branched alkynyl groups such as 3,3-dimethyl-1-butynyl group.

[0105] Among them, R X1 In this context, the aliphatic hydrocarbon group having a carbon-carbon unsaturated bond is preferably a linear alkenyl group or a linear alkynyl group, and more preferably a linear alkenyl group.

[0106] R X1 In this, the aliphatic hydrocarbon group having a carbon-carbon unsaturated bond may have substituents. X1 Preferred substituents that the aliphatic hydrocarbon group in the compound may have include, for example, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, oxo groups (=O), nitro groups, amino groups, and the like.

[0107] The above formula (R 0 -1) Medium, R Y1 and R Z1 Each of these groups is independently a chain-like saturated hydrocarbon group which may have substituents, or they are bonded to each other to form a saturated aliphatic cyclic group which may have substituents. The above formula (R 0 -1) Medium, R Y1 and R Z1 The chain-like saturated hydrocarbon group in the above formula (a0-r2-4) is Ra' 12 and Ra' 13 Examples include those similar to the chain-like saturated hydrocarbon groups in [the text]. The above formula (R 0 -1) Medium, R Y1 and R Z1Among these, the linear saturated hydrocarbon group is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, even more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. Some or all of the hydrogen atoms in this chain-like saturated hydrocarbon group may be substituted with substituents. Examples of such substituents include the aforementioned Ra x5 Similar bases can be cited.

[0108] The above formula (R 0 -1) Medium, R Y1 and R Z1 However, the saturated aliphatic cyclic groups formed by bonding with each other may be polycyclic or monocyclic groups. As monocyclic saturated aliphatic cyclic groups, groups obtained by removing one or more hydrogen atoms from a monocycloalkane are preferred. The monocycloalkanes preferably have 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. As polycyclic saturated aliphatic cyclic groups, groups obtained by removing one or more hydrogen atoms from a polycycloalkane are preferred, and the polycycloalkanes preferably have 7 to 12 carbon atoms, and specific examples include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0109] The saturated aliphatic cyclic group referred to here may also be a saturated aliphatic heterocycle in which some of the carbon atoms constituting it are replaced by heteroatoms. Examples of heteroatoms in a saturated aliphatic heterocycle include oxygen, sulfur, and nitrogen atoms. Specific examples of saturated aliphatic heterocycles include tetrahydrofuran rings and tetrahydropyran rings. Some or all of the hydrogen atoms in this saturated aliphatic cyclic group may be substituted with substituents. Examples of such substituents include hydroxyl groups, carboxyl groups, halogen atoms, oxo groups (=O), alkoxy groups (methoxy, ethoxy, propoxy, butoxy, etc.), and the aforementioned Ra x5 Similar groups can be mentioned. Preferred substituents that this saturated aliphatic cyclic group may have include, for example, halogen atoms, oxo groups (=O), and methyl groups.

[0110] The general formula (R 0 Specific examples of the acid-dissociable groups represented in (-1) include the groups represented by the chemical formulas (r-pr-sa1) to (r-pr-sa21), the groups represented by the chemical formulas (r-pr-ma1) to (r-pr-ma3), the groups represented by the chemical formulas (r-pr-cm5) to (r-pr-cm8), the groups represented by the chemical formulas (r-pr-cs4) to (r-pr-cs7), the group represented by the chemical formula (r-pr-c4), the groups represented by the chemical formulas (r-pr-sv1) to (r-pr-sv13), and the groups represented by the chemical formulas (r-pr-mv1) to (r-pr-mv21).

[0111] In the above equation (a0-m0), R 01 As for the above general formula (R 0 -1) or the following general formula (R 0 It is preferable that the acid-dissociable group is represented by (-2).

[0112] [ka] [In the formula, C* S This indicates that it is a secondary carbon atom. X2 is the aforementioned secondary carbon atom (C* S ) at the α position and the secondary carbon atom (C* S It is an aromatic group having a carbon-carbon bond other than a single bond formed with the β position of the secondary carbon atom (C* S ) at the α position and the secondary carbon atom (C* S It is an aliphatic hydrocarbon group having a carbon-carbon unsaturated bond formed at the β position of (the aliphatic hydrocarbon group may have substituents). Y2 R is a chain-like saturated hydrocarbon group which may have substituents, or a saturated aliphatic cyclic group which may have substituents. However, R X2 and R Y2 This refers to the secondary carbon atoms (C*) bonding with each other. S ) at the α position and the secondary carbon atom (C* SThe β-position of ) may form a cyclic group having a carbon-carbon bond other than a single bond (the cyclic group may have substituents). *2 indicates a bond that connects to an adjacent oxygen atom (-O-).

[0113] The above formula (R 0 -2) Medium, R X2 In the aforementioned secondary carbon atoms (C* S ) at the α position and the secondary carbon atom (C* S The aromatic group having a carbon-carbon bond other than a single bond, formed at the β position of ) is the one of the following formulas (R 0 -1) R in the middle X1 Examples include aromatic groups that have carbon-carbon bonds other than single bonds, similar to those found in [the relevant section]. Among them, R X2 In this context, the aromatic group having carbon-carbon bonds other than single bonds is preferably a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or the aromatic heterocycle (aryl group or heteroaryl group), more preferably having 4 to 15 carbon atoms, and even more preferably having 4 to 10 carbon atoms. Among them, R X2 In this context, the aromatic group having a carbon-carbon bond other than a single bond is preferably a group obtained by removing one or more hydrogen atoms from benzene, naphthalene, anthracene, phenanthrene, or thiophene; more preferably a group obtained by removing one or more hydrogen atoms from benzene, naphthalene, anthracene, or thiophene; even more preferably a group obtained by removing one or more hydrogen atoms from benzene, naphthalene, or thiophene; particularly preferably a group obtained by removing one or more hydrogen atoms from benzene or thiophene; and most preferably a group obtained by removing one or more hydrogen atoms from benzene.

[0114] R X2 In this, aromatic groups having carbon-carbon bonds other than single bonds may have substituents. X2 Preferred substituents that the aromatic group in the compound may have include, for example, a methyl group, an ethyl group, a propyl group, a hydroxyl group, a halogen atom, and an alkoxy group (such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group).

[0115] The above formula (R 0 -2) Medium, R X2 In the aforementioned secondary carbon atoms (C* S An aliphatic hydrocarbon group having a carbon-carbon unsaturated bond formed between the α and β positions of the above formula (R 0 -1) R in the middle X1 Examples include aliphatic hydrocarbon groups having carbon-carbon unsaturated bonds, as seen in [reference]. Among them, R X2 In this context, the aliphatic hydrocarbon group having a carbon-carbon unsaturated bond is preferably a linear alkenyl group or a linear alkynyl group.

[0116] R X2 In this, the aliphatic hydrocarbon group having a carbon-carbon unsaturated bond may have substituents. X2 Preferred substituents that the aliphatic hydrocarbon group in the compound may have include, for example, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, oxo groups (=O), nitro groups, amino groups, and the like.

[0117] The above formula (R 0 -2) Medium, R Y2 The chain-like saturated hydrocarbon group and the saturated aliphatic cyclic group in the above formula (R 0 -1) R in the middle Y1 and R Z1 Examples include chain-like saturated hydrocarbon groups and saturated aliphatic cyclic groups similar to those found in [the text]. R Y2 In this, the chain-like saturated hydrocarbon group is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, even more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. Some or all of the hydrogen atoms of this chain-like saturated hydrocarbon group may be substituted with substituents. Examples of such substituents include the above-mentioned Ra. x5 Similar bases can be cited. R Y2In this context, the saturated aliphatic cyclic group is preferably a monocyclic saturated aliphatic cyclic group having 3 to 6 carbon atoms, and more preferably a group obtained by removing one or more hydrogen atoms from cyclopentane or cyclohexane. The saturated aliphatic cyclic group here may also be a saturated aliphatic heterocycle in which some of the carbon atoms constituting it are substituted with heteroatoms. Some or all of the hydrogen atoms of this saturated aliphatic cyclic group may be substituted with substituents. Examples of substituents include halogen atoms, oxo groups (=O), and methyl groups.

[0118] However, R X2 and R Y2 This refers to the secondary carbon atoms (C*) bonding with each other. S A cyclic group having carbon-carbon bonds other than the single bond formed between the α and β positions of ) may be formed (the cyclic group may have substituents). R X2 and R Y2 The cyclic group having carbon-carbon bonds other than single bonds, which may be formed by the bonding of these elements to one another, may be polycyclic or monocyclic, and may be alicyclic or aromatic. The alicyclic and aromatic rings may also be heterocyclic rings containing heteroatoms.

[0119] R X2 and R Y2 The following are preferred as cyclic groups having carbon-carbon bonds other than single bonds, which may be formed by bonding with each other: specifically, groups obtained by removing one or more hydrogen atoms from a monocycloalkene, groups obtained by removing one or more hydrogen atoms from a ring in which some of the carbon atoms constituting the monocycloalken are substituted with heteroatoms (oxygen atoms, sulfur atoms, etc.), groups obtained by removing one or more hydrogen atoms from a monocycloalkadiene, groups obtained by removing one or more hydrogen atoms from a cycloalkene having 3 to 6 carbon atoms, and more preferably groups obtained by removing one or more hydrogen atoms from cyclopentene or cyclohexene. Alternatively, R X2 and R Y2The cyclic group having carbon-carbon bonds other than single bonds, which may be formed by the bonding of these elements with each other, may be a group obtained by removing one or more hydrogen atoms from a fused ring. Specific examples of such fused rings include indan, tetralin, dihydrobenzofuran (coumaran), and benzodihydropyran (chroman).

[0120] R X2 and R Y2 A cyclic group having carbon-carbon bonds other than single bonds, which may be formed by the bonding of these elements to one another, may have substituents. For example, the above-mentioned Ra x5 These are some examples.

[0121] The general formula (R 0 Specific examples of the acid-dissociable group represented by (-2) include the groups represented by formulas (r-sp-01) to (r-sp-09), respectively.

[0122] In the above equation (a0-m0), X 0 is a hydrogen atom, an alkyl group, or *-L 02 -COOR 02 It represents a base that is expressed as [this].

[0123] X 0 The alkyl group in is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group, and even more preferably a methyl group or an ethyl group.

[0124] X 0 *-L in 02 -COOR 02 In a group represented by L 02 represents a chain or cyclic aliphatic hydrocarbon group which may have substituents. L 02 The chain-like aliphatic hydrocarbon group in the above L 01 Examples include chain-like aliphatic hydrocarbon groups. Among them, L 02The linear aliphatic hydrocarbon group in is preferably one to ten carbon atoms, more preferably one to six carbon atoms, even more preferably one to four carbon atoms, particularly preferably one to three carbon atoms, and most preferably one or two carbon atoms. L 02 The branched aliphatic hydrocarbon group in this compound 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. L 02 The substituents that the chain-like aliphatic hydrocarbon group in the above L may have are 01 Examples include substituents similar to those that may be present on the chain-like aliphatic hydrocarbon group in the above.

[0125] L 02 The cyclic aliphatic hydrocarbon group in the above L 01 Examples include cyclic aliphatic hydrocarbon groups similar to those found in [the relevant context]. Among them, L 02 The cyclic aliphatic hydrocarbon group in this compound preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms, and even more preferably 3 to 6 carbon atoms. L 02 The substituents that the cyclic aliphatic hydrocarbon group in the above L may have are 01 Examples include substituents similar to those that may be present on the cyclic aliphatic hydrocarbon group in [the relevant product]. L 02 In the cyclic aliphatic hydrocarbon group, some of the carbon atoms constituting the ring structure may be substituted with substituents containing heteroatoms. Preferred substituents containing heteroatoms are -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0126] X 0 *-L in 02 -COOR 02 In a base represented by R 02 R represents an acid-dissociable group. 02 The acid-dissociating group in is the above R 01Examples include those similar to the acid-dissociating groups in [the relevant context]. Among them, R 02 The acid-dissociating group in this is the aforementioned (R 0 -1) or (R 0 A group represented by -2) is preferred.

[0127] In the above formula (a0-m0), n0 is either 1 or 2. When n0 is 1, the X 0 The above *-L 02 -COOR 02 It is a base represented by . When n0 is 2, the X 0 This is a hydrogen atom or an alkyl group. When n0 is 2, two R 01 They may be the same or they may be different. When n0 is 2, L 01 One of the hydrogen atoms in the aliphatic hydrocarbon group in the formula is *3-COOR 01 It is replaced by *3 is L 01 This represents a combination of two things. When n0 is 2, two *3-COOR 01 L 01 The carbon atoms inside may be the same or different. From the viewpoint of improving exposure margin, it is more preferable that n0 is 2.

[0128] The constituent unit (a0) may be the constituent unit (a0-1) derived from the compound represented by the following general formula (a0-m0-1).

[0129] [ka] [In the formula, W 01 X represents a polymerizable group-containing group. 01 L represents a hydrogen atom or an alkyl group. 011 R represents a linear or cyclic aliphatic hydrocarbon group which may have substituents. 03 and R 04 Each of these independently represents an acid-dissociating group.

[0130] In the above formula (a0-m0-1), W 01 This is W in the above formula (a0-m0). 0 It is similar to that. In the above equation (a0-m0-1), X 01 The alkyl group in the above formula (a0-m0) is X 0 This is similar to the alkyl group in [the given context]. In the above formula (a0-m0-1), L 011 L in the above formula (a0-m0) is 01 It is a group similar to the chain-like or cyclic aliphatic hydrocarbon group in [the relevant context], but with one hydrogen atom removed. In the above formula (a0-m0-1), R 03 and R 04 R in the above formula (a0-m0) is 01 These are similar in each case.

[0131] In the above formula (a0-m0-1), W 01 Among them, C(R X11 )(R X12 )=C(R X13 )-Ya x0 A group represented by - is preferred. x0 In this compound, the divalent linking group is preferably a single bond or a phenylene group which may have a hydroxyl group as a substituent, with a single bond being more preferable.

[0132] In the above equation (a0-m0-1), X 01 The alkyl group in is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group, and even more preferably a methyl group or an ethyl group. In the above equation (a0-m0-1), X 01 Among these, hydrogen atoms or linear alkyl groups having 1 to 5 carbon atoms are preferred, hydrogen atoms, methyl groups, or ethyl groups are more preferred, and hydrogen atoms are even more preferred.

[0133] In the above formula (a0-m0-1), L 011In particular, a chain-like aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a cyclic aliphatic hydrocarbon group having 3 to 12 carbon atoms is preferred, a chain-like aliphatic hydrocarbon group having 1 to 3 carbon atoms is more preferred, and an aliphatic hydrocarbon group having 1 or 2 carbon atoms is even more preferred.

[0134] In the above formula (a0-m0-1), R 03 and R 04 Preferably, each of these is independently a group represented by the above general formula (a0-r-1), a group represented by the above general formula (a0-r-2), or a group represented by the above general formula (a0-r-4), and the above general formula (R 0 -1) or the above general formula (R 0 The acid-dissociable group represented by (-2) is more preferable. In the above formula (a0-m0-1), *-COOR 03 And, *-COOR 04 L 011 The carbon atoms inside may be the same or different. * represents a bond.

[0135] The constituent unit (a0) may be the constituent unit (a0-2) derived from the compound represented by the following general formula (a0-m0-2).

[0136] [ka] [In the formula, W 02 L represents a polymerizable group-containing group. 021 and L 022 Each of these independently represents a chain or cyclic aliphatic hydrocarbon group which may have substituents. 05 and R 06 Each of these independently represents an acid-dissociating group.

[0137] In the above formula (a0-m0-2), W 02 , L 021 and L 022 This is W in the above formula (a0-m0). 0 , L 01 and L 02 The same applies to each of them. In the above formula (a0-m0-2), R05 and R 06 R in the above formula (a0-m0) is 01 These are similar in each case.

[0138] In the above formula (a0-m0-2), W 02 Among them, C(R X11 )(R X12 )=C(R X13 )-Ya x0 A group represented by - is preferred. x0 In this compound, the divalent linking group is preferably a single bond or a phenylene group which may have a hydroxyl group as a substituent, with a single bond being more preferable.

[0139] In the above formula (a0-m0-2), L 021 and L 022 Among these, a chain-like aliphatic hydrocarbon group having 1 to 10 carbon atoms or a cyclic aliphatic hydrocarbon group having 3 to 12 carbon atoms is preferred, a chain-like aliphatic hydrocarbon group having 1 to 3 carbon atoms is more preferred, a methylene group [-CH2-] or an ethylene group [-(CH2)2-] is even more preferred, and a methylene group [-CH2-] is particularly preferred.

[0140] In the above formula (a0-m0-2), R 05 and R 06 Preferably, each of these is independently a group represented by the above general formula (a0-r-1), a group represented by the above general formula (a0-r-2), or a group represented by the above general formula (a0-r-4), and the above general formula (R 0 -1) or the above general formula (R 0 The acid-dissociable group represented by (-2) is more preferable.

[0141] The constituent unit (a0) is preferably the constituent unit represented by the following general formula (a0-u0).

[0142] [ka] [In the formula, R X131 This represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, or an alkyl halide having 1 to 5 carbon atoms.x01 X represents a divalent linking group or a single bond. 02 is a hydrogen atom, an alkyl group, or *-L 032 -COOR 08 This represents a group represented by *. * represents a bond to an adjacent nitrogen atom. 031 and L 032 Each of these independently represents a chain or cyclic aliphatic hydrocarbon group which may have substituents. 07 and R 08 These are each independently acid-dissociable groups. n01 is 1 or 2. When n01 is 1, the X 02 is, *-L 032 -COOR 08 The group is represented by . When n01 is 2, the X 02 is a hydrogen atom or an alkyl group. When n01 is 2, two R 07 They may be the same or they may be different.

[0143] In the above equation (a0-u0), R X131 The alkyl group having 1 to 5 carbon atoms 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. A C1-C5 alkyl halide 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 in the alkyl halide. R X13 Preferably, the elements are hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, or fluorinated alkyl groups having 1 to 5 carbon atoms, with hydrogen atoms or methyl groups being the most preferred due to their industrial availability.

[0144] In the above equation (a0-u0), Ya x01 In this, the divalent linking group can be a divalent hydrocarbon group which may have substituents, or a divalent linking group which contains a heteroatom. Among these, Ya x01Preferably, the group is an ester bond [-C(=O)-O-, -OC(=O)-], an ether bond (-O-), a linear or branched alkylene group, an aromatic group or a combination thereof, or a single bond. Among these, Ya x01 Preferably, the phenylene group may have a single bond or a hydroxyl group as a substituent, and a single bond is more preferred.

[0145] In the above equation (a0-u0), X 02 The alkyl group in is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group, and even more preferably a methyl group or an ethyl group.

[0146] In the above equation (a0-u0), L 031 and L 032 The linear or cyclic aliphatic hydrocarbon group in is preferably a linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a cyclic aliphatic hydrocarbon group having 3 to 12 carbon atoms, more preferably a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, and even more preferably a methylene group [-CH2-] or an ethylene group [-(CH2)2-].

[0147] In the above equation (a0-u0), R 07 or R 08 The acid-dissociable groups are preferably, independently, the group represented by the above general formula (a0-r-1), the group represented by the above general formula (a0-r-2), or the group represented by the above general formula (a0-r-4), and the above general formula (R 0 -1) or the above general formula (R 0 The acid-dissociable group represented by (-2) is more preferable.

[0148] In the above formula (a0-u0), when n01 is 2, the above L 031 One of the hydrogen atoms in the chain-like or cyclic aliphatic hydrocarbon group in the formula is *4-COOR 07 It is replaced by L. *4 is L 031 This represents a combination of two things. When n0 is 2, two *4-COOR 07L 031 The carbon atoms inside may be the same or different. From the viewpoint of improving exposure margin, it is more preferable that n0 is 2.

[0149] The following are specific examples of constituent units (a0), but are not limited to these. In each of the following equations, R β This represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0150] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0151] The constituent unit (a0) is preferably selected from the group consisting of constituent units represented by the above chemical formulas (a0-001) to (a0-007), the group consisting of constituent units represented by the above chemical formulas (a0-008) to (a0-018), the group consisting of constituent units represented by the above chemical formulas (a0-019) to (a0-022), the group consisting of constituent units represented by the above chemical formulas (a0-023) to (a0-047), the group consisting of constituent units represented by the above chemical formulas (a0-038) to (a0-042), and the group consisting of constituent units represented by the chemical formulas (a0-043) to (a0-044).

[0152] 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 20 to 80 mol%, more preferably 25 to 75 mol%, even more preferably 30 to 70 mol%, and particularly preferably 35 to 65 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 (a0) to above the lower limit of the preferred range described above, lithography characteristics such as resolution, pattern roughness, and exposure margin can be easily improved. 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 in various aspects.

[0153] <<Other constituent units>> Component (A1) may have other constituent units in addition to the constituent unit (a0) described above, as necessary. Examples of such other constituent units include a constituent unit (a1) containing an acid-degradable group whose polarity increases with the action of an acid; a constituent unit (a10) represented by the general formula (a10-1) described later; a constituent unit (a2) containing a lactone-containing cyclic group; a constituent unit (a5) that generates acid upon exposure; a constituent unit (a6) that has acid diffusion controllability; and a constituent unit (a8) derived from a compound represented by the general formula (a8-1) described later. Furthermore, these other constituent units shall not include those corresponding to the constituent unit (a0) described above.

[0154] Unit of composition (a1): The constituent unit (a1) is a constituent unit that contains an acid-degradable group whose polarity increases upon the action of an acid. 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 these 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).

[0155] Examples of acid-dissociable groups include those previously proposed as acid-dissociable groups for base resins used in chemically amplified resist compositions. Examples of acid-dissociable groups proposed for base resins used in chemically amplified resist compositions include acetal-type acid-dissociable groups, tertiary alkyl ester-type acid-dissociable groups, tertiary alkyloxycarbonyl acid-dissociable groups, and secondary alkyl ester-type acid-dissociable groups.

[0156] 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.

[0157] [ka]

[0158] [ka]

[0159] [ka]

[0160] [ka]

[0161] [ka]

[0162] [ka]

[0163] [ka]

[0164] [ka]

[0165] [ka]

[0166] In the following equations, R α Rz represents a hydrogen atom, a methyl group, or a trifluoromethyl group. Rz represents a hydrogen atom, an alkyl group, a halogen atom, an alkyl halide, a hydroxyl group, or an alkoxy group.

[0167] [ka]

[0168] [ka]

[0169] [ka]

[0170] [ka]

[0171] [ka]

[0172] 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) or the constituent unit represented by formula (a1-3) is more preferable because it is easier to improve the characteristics (sensitivity, shape, etc.) in electron beam or EUV lithography.

[0173] The proportion of constituent units (a1) in component (A1) is preferably 0 to 40 mol%, more preferably 5 to 35 mol%, even more preferably 10 to 30 mol%, and particularly preferably 15 to 25 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, resolution, and CDU 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.

[0174] Unit of composition (a10): The constituent unit (a10) is a constituent unit represented by the following general formula (a10-1).

[0175] [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 group. ax1 [ is an integer greater than or equal to 1.]

[0176] In formula (a10-1), R is the same as R in general formula (a1-1). 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, and a hydrogen atom or a methyl group is particularly preferred due to their industrial availability.

[0177] In the above formula (a10-1), Ya x1 It is a single bond or a divalent linking group. In the above chemical formula, Ya x1 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.

[0178] • Divalent hydrocarbon groups which may have substituents: The divalent hydrocarbon group, which may have substituents, may be an aliphatic hydrocarbon group or an aromatic group.

[0179] Aliphatic hydrocarbon groups An aliphatic hydrocarbon group refers to a hydrocarbon group that does not possess aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, but is usually preferable to be saturated. Examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups containing a ring in their structure.

[0180] ...linear or branched aliphatic hydrocarbon groups 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.

[0181] The linear or branched aliphatic hydrocarbon group may or may not have substituents. Examples of substituents include fluorine atoms, fluorinated alkyl groups having 1 to 5 carbon atoms substituted with fluorine atoms, and carbonyl groups.

[0182] ...Aliphatic hydrocarbon groups containing a ring in their structure Examples of aliphatic hydrocarbon groups containing a ring in the structure include cyclic aliphatic hydrocarbon groups that may contain substituents containing heteroatoms in the ring structure (groups obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), groups in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which the cyclic aliphatic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group are the same as those described above. The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. A preferred monocyclic alicyclic hydrocarbon group is a group obtained by removing two 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 two hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 Examples include decane and tetracyclododecane.

[0183] The cyclic aliphatic hydrocarbon group may or may not have substituents. Examples of substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, and carbonyl groups. The alkyl group used as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group. As the alkoxy group used 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 even more preferred. A fluorine atom is preferred as the halogen atom used as the substituent. Examples of halogenated alkyl groups as substituents include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with halogen atoms. A cyclic aliphatic hydrocarbon group may have some of the carbon atoms constituting its ring structure replaced by substituents containing heteroatoms. Preferred substituents containing heteroatoms are -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0184] ·Aromatic group The aromatic group is a hydrocarbon group having at least one aromatic ring. This aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic, polycyclic, or have substituents that substitute for the hydrogen atoms of the aromatic ring. Examples of aromatic rings include aromatic hydrocarbon rings and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced by heteroatoms. The number of carbon atoms in the aromatic hydrocarbon ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 5 to 15, and particularly preferably 6 to 12. However, this number of carbon atoms does not include the number of carbon atoms in substituents that substitute for hydrogen atoms in the aromatic hydrocarbon ring. Specific examples of aromatic hydrocarbon rings include benzene, naphthalene, anthracene, and phenanthrene. 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.

[0185] The aromatic group preferably has 4 to 30 carbon atoms, more preferably 4 to 20, even more preferably 4 to 15, and particularly preferably 4 to 12 carbon atoms. Specific examples of aromatic groups include groups obtained by removing two hydrogen atoms from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); groups obtained by removing two hydrogen atoms from aromatic compounds containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and groups in which one hydrogen atom of an aryl group (aryl group or heteroaryl group) obtained by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle is substituted with an alkylene group (e.g., groups obtained by removing one more hydrogen atom from an aryl group in an arylalkyl group such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms in the alkylene group bonded to the aryl group or heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0186] The aromatic group may have its hydrogen atoms substituted with substituents. For example, the hydrogen atoms bonded to the aromatic ring in the aromatic group may be substituted with substituents. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, and the like. The alkyl group used as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group. Examples of the substituents include alkoxy groups, halogen atoms, and alkyl halides that substitute for hydrogen atoms on the cyclic aliphatic hydrocarbon group.

[0187] • Divalent linking groups containing heteroatoms: Examples of divalent linking groups containing heteroatoms include -O-, -C(=O)-O-, -OC(=O)-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)- (H may be substituted with substituents such as alkyl groups or acyl groups), -S-, -S(=O)2-, -S(=O)2-O-, and the general formula -Y 21 -OY 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 -,-[Y 21 -C(=O)-O] m” -Y 22 -, -Y 21 -OC(=O)-Y 22 - or -Y 21 -S(=O)2-OY 22 - is represented by the base [wherein Y 21 and Y 22 Each of these is a divalent hydrocarbon group which may have substituents independently, O is an oxygen atom, and m'' is an integer from 1 to 3. When the divalent linking group containing the heteroatom is -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, or -NH-C(=NH)-, the H may be substituted with substituents such as alkyl groups or acyl groups. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and particularly preferably 1 to 5. General formula-Y 21 -OY 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 -,-[Y 21 -C(=O)-O] m” -Y 22 -, -Y 21 -OC(=O)-Y 22 - or -Y 21 -S(=O)2-OY 22 - Middle, Y 21 and Y 22 Each of these is independently a divalent hydrocarbon group which may have substituents. Examples of such divalent hydrocarbon groups are the same as those described above. Y 21 Preferably, the group is a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, even more preferably a linear alkylene group having 1 to 5 carbon atoms, and particularly preferably a methylene group or an ethylene group. Y 22 The group is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group, or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group. Formula - [Y 21 -C(=O)-O] m” -Y 22 In the base represented by -, m'' is an integer from 1 to 3, preferably 1 or 2, and more preferably 1. That is, in the formula -[Y 21 -C(=O)-O] m” -Y 22 As a base represented by -, formula -Y21 -C(=O)-OY 22 Groups represented by - are particularly preferred. Among them, the group represented by formula -(CH2) a’ -C(=O)-O-(CH2) b’ A base represented by - is preferred. In the formula, a' is an integer from 1 to 10, preferably an integer from 1 to 8, more preferably an integer from 1 to 5, even more preferably 1 or 2, and most preferably 1. b' is an integer from 1 to 10, preferably an integer from 1 to 8, more preferably an integer from 1 to 5, even more preferably 1 or 2, and most preferably 1.

[0188] Ya x1 Preferred members include single bonds, ester bonds [-C(=O)-O-, -OC(=O)-], ether bonds (-O-), linear or branched alkylene groups, or combinations thereof, with single bonds and ester bonds [-C(=O)-O-, -OC(=O)-] being more preferred.

[0189] In the above formula (a10-1), Wa x1 It is an aromatic group. Wa x1 The aromatic group in this case is an aromatic ring which 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. Specifically, examples of such 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. Specifically, examples of aromatic heterocycles include pyridine rings and thiophene rings. Wa x1 The aromatic group in this compound preferably has 4 to 30 carbon atoms, more preferably 4 to 20, even more preferably 4 to 15, and particularly preferably 4 to 12 carbon atoms. Also, Wa x1The aromatic group in this can be 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 ax1 A 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.

[0190] Wa x1 The aromatic 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 for cyclic aliphatic hydrocarbon groups in are similar to those listed above. The substituents are preferably linear or branched alkyl groups having 1 to 5 carbon atoms, more preferably linear or branched alkyl groups having 1 to 3 carbon atoms, even more preferably ethyl or methyl groups, and particularly preferably methyl groups. x1 In this case, the aromatic group preferably has no substituents.

[0191] 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.

[0192] The following are specific examples of the constituent unit (a10) represented by the above formula (a10-1). In the following equations, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0193] [ka]

[0194] [ka]

[0195] [ka]

[0196] The constituent units (a10) of component (A1) may be one type or two or more types. Component (A1) may or may not have constituent units (a10), but it is preferable that it has constituent units (a10). If component (A1) has constituent units (a10), the proportion of constituent units (a10) in component (A1) is preferably 20 to 80 mol%, more preferably 25 to 75 mol%, even more preferably 30 to 70 mol%, and particularly preferably 35 to 65 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.

[0197] Unit of composition (a2): Component (A1) may or may not 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.

[0198] 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).

[0199] [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).

[0200] 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' 21Examples 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 groups, and perfluoroalkyl groups are particularly preferred.

[0201] Ra' 21 In -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; groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as bicycloalkanes, tricycloalkanes, and tetracycloalkanes. More specifically, groups obtained by removing one or more hydrogen atoms from monocycloalkanes such as cyclopentane and cyclohexane; adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 Examples include groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as decane 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.

[0202] Ra' 21 Among the above, it is preferable that each is independently a hydrogen atom or a cyano group.

[0203] 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, isopropylene group, etc. If 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-, -CH2-S-CH2-, etc. As A'', an alkylene group having 1 to 5 carbon atoms or -O- is preferred, an alkylene group having 1 to 5 carbon atoms is more preferred, and a methylene group is most preferred.

[0204] The following are specific examples of groups represented by the general formulas (a²-r-1) to (a²-r-7).

[0205] [ka]

[0206] [ka]

[0207] 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).

[0208] [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. 21 The 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.

[0209] 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.

[0210] 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. 21 The divalent linking group in the above general formula (a10-1) is Ya x1 Examples include divalent linking groups similar to those in [the relevant context].

[0211] 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.

[0212] In the above formula (a2-1), Ya 21 It is a single bond, La 21 It is preferable that it be -COO- or -OCO-.

[0213] 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.

[0214] The constituent units (a2) of component (A1) may be one type or two or more types. Component (A1) may or may not have constituent units (a2). If component (A1) has constituent units (a2), the proportion of constituent units (a2) is preferably 1 to 25 mol%, more preferably 2 to 20 mol%, and even more preferably 5 to 15 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.

[0215] Unit of composition (a5): Component (A1) may or may not have a constituent unit (a5) that generates acid upon exposure. Known constituent units (a5) can be used. Having constituent unit (a5) makes it easier for the acid generated upon exposure to be uniformly distributed within the resist film. Examples of constituent unit (a5) include a constituent unit containing the structure described in component (B) below. For example, a constituent unit containing a structure represented by any of the general formulas (b-1) to (b-3) below can be used. Suitable constituent units (a5) include, for example, the constituent unit represented by the following general formula (a5-1).

[0216] [ka] [In the formula, R mThis is an alkyl group having 1 to 5 carbon atoms, an alkyl halide having 1 to 5 carbon atoms, a halogen atom, or a hydrogen atom. 50 This is a divalent linking group or a single bond. 50 n is a divalent hydrocarbon group which may have substituents. a5 is an integer between 0 and 2. 51 It is a divalent linking group. 5 This is a divalent linking group that may have a heteroatom, or a single bond. 51 and Ra 52 Each of these is independently a hydrogen atom, a fluorine atom, or a fluorinated alkyl group. n5 is an integer from 1 to 4. m is an integer of 1 or more, and M' m+ This is an onium cation with a valence of m.

[0217] {Anion Division} In the above formula (a5-1), R m These are alkyl groups having 1 to 5 carbon atoms, alkyl halides having 1 to 5 carbon atoms, halogen atoms, or hydrogen atoms. R m The alkyl group having 1 to 5 carbon atoms is preferably a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, 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. A halogenated alkyl group having 1 to 5 carbon atoms is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. Fluorine is particularly preferred as the halogen atom in alkyl halides. R m Preferably, the elements are hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, or fluorinated alkyl groups having 1 to 5 carbon atoms, with hydrogen atoms or methyl groups being the most preferred due to their industrial availability.

[0218] In the above formula (a5-1), La 50This is a divalent linking group or a single bond. La 50 The divalent linking group in is not particularly limited, but preferred examples include a divalent hydrocarbon group which may have substituents, and a divalent linking group which contains a heteroatom, respectively. x1 This is similar to the divalent linking groups exemplified in the above, such as divalent hydrocarbon groups which may have substituents, and divalent linking groups which contain heteroatoms. Among the above, La 50 Preferably, the group is an ester bond [-C(=O)-O-, -OC(=O)-], an ether bond (-O-), a linear or branched alkylene group, an aromatic group or a combination thereof, or a single bond. Among these, La 50 As such, ester bonds [-C(=O)-O-, -OC(=O)-] and single bonds are more preferable, and ester bonds [-C(=O)-O-, -OC(=O)-] are even more preferable.

[0219] In the above formula (a5-1), Ra 50 This is a divalent hydrocarbon group which may have substituents. Ra 50 The divalent hydrocarbon group in this expression may be an aliphatic hydrocarbon group or an aromatic group.

[0220] ··Ra 50 Aliphatic hydrocarbon groups in The aliphatic hydrocarbon group refers to a hydrocarbon group that does not possess aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, but is usually preferred to be saturated. Examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups containing a ring in their structure.

[0221] ...linear or branched aliphatic hydrocarbon groups 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.

[0222] The linear or branched aliphatic hydrocarbon group described above may or may not have substituents. Examples of substituents include fluorine atoms, fluorinated alkyl groups having 1 to 5 carbon atoms substituted with fluorine atoms, and carbonyl groups.

[0223] ...Aliphatic hydrocarbon groups containing a ring in their structure Examples of aliphatic hydrocarbon groups containing a ring in the structure include cyclic aliphatic hydrocarbon groups that may contain substituents containing heteroatoms in the ring structure (groups from which two hydrogen atoms have been removed from an aliphatic hydrocarbon ring), groups in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which the cyclic aliphatic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group are the same as those described above. The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms. The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. A preferred monocyclic alicyclic hydrocarbon group is a group obtained by removing two 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 two hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 Examples include decane and tetracyclododecane.

[0224] The cyclic aliphatic hydrocarbon group may or may not have substituents. Examples of substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, and carbonyl groups. The alkyl group used as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group. As the alkoxy group used 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. Examples of halogen atoms used as substituents include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, and the like, with fluorine atoms being preferred. Examples of halogenated alkyl groups as substituents include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with halogen atoms. A cyclic aliphatic hydrocarbon group may have some of the carbon atoms constituting its ring structure replaced by substituents containing heteroatoms. Preferred substituents containing heteroatoms are -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0225] ··Ra 50 Aromatic group in The aromatic group is a group having at least one aromatic ring. This aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic, and may have substituents that substitute for the hydrogen atoms of the aromatic ring. Examples of aromatic rings include aromatic hydrocarbon rings and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced by heteroatoms. The number of carbon atoms in the aromatic hydrocarbon ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 5 to 15, and particularly preferably 6 to 12. However, this number of carbon atoms does not include the number of carbon atoms in substituents that substitute for hydrogen atoms in the aromatic hydrocarbon ring. Specific examples of aromatic hydrocarbon rings include benzene, naphthalene, anthracene, and phenanthrene. 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.

[0226] The aromatic ring preferably has 4 to 30 carbon atoms, more preferably 4 to 20, even more preferably 4 to 15, and particularly preferably 4 to 12. However, this number of carbon atoms does not include the number of carbon atoms in substituents. Specific examples of aromatic groups include groups obtained by removing two hydrogen atoms from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); groups obtained by removing two hydrogen atoms from aromatic compounds containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and groups in which one hydrogen atom of an aryl group or heteroaryl group obtained by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group) is substituted with an alkylene group (for example, a group obtained by removing one more hydrogen atom from an 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 bonded to the aforementioned aryl group or heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0227] The aromatic group may have its hydrogen atoms substituted with substituents. For example, the hydrogen atoms bonded to the aromatic ring in the aromatic group may be substituted with substituents. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, and the like. The alkyl group used as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group. Examples of the substituents include alkoxy groups, halogen atoms, and alkyl halogens that substitute for hydrogen atoms on the cyclic aliphatic hydrocarbon group.

[0228] In the above formula (a5-1), n a5 This is an integer between 0 and 2. Among the above, 50 The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group containing a ring in its structure, more preferably a cyclic aliphatic hydrocarbon group which may contain substituents containing heteroatoms in its ring structure, and even more preferably an alicyclic hydrocarbon group which may have substituents and is a polycyclic or monocyclic group. Alternatively, among the above, Ra 50 Aromatic groups are preferred.

[0229] n a5 If it is 2, then 2 Ra 50 These may all be alicyclic hydrocarbon groups which may have substituents, or they may all be aromatic groups which may have substituents, or they may be a combination of alicyclic hydrocarbon groups which may have substituents and aromatic groups which may have substituents.

[0230] In the above formula (a5-1), La 51 It is a divalent linking group. La 51 Examples of divalent linking groups in this context include non-hydrocarbon oxygen-containing linking groups such as oxygen atoms (ether bond: -O-), ester bonds (-C(=O)-O-), oxycarbonyl groups (-OC(=O)-), amide bonds (-C(=O)-NH-), carbonyl groups (-C(=O)-), and carbonate bonds (-OC(=O)-O-); and combinations of these non-hydrocarbon oxygen-containing linking groups with alkylene groups. A sulfonyl group (-SO2-) may be further linked to this combination. Examples of such divalent linking groups include the linking groups represented by the following general formulas (L-al-1) to (L-al-8). Note that in the following general formulas (L-al-1) to (L-al-8), Ra in formula (a5-1) above 50 The combination with this is V' in the following general formulas (L-al-1)~(L-al-8). 101 That is the case.

[0231] [ka] [In the formula, V' 101 V' is a single bond or an alkylene group with 1 to 5 carbon atoms. 102 It is a divalent saturated hydrocarbon group with 1 to 30 carbon atoms.

[0232] V' 102The 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.

[0233] 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 (a0-r-1). 3 A 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.

[0234] La 51Preferably, the linking group is a divalent linking group containing an ester bond or a divalent linking group containing an ether bond, more preferably the linking groups represented by the above formulas (L-al-1) to (L-al-5) and (L-al-8), and even more preferably the linking group represented by (L-al-3) or (L-al-8).

[0235] In the above formula (a5-1), Ya 5 This is a divalent linking group that may have a heteroatom, or a single bond. Ya 5 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. Ya 5 In the above, the divalent hydrocarbon group which may have substituents, and the divalent linking group which contains a heteroatom, are as follows: x1 This is similar to the divalent linking groups exemplified in the above, such as divalent hydrocarbon groups which may have substituents, and divalent linking groups which contain heteroatoms. Among the above, Ya 5 The alkylene group is preferably a linear or branched alkylene group, or a single bond, with a single bond being more preferable.

[0236] In the above formula (a5-1), Ra 51 and Ra 52 Each of these is independently a hydrogen atom, a fluorine atom, or a fluorinated alkyl group. Ra 51 and Ra 52 The fluorinated alkyl groups in this compound are preferably linear or branched fluorinated alkyl groups having 1 to 5 carbon atoms, with a trifluoromethyl group being more preferred. In the above formula (a5-1), SO3 - Ra bonds to the adjacent carbon atom. 51 and Ra 52 From the viewpoint of acid strength, it is preferable that at least one of these atoms is a fluorine atom.

[0237] In the above formula (a5-1), n5 is an integer from 1 to 4, and is preferably 1, 2, or 3.

[0238] {cation part} In the above formula (a5-1), M' m+ This represents an m-valent onium cation. Among these, M' m+ The sulfonium cation and iodonium cation are preferred. m is an integer of 1 or more.

[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 optionally substituted aryl group, an optionally substituted alkyl group, or an optionally substituted alkenyl group. 201 ~R 203 , R 206 ~R 207 These 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. R201 ~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 group or an aliphatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group that does not possess aromaticity. Furthermore, the aliphatic hydrocarbon group may be saturated or unsaturated, but is usually preferred to be saturated.

[0244] R' 201 In this context, an aromatic group is a group that has at least one aromatic ring. This aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic, polycyclic, or have substituents that substitute for the hydrogen atoms of the aromatic ring. Examples of aromatic rings include aromatic hydrocarbon rings and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced by heteroatoms. The number of carbon atoms in the aromatic hydrocarbon ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 5 to 15, and particularly preferably 6 to 12. However, this number of carbon atoms does not include the number of carbon atoms in substituents that substitute for hydrogen atoms in the aromatic hydrocarbon ring. Specific examples of aromatic hydrocarbon rings include benzene, naphthalene, anthracene, and phenanthrene. 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.

[0245] The aromatic group preferably has 4 to 30 carbon atoms, more preferably 4 to 30, even more preferably 4 to 20, particularly preferably 4 to 15, and most preferably 4 to 10. However, this number of carbon atoms does not include the number of carbon atoms in substituents. R' 201 Specific examples of aromatic 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.

[0246] 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, adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 Polycycloalkanes having a cross-linked ring polycyclic skeleton, such as decane and tetracyclododecane; polycycloalkanes having a fused ring polycyclic skeleton, such as a cyclic group having a steroid skeleton, are more preferred.

[0247] 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.

[0248] 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.

[0249] Also, R' 201 The cyclic hydrocarbon group in this 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) mentioned above, -SO2--containing cyclic groups represented by the general formulas (b5-r-1) to (b5-r-4) described below, and heterocyclic groups represented by the chemical formulas (r-hr-1) to (r-hr-16) below.

[0250] [ka]

[0251] R' 201 Examples of substituents on the cyclic group include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, and nitro groups. Preferably, alkyl groups with 1 to 5 carbon atoms are used as substituents, 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.

[0252] 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.

[0253] 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 2 carbon atoms. Examples of linear alkenyl groups include vinyl groups, propenyl groups (allyl groups), and butenyl groups. Examples of branched alkenyl groups include 1-methylvinyl groups, 2-methylvinyl groups, 1-methylpropenyl groups, and 2-methylpropenyl groups. Among the chain-like alkenyl groups mentioned above, linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred.

[0254] R' 201 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' 201 Examples include cyclic groups in this context.

[0255] 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 (a0-r-2) above, as optionally substituted cyclic groups or optionally substituted linear alkyl groups.

[0256] 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) mentioned above; and -SO2--containing cyclic groups represented by the general formulas (b5-r-1) to (b5-r-4) mentioned below.

[0257] 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 )-(applicable R N is an alkyl group having 1 to 5 carbon atoms. ) may be bonded via functional groups such as ). The formed ring is preferably a 3 to 10-membered ring, and particularly preferably a 5 to 7-membered ring, 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, a tetrahydrothiopyranium ring, and the like.

[0258] 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 to each other to form a ring.

[0259] 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, any -SO2-containing cyclic group can be used without particular limitations. Specifically, groups represented by the following general formulas (b5-r-1) to (b5-r-4) are examples, with "-SO2-containing polycyclic groups" being preferred, and the group represented by general formula (b5-r-1) being more preferred.

[0260] [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.

[0261] 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.

[0262] 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.

[0263] 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.

[0264] [ka]

[0265] [ka]

[0266] [ka]

[0267] Specific examples of suitable cations represented by the above formula (ca-1) include the cations represented by the following chemical formulas.

[0268] [ka]

[0269] [ka]

[0270] [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 1 to 20.]

[0271] [ka]

[0272] [ka]

[0273] [ka] [In the formula, R” 201is a hydrogen atom or a substituent, and the substituent is the aforementioned R 201 ~R 207 , and R 210 These are the same substituents that may be present.

[0274] [ka]

[0275] [ka]

[0276] [ka]

[0277] Suitable cations represented by the formula (ca-2) include, specifically, diphenyliodonium cation and bis(4-tert-butylphenyl)iodonium cation.

[0278] 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).

[0279] [ka]

[0280] The cation portion in the above formula (a5-1) ((M' m+ ) 1 / m As for the cation, a sulfonium cation is preferred, the cations represented by formulas (ca-1) to (ca-3) are more preferred, the cation represented by formula (ca-1) is even more preferred, and the cations represented by formulas (ca-1-1) to (ca-1-104) are particularly preferred.

[0281] In particular, from the viewpoint of reducing roughness, the cation portion is preferably a cation represented by the formula (ca-1), preferably having electron-withdrawing groups such as halogen atoms, alkyl halides, and sulfonyl groups as substituents, preferably an m-valent organic cation having a halogen atom as a substituent, more preferably having at least one selected from the group consisting of halogen atoms and alkyl halides, particularly preferably having at least one selected from the group consisting of fluorine atoms, iodine atoms, bromine atoms, and alkyl fluorides, and most preferably having at least one selected from the group consisting of fluorine atoms and alkyl fluorides. The alkyl halide may be linear or branched. The alkyl halide preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 or 2 carbon atoms. The alkyl halide preferably has a trifluoromethyl group.

[0282] Cation part ((M' m+ ) 1 / m The cation is particularly preferably represented by the following general formula (ca-h-1).

[0283] [ka] [In the formula, Rf 201 ~Rf 203 Each of these independently represents an optionally substituted aryl group, an optionally substituted alkyl group, or an optionally substituted alkenyl group. 201 ~Rf 203 These atoms may bond to each other to form a ring with the sulfur atom in the formula. However, Rf 201 ~Rf 203 At least one of them has at least one halogen atom.

[0284] Rf in the above equation (ca-h-1) 201 ~Rf 203 R in the above formula (ca-1) is 201 ~R 203The same applies to each of the above. However, Rf 201 ~Rf 203 At least one of the components has at least one halogen atom. The halogen atom is preferably at least one selected from the group consisting of fluorine, iodine, and bromine atoms, and more preferably fluorine. The cation represented by formula (ca-h-1) preferably contains three or more halogen atoms, more preferably four or more halogen atoms, even more preferably five or more halogen atoms, and particularly preferably six or more halogen atoms. Rf 201 ~Rf 203 Any one of them may have three or more halogen atoms, Rf 201 ~Rf 203 The total number of halogen atoms contained in it may be three or more. Rf 201 ~Rf 203 The substituent is preferably an aryl group which may have substituents, and more preferably an aryl group which has substituents containing a halogen atom. The substituent containing a halogen atom is preferably at least one selected from the group consisting of halogen atoms and alkyl halides, more preferably at least one selected from the group consisting of fluorine atoms, iodine atoms and alkyl fluorides, even more preferably at least one selected from the group consisting of fluorine atoms, iodine atoms and trifluoromethyl groups, and particularly preferably at least one selected from the group consisting of fluorine atoms and iodine atoms. As such a cation portion, a cation selected from the group consisting of cations represented by the chemical formulas (ca-1-44) and (ca-1-71) to (ca-1-104), respectively, is particularly preferred.

[0285] The following are some preferred examples of the constituent unit (a5). In the following equation, R α m and M' represent a hydrogen atom, a methyl group, or a trifluoromethyl group. m+ These are m and M' in the general formula (a5-1) above. m+ It is similar to that.

[0286] [ka]

[0287] [ka]

[0288] [ka]

[0289] (A1) The constituent units (a5) of component (A1) may be one type or two or more types. If component (A1) has constituent units (a5), the proportion of constituent units (a5) in component (A1) is preferably 2 to 30 mol%, more preferably 5 to 25 mol%, and even more preferably 10 to 20 mol%, relative to the total amount (100 mol%) of all constituent units that make up component (A1). If the proportion of the constituent unit (a5) is above the lower limit of the preferred range mentioned above, it becomes easier to achieve further increases in sensitivity and resolution. On the other hand, if it is below the upper limit of the preferred range mentioned above, it becomes easier to balance it with the other constituent units.

[0290] Unit of composition (a6): The constituent unit (a6) is a constituent unit that has acid diffusion control properties. Component (A1) may or may not contain constituent unit (a6). Known constituent units can be used for constituent unit (a6). Examples of constituent unit (a6) include constituent units containing the structures described in components (D1) and (D2) below. For example, a constituent unit containing a structure represented by any of the general formulas (d1-1) to (d1-3) below can be used.

[0291] The constituent units (a6) of component (A1) may be one type or two or more types. If component (A1) has constituent units (a6), the proportion of constituent units (a6) in component (A1) is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and even more preferably 3 to 10 mol%, relative to the total amount (100 mol%) of all constituent units that make up component (A1). If the proportion of the constituent unit (a6) is above the lower limit of the preferred range mentioned above, it becomes easier to achieve even higher sensitivity. On the other hand, if it is below the upper limit of the preferred range mentioned above, it becomes easier to balance it with the other constituent units.

[0292] Unit of composition (a8): The constituent unit (a8) is a constituent unit derived from the compound represented by the following general formula (a8-1). Component (A1) may or may not have the constituent unit (a8).

[0293] [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.]

[0294] 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.

[0295] 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.

[0296] 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.

[0297] 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.

[0298] [ka]

[0299] 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).

[0300] The constituent units (a8) of component (A1) may be one type or two or more types. Component (A1) may or may not have constituent units (a8). The proportion of constituent units (a8) in component (A1) is preferably 1 to 30 mol%, more preferably 2 to 25 mol%, and even more preferably 5 to 20 mol%, relative to the total amount (100 mol%) of all constituent units that make up component (A1).

[0301] The (A1) component contained in the resist composition may be used alone or in combination of two or more types.

[0302] Examples of component (A1) include polymer compounds having structural units (a0) and (a10); polymer compounds having structural units (a0), (a10), and (a2); polymer compounds having structural units (a0), (a10), and (a5); polymer compounds having structural units (a0), (a10), and (a8). Component (A1) is preferably a polymer compound consisting of structural units (a0) and (a10); a polymer compound consisting of structural units (a0), (a10), and (a2); a polymer compound consisting of structural units (a0), (a10), and (a5); or a polymer compound consisting of structural units (a0), (a10), and (a8).

[0303] In a polymer compound consisting of constituent units (a0) and (a10), the proportion of constituent unit (a0) is more preferably 20 to 80 mol%, even more preferably 25 to 75 mol%, even more preferably 30 to 70 mol%, and particularly preferably 35 to 65 mol%, relative to the total amount (100 mol%) of all constituent units that make up the polymer compound. The proportion of constituent units (a10) in the polymer compound is preferably 20 to 80 mol%, more preferably 25 to 75 mol%, even more preferably 30 to 70 mol%, and particularly preferably 35 to 65 mol%, relative to the total amount (100 mol%) of all constituent units that make up the polymer compound.

[0304] In a polymer compound comprising constituent unit (a0), constituent unit (a10), and other constituent units (any of constituent units (a8), (a2), or (a5)), the proportion of constituent unit (a0) is preferably 20 to 80 mol%, more preferably 25 to 75 mol%, even more preferably 30 to 70 mol%, and even more preferably 35 to 65 mol%, relative to the total amount (100 mol%) of all constituent units that make up the polymer compound. The proportion of constituent units (a10) in the polymer compound is preferably 15 to 60 mol%, more preferably 20 to 55 mol%, even more preferably 25 to 50 mol%, and particularly preferably 30 to 50 mol%, relative to the total amount (100 mol%) of all constituent units that make up the polymer compound. The proportion of other constituent units (each of constituent units (a8), (a2), or (a5)) in the polymer compound is preferably 5 to 20 mol%, and more preferably 5 to 15 mol%, relative to the total amount (100 mol%) of all constituent units that make up the polymer compound.

[0305] 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. Examples of monomers that induce each constituent unit include monomers that induce constituent unit (a10), monomers that induce constituent unit (a1), and monomers that induce other arbitrary constituent units (e.g., constituent unit (a4), constituent unit (st), etc.). These monomers (e.g., monomers that induce constituent unit (a10)) may have their hydroxyl groups or the like protected as needed. In this case, component (A1) can be produced by carrying out a deprotection reaction after the polymerization reaction as described above. 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 in this way are effective in reducing development defects and LER (line edge roughness: uneven unevenness of the line sidewall).

[0306] 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 3,000 to 40,000, and even more preferably 4,000 to 30,000. 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.

[0307] (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 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.

[0308] 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, sensitivity tends to improve, and a resist pattern with excellent lithography characteristics such as resolution and roughness is more easily formed.

[0309] In the resist composition of this embodiment, the content of component (A) may be adjusted according to the resist film thickness to be formed.

[0310] <Other ingredients> The resist composition of this embodiment may further contain other components in addition to the above-described component (A). Examples of such other components include the following components (B), (D), (E), (F), and (S).

[0311] <Acid generating agent component (B)> The resist composition of this embodiment may contain an acid-generating agent 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. The form in which component (B) is contained may be in the form of a compound, or it may be incorporated into component (A1) as the above-mentioned constituent unit (a5), or it may be in both of these forms.

[0312] 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)").

[0313] [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 Each of these is independently a single bond, an alkylene group, or a fluorinated alkylene group. However, Y 101 and V 101 L cannot be a single bond at the same time. 101 ~L 102 Each of these is independently either a single bond or an oxygen atom. 103 ~L 105These 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.

[0314] {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.

[0315] Cyclic groups that may have substituents: The cyclic group is preferably a cyclic hydrocarbon group, which may be an aromatic 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.

[0316] R 101 The aromatic group in this context is a group having at least one aromatic ring. This aromatic ring is not particularly limited as long as it is a cyclic conjugated system with 4n+2 π electrons, and may be monocyclic, polycyclic, or have substituents that substitute for the hydrogen atoms of the aromatic ring. Examples of aromatic rings include aromatic hydrocarbon rings and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced by heteroatoms. Examples of aromatic rings include aromatic hydrocarbon rings and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced by heteroatoms. The number of carbon atoms in the aromatic hydrocarbon ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 5 to 15, and particularly preferably 6 to 12. However, this number of carbon atoms does not include the number of carbon atoms in substituents that substitute for hydrogen atoms in the aromatic hydrocarbon ring. Specific examples of aromatic hydrocarbon rings include benzene, naphthalene, anthracene, and phenanthrene. 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.

[0317] The aromatic group preferably has 4 to 30 carbon atoms, more preferably 4 to 25, even more preferably 4 to 20, particularly preferably 4 to 15, and most preferably 4 to 10 carbon atoms. However, this number of carbon atoms does not include the number of carbon atoms in substituents. R 101 Specific examples of aromatic 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.

[0318] 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, adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 Polycycloalkanes having a cross-linked ring polycyclic skeleton, such as decane and tetracyclododecane; polycycloalkanes having a fused ring polycyclic skeleton, such as a cyclic group having a steroid skeleton, are more preferred.

[0319] Among them, R 101 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, even more preferably an adamantyl group or a norbornyl group, and particularly preferably an adamantyl group.

[0320] 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.

[0321] Also, R 101 The cyclic hydrocarbon group in the above 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 chemical formulas (r-hr-1) to (r-hr-16).

[0322] 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.

[0323] 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 the groups 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.

[0324] [ka]

[0325] R 101Examples 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 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. Aromatic 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 hydrogen atom 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 aforementioned fused ring group include groups obtained by removing one hydrogen atom from monocycloalkanes such as cyclopentane and cyclohexane; adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 Examples include groups obtained by removing one hydrogen atom from polycycloalkanes such as decane 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).

[0326] 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.

[0327] A chain-like alkenyl group which may have substituents: R 101 The 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 2. Examples of linear alkenyl groups include vinyl groups, propenyl groups (allyl groups), and butenyl groups. Examples of branched alkenyl groups include 1-methylvinyl groups, 2-methylvinyl groups, 1-methylpropenyl groups, and 2-methylpropenyl groups. Among the chain-like alkenyl groups mentioned above, linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred.

[0328] 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.

[0329] 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 general formulas (L-al-1) to (L-al-8) above. Note that in the general formulas (L-al-1) to (L-al-8) below, R in formula (b-1) above 101 The combination with this is V' in the following general formulas (L-al-1)~(L-al-8). 101 That is the case.

[0330] 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.

[0331] 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.

[0332] 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).

[0333] [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-16), 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.]

[0334] 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.

[0335] 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 group exemplified as an aromatic group in the cyclic hydrocarbon group in the above formula (b-1). 101 Examples include substituents similar to those that may be substituted for the aromatic group in the above.

[0336] 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.

[0337] • 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 higher 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.

[0338] • 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-.

[0339] Among the above, the anion portion of component (B) is preferably the anion in component (b-1), and more preferably the anion represented by the formula (an-1).

[0340] {cation part} In the above equations (b-1), (b-2), and (b-3), M' m+ This represents an m-valent onium cation. Among these, sulfonium cations and iodonium cations are preferred. m is an integer of 1 or greater.

[0341] As the cation portion of component (B), a sulfonium cation is preferred, the cations represented by formulas (ca-1) to (ca-3) are more preferred, the cation represented by formula (ca-1) is even more preferred, and the cations represented by formulas (ca-1-1) to (ca-1-104) are particularly preferred. Particularly from the viewpoint of reducing roughness, the cationic portion of component (B) is more preferably a cation represented by the general formula (ca-h-1), and is especially preferred to be a cation selected from the group consisting of cations represented by the chemical formulas (ca-1-44) and (ca-1-71) to (ca-1-104), respectively.

[0342] 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 70 parts by mass, more preferably 5 to 60 parts by mass, and even more preferably 10 to 50 parts by mass, per 100 parts by mass of component (A). (B) It is preferable to set the content of component (B) within the above preferred range, as this makes it easier to obtain a uniform solution when each component of the resist composition is dissolved in an organic solvent, resulting in good storage stability of the resist composition.

[0343] <Basic component (D)> The resist composition of this embodiment may contain, in addition to component (A), a basic component (component (D)) that traps the acid generated by exposure (i.e., controls the diffusion of the acid). 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. The components (D1) and (D2) may be in the form of compounds, incorporated into component (A1) as the aforementioned structural unit (a6), or in both forms. The compound exemplified as component (D1) described later may be used as the aforementioned acid-generating component (component (B)) depending on the combination with other compounds.

[0344] • About the (D1) component 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.

[0345] [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.

[0346] {(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 1Preferred 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 preferred substituents in this case are the linking groups represented by the general formulas (L-al-1) to (L-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 (L-al-1) to (L-al-8) as a substituent, then in the general formulas (L-al-1) to (L-al-8), Rd in formula (d1-1) 1 The carbon atom constituting the aromatic hydrocarbon group, aliphatic cyclic group, or linear alkyl group in the above general formula (L-al-1) to (L-al-8) 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). Examples of the aliphatic cyclic group include adamantane, norbornane, isobornane, and tricyclo[5.2.1.0 2,6 It is more preferable that the group is obtained by removing one or more hydrogen atoms from a polycycloalkane such as decane 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.

[0347] 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.

[0348] The following are preferred specific examples of the anionic portion of component (d1-1).

[0349] [ka]

[0350] ··Cation section In formula (d1-1), M m+ This is an m-valent organic cation. M m+ Suitable organic cations include those similar to those represented by the general formulas (ca-1) to (ca-3), 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-1-104) being even more preferred. Particularly from the viewpoint of reducing roughness, the cationic portion of component (d1-1) is more preferably a cation represented by the general formula (ca-h-1), and a cation selected from the group consisting of cations represented by the chemical formulas (ca-1-44) and (ca-1-71) to (ca-1-104), respectively, is especially preferred. (d1-1) Component may be used alone or in combination of two or more types.

[0351] {(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 Preferably, the group is a chain-like alkyl group which may have substituents, or an aliphatic cyclic group which may have substituents, and more preferably an aliphatic cyclic group which may have substituents.

[0352] The chain-like alkyl group preferably has 1 to 10 carbon atoms, and more preferably 3 to 10 carbon atoms. Examples of the aliphatic cyclic group include adamantane, norbornane, isobornane, and tricyclo[5.2.1.0 2,6 A group obtained by removing one or more hydrogen atoms from decane, tetracyclododecane, etc. (which may have substituents); more preferably a group obtained by removing one or more hydrogen atoms from camphor.

[0353] Rd 2 The hydrocarbon group may have substituents, and such substituents may be Rd of formula (d1-1). 1Examples 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.

[0354] The following are preferred specific examples of the anionic portion of component (d1-2).

[0355] [ka]

[0356] ··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.

[0357] {(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.

[0358] 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 4The 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.

[0359] Rd 4 The alkenyl group in R' 201 Examples 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.

[0360] Rd 4 The cyclic group in is the R' 201 Examples of cyclic groups similar to those in [5.2.1.0] include cyclopentane, cyclohexane, adamantane, norbornane, isobornane, and tricyclo[5.2.1.0]. 2,6 A preferred alicyclic group is obtained by removing one or more hydrogen atoms from a cycloalkane such as decane or tetracyclododecane, or an aromatic group such as a phenyl group or naphthyl group. 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.

[0361] In formula (d1-3), Yd1 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 [the relevant section]. 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.

[0362] The following are preferred specific examples of the anionic parts of components (d1-3).

[0363] [ka]

[0364] [ka]

[0365] ··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.

[0366] 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 1 to 30 parts by mass, more preferably 2 to 25 parts by mass, and even more preferably 3 to 20 parts by mass, per 100 parts by mass of component (A).

[0367] Component (D1) preferably contains the above-mentioned component (d1-1). The content of component (d1-1) in the total amount of component (D1) is preferably 50% by mass or more, preferably 70% by mass or more, and more preferably 90% by mass or more, and component (D1) may consist only of compound (d1-1).

[0368] In the resist composition of this embodiment, when an onium salt-based acid generator (components (b-1), (b-2), (b-3), etc.) and component (D1) are used in combination as component (B), it is preferable that the cationic portions of both components be cations represented by the general formula (ca-h-1), and particularly preferable that they be cations selected from the group consisting of cations represented by the chemical formulas (ca-1-44) and (ca-1-71) to (ca-1-104), respectively, from the viewpoint of increasing sensitivity and reducing roughness.

[0369] (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. As an example of a basic component (component (D)) that traps the acid generated by exposure, a compound of component (D1) is shown, but the compound of component (D1) may also be used as component (B). For example, in the resist composition of this embodiment, the compound of component (D1) may be used as component (B), and the compound that generates an acid with lower acidity than the acid generated by the compound of component (D1) upon exposure may be used as component (D). Alternatively, in the resist composition of this embodiment, the compound of component (D1) may be used as component (B), and the component (D2), which will be described later, may be used as component (D).

[0370] • 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 6 to 30 carbon atoms are more preferred, and tri-n-pentylamine or tri-n-octylamine are particularly preferred.

[0371] 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.

[0372] 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.

[0373] 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.

[0374] (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 (A). By using this range, the resist pattern shape, aging stability, etc., are improved.

[0375] <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.

[0376] 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, the lithography characteristics are further improved.

[0377] <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.

[0378] [ka] [In the formula, R is the same as above, and Rf 102 and Rf 103 Each 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.

[0379] 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 Rf103 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.

[0380] 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.

[0381] 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.

[0382] 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).

[0383] <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)"). In the resist composition of this embodiment, component (S) may be used alone or as a mixture of two or more solvents. Among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), γ-butyrolactone, ethyl lactate (EL), and cyclohexanone are preferred.

[0384] 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. As component (S), 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.

[0385] 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.

[0386] The resin component (A1) contained in the resist composition of this embodiment described above has a constituent unit (a0) derived from a compound represented by the general formula (a0-m0). Since the constituent unit (a0) has two acid-dissociable groups, the solubility of the exposed areas of the resist film in the developer is improved during resist pattern formation, resulting in improved resolution. Furthermore, the constituent unit (a0) has an amide bond. The amide bond forms appropriate hydrogen bonds with other constituent units (a0) and with hydroxyl groups contained in other constituent units of the resin component (A1), for example. This increases the glass transition temperature (Tg) of the resin component (A1), suppressing acid diffusion, which in turn suppresses reactions caused by the acid in the unexposed areas of the resist film, improving pattern roughness and exposure margin. It is presumed that the resist composition of this embodiment works synergistically to enhance lithography characteristics such as resolution, pattern roughness, and exposure margin when forming a resist pattern, due to the synergistic effects of the above-mentioned actions.

[0387] (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.

[0388] First, the resist composition of the above-described 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.

[0389] 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.

[0390] 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.

[0391] 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. The resist pattern formation method of this embodiment is particularly useful in the step of exposing the resist film to EUV (extreme ultraviolet) or EB (electron beam). The method for exposing the resist film may be a normal exposure (dry exposure) performed in an inert gas such as air or nitrogen.

[0392] 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.

[0393] 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.

[0394] Examples of nitrile solvents include acetonitrile, propionitrile, valeronitrile, and butyronitrile.

[0395] Organic developers may contain known additives as needed. Examples of such additives include surfactants. While not particularly limited, surfactants such as ionic or nonionic fluorine-based and / or silicon-based surfactants can be used.

[0396] 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).

[0397] 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.

[0398] 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).

[0399] According to the resist pattern formation method of this embodiment described above, since the above-mentioned resist composition is used, it is possible to form a resist pattern with improved lithography characteristics such as resolution, pattern roughness, and exposure margin.

[0400] The resist compositions of the embodiments described above, and the various materials used in the pattern forming methods of the embodiments described above (for example, resist solvents, developers, rinse solutions, anti-reflective film forming compositions, topcoat forming compositions, etc.) are preferably free from impurities such as metals, metal salts containing halogens, acids, alkalis, sulfur atoms, or phosphorus atoms. Examples of metal atom-containing impurities include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Cr, Ni, Zn, Ag, Sn, Pb, Li, or salts thereof. The impurity content 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 free (below the detection limit of the measuring device).

[0401] (compound) The compound according to the third aspect of the present invention is a compound represented by the following general formula (a0-m0) (hereinafter also referred to as "compound (m0)").

[0402] [ka] [In the formula, W 0 X represents a polymerizable group-containing group. 0 is a hydrogen atom, an alkyl group, or *-L 02 -COOR 02 This represents a group represented by *. * represents a bond to an adjacent nitrogen atom. 01 and L 02 Each of these independently represents a chain or cyclic aliphatic hydrocarbon group which may have substituents. 01 and R 02 Each of these independently represents an acid-dissociable group. n0 is either 1 or 2. When n0 is 1, the X 0 is, *-L 02 -COOR 02 The group is represented by . When n0 is 2, the X 0 is a hydrogen atom or an alkyl group. When n0 is 2, two R 01They may be the same or they may be different.

[0403] The description of the aforementioned compound (m0) is the same as the description of the compound represented by the general formula (a0-m0) described in the above section on "Constituent Unit (a0)".

[0404] The aforementioned compound (m0) may be a compound represented by the following general formula (a0-m0-1) (hereinafter also referred to as "compound (m0-1)").

[0405] [ka] [In the formula, W 01 X represents a polymerizable group-containing group. 01 L represents a hydrogen atom or an alkyl group. 011 R represents a linear or cyclic aliphatic hydrocarbon group which may have substituents. 03 and R 04 Each of these independently represents an acid-dissociating group.

[0406] The description of the aforementioned compound (m0-1) is the same as the description of the compound represented by the general formula (a0-m0-1) described in the above section on "Constituent Unit (a0)".

[0407] The aforementioned compound (m0) may be a compound represented by the following general formula (a0-m0-2) (hereinafter also referred to as "compound (m0-2)").

[0408] [ka] [In the formula, W 02 L represents a polymerizable group-containing group. 021 and L 022 Each of these independently represents a chain or cyclic aliphatic hydrocarbon group which may have substituents. 05 and R 06 Each of these independently represents an acid-dissociating group.

[0409] The description of the aforementioned compound (m0-2) is the same as the description of the compound represented by the general formula (a0-m0-2) described in the above section on "Constituent Unit (a0)".

[0410] Specific examples of compound (m0) are given below, but are not limited to these. In each of the following formulas, R β This represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0411] [ka]

[0412] [ka]

[0413] [ka]

[0414] [ka]

[0415] [ka]

[0416] [ka]

[0417] [ka]

[0418] [ka]

[0419] [ka]

[0420] <Method for producing compounds> Compound (m0) can be produced by appropriately combining known methods, as shown in the <Synthesis Example of Compound> in the [Examples] section below.

[0421] The compounds of this embodiment described above can be used in the production of the resist composition according to the first embodiment. Furthermore, the compounds of this embodiment can be used in the production of the polymer compound according to the fourth embodiment, which will be described later.

[0422] (polymer compound) A polymer compound according to a fourth aspect of the present invention has a constituent unit (a0) derived from the compound represented by the general formula (a0-m0). The constituent unit (a0) is the same as described above. The polymer compound of this embodiment can be used in the production of the resist composition according to the first embodiment described above. By incorporating the polymer compound of this embodiment into the resist composition, lithography characteristics such as resolution, pattern roughness, and exposure margin can be improved. [Examples]

[0423] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0424] <Examples of compound synthesis> (Example of compound (m0-1) synthesis) A mixed solution of 6.4 g of compound (m0-1a), 7.0 g of compound (m0-1b), 0.4 g of N,N-dimethylaminopyridine (DMAP), and 40 g of dichloromethane was gradually added to a 20 g solution of dichloromethane containing 8.5 g of diisopropylcarbodiimide (DIC). After stirring at room temperature for 18 hours, insoluble matter was removed by filtration, and the mixture was washed with 40 g of water. After removing the solvent by distillation, compound (m0-1) was obtained by purification by column chromatography (5.2 g, yield 52%).

[0425] [ka]

[0426] The obtained compound (m0-1) was subjected to NMR measurement, and its structure was identified based on the analytical results shown below. 1H-NMR (dmso-d6, 400MHz): δ(ppm)=8.31(d,-NH-,1H),5.68(s,-C=CH2,1H),5.40(s,-C=C H2,1H),4.78(m,-CH-,1H),2.7-2.9(dd,-CH2-,2H),1.83(s,-CH3,3H),1.49(s,-CH3,18H)

[0427] (Synthesis of compounds (m0-2) to (m0-9)) Compounds (m0-2) to (m0-9) were synthesized in the same manner as compound (m0-1), except that compounds (m0-2b) to (m0-9b) were used instead of compound (m0-1b).

[0428] [ka]

[0429] The obtained compounds (m0-2) to (m0-9) are shown below.

[0430] [ka]

[0431] (Synthesis of compounds (m0-11) to (m0-15)) Compounds (m0-11) to (m0-15) were synthesized in the same manner as compound (m0-1), except that compounds (m0-2a) to (m0-6a) were used instead of compound (m0-1a), and compound (m0-2b) was used instead of compound (m0-1b).

[0432] [ka]

[0433] The obtained compounds (m0-11) to (m0-15) are shown below.

[0434] [ka]

[0435] (Synthesis of compound (m0-10)) 7.7 g of the compound (m0-3) obtained above was dissolved in 40 g of dimethylformamide (DMF). 1.0 g of sodium hydride (60%) and 3.6 g of iodomethane were added to the solution, and the mixture was stirred at room temperature for 24 hours. Then, 60 g of dichloromethane was added, and the mixture was washed with 40 g of water. After removing the solvent by distillation, the compound (m0-10) was obtained by purification by column chromatography (5.0 g, yield 62%).

[0436] [ka]

[0437] The obtained compounds (m0-2) to (m0-15) were subjected to NMR measurements, and their structures were identified based on the analytical results shown below.

[0438] Compound (m0-2): 1H-NMR (dmso-d6, 400MHz): δ(ppm)=8.31(d,-NH-,1H),7.68(m,-Ar,4H),7.15(m,-Ar,4H),5.68(s,-C=CH2, 1H),5.40(s,-C=CH2,1H),4.78(m,-CH-,1H),2.7-2.9(dd,-CH2-,2H),1.83(s,-CH3,3H),1.71(s,-CH3,12H)

[0439] Compound (m0-3): 1H-NMR (dmso-d6, 400MHz): δ(ppm)=8.31(d,-NH-,1H),5.68(s,-C=CH2,1H),5.40(s,-C=CH2,1H),4.78(m,-CH- ,1H),2.7-2.9(dd,-CH2-,2H),2.2(m,-CH2-,4H),1.83(s,-CH3,3H),1.6-1.8(m,-CH2-,12H),1.62(s,-CH3,6H)

[0440] Compound (m0-4): 1H-NMR (dmso-d6, 400MHz): δ(ppm)=8.31(d,-NH-,1H),6.22(m,-CH=CH2,2H),5.68(s,-C=CH2,1H),5.40(s,-C=CH2,1H),5.1-5.2(m,-CH=CH2 ,4H),4.78(m,-CH-,1H),2.7-2.9(dd,-CH2-,2H),2.15-2.25(m,-CH2-,4H),1.9-2.0(m,-CH2-,4H),1.83(s,-CH3,3H),1.6-1.8(m,-CH2-,8H)

[0441] Compound (m0-5): 1H-NMR (dmso-d6, 400MHz): δ(ppm)=8.31(d, -NH-, 1H), 7.2-7.3(m, -Ar, 10H), 5.68(s, -C=CH2, 1H), 5.40(s, -C=CH2, 1H), 4.78(m, -CH-, 1H), 2.7-2.9(dd, -CH2-, 2H), 2.4(m, -CH2-, 4H), 1.83(s, -CH3, 3H), 1.7-1.8(m, -CH2-, 4H), 1.5-1.7(m, -CH2-, 10H), 1.3(m, -CH2-, 2H)

[0442] Compound (m0-6): 1H-NMR (dmso-d6, 400MHz): δ(ppm)=8.31(d, -NH-, 1H), 7.3-7.4(m, -Ar, 8H), 7.25(m, -Ar, 2H), 5.68(s, -C=CH2, 1H), 5.40(s, -C=CH2, 1H), 4.78(m, -CH-, 1H), 3.81(m, -CH2-, 4H), 3.66(m, -CH2-, 4H), 2.7-2.9(dd, -CH2-, 2H), 2.37(m, -CH2-, 4H), 2.08(m, -CH2-, 4H), 1.83(s, -CH3, 3H)

[0443] Compound (m0-7): 1H-NMR (dmso-d6, 400MHz): δ(ppm)=8.31(d, -NH-, 1H), 5.68(s, -C=CH2, 1H), 5.40(s, -C=CH2, 1H), 4.78(m, -CH-, 1H), 2.7-2.9(dd, -CH2-, 2H), 2.34(m, -CH-, 4H), 2.04(m, -CH2-, 4H), 1.92(m, -CH2-, 4H), 1.83(s, -CH3, 3H), 1.7-1.8(m, -CH2-, 12H), 1.66(s, -CH3, 6H), 1.58(m, -CH-, 4H)

[0444] Compound (m0-8): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 8.31 (d, -NH-, 1H), 7.47 (d, Thiophene, 2H), 7.10 (d, Thiophene, 2H), 6.98 (m, Thiophene, 2H), 5.68 (s, -C=CH2, 1H), 5.40 (s, -C=CH2, 1H), 4.78 (m, -CH-, 1H), 4.24 (d, -CH2-, 2H), 4.07 (d, -CH2-, 2H), 3.92 (m, -CH2-, 4H), 2.7-2.9 (dd, -CH2-, 4H), 2.52 (m, -CH2-, 2H), 1.83 (s, -CH 3 , 3H)

[0445] Compound (m0-9): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 8.31 (d, -NH-, 1H), 5.68 (s, -C=CH2, 1H), 5.55 (s, -CH=C, 2H), 5.40 (s, -C=CH2, 1H), 5.19 (s, -CH-, 2H), 4.78 (m, -CH-, 1H), 2.7-2.9 (dd, -CH2-, 2H), 1.9-2.1 (m, -CH2-, 4H), 1.6-1.9 (m, -CH2-, 8H), 1.83 (s, -CH3, 3H), 1.70 (s, -CH3, 6H)

[0446] Compound (m0-10): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 5.63 (s, -C=CH2, 1H), 5.37 (s, -C=CH2, 1H), 4.72 (m, -CH-, 1H), 3.10 (s, -CH3, 3H), 2.7-2.9 (dd, -CH2-, 2H), 2.2 (m, -CH2-, 4H), 1.83 (s, -CH3, 3H), 1.6-1.8 (m, -CH2-, 12H), 1.62 (s, -CH3, 6H)

[0447] Compound (m0-11): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 8.53 (d, -NH-, 1H), 7.94 (d, -Ar, 2H), 7.59 (d, -Ar, 2H), 6.82 (dd, -CH=CH2, 1H), 5.98 (d, -CH=CH2, 1H), 5.38 (d, -CH=CH2, 1H), 4.82 (m, -CH-, 1H), 2.7-2.9 (dd, -CH2-, 2H), 2.2 (m, -CH2-, 4H), 1.6-1.8 (m, -CH2-, 12H), 1.62 (s, -CH3, 6H)

[0448] Compound (m0-12): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 10.72 (s, -OH, 1H), 8.49 (d, -NH-, 1H), 7.72 (s, -Ar, 1H), 7.68 (d, -Ar, 1H), 6.96 (d, -Ar, 1H), 6.70 (dd, -CH=CH2, 1H), 5.70 (d, -CH=CH2, 1H), 5.16 (d, -CH=CH2, 1H), 4.82 (m, -CH-, 1H), 2.7-2.9 (dd, -CH2-, 2H), 2.2 (m, -CH2-, 4H), 1.6-1.8 (m, -CH2-, 12H), 1.62 (s, -CH3, 6H)

[0449] Compound (m0-13): 1H-NMR (dmso-d6, 400 MHz): δ (ppm) = 8.70 (d, -NH-, 1H), 5.80 (s, -C=CH2, 1H), 5.46 (s, -C=CH2, 1H), 5.12 (d, -CH-, 1H), 2.2 (m, -CH2-, 4H), 1.83 (s, -CH3, 3H), 1.6-1.8 (m, -CH2-, 12H), 1.62 (s, -CH3, 6H)

[0450] Compound (m0-14): 1H-NMR (dmso-d6, 400MHz): δ(ppm)=8.31(d,-NH-,1H),5.68(s,-C=CH2,1H),5.40(s,-C=CH2,1H),4.56(m,-CH-,1H),2.25-2.35(m,-CH2 -,2H),2.2(m,-CH2-,4H),2.0-2.1(m,-CH2-,1H),1.8-1.9(m,-CH2-,1H),1.83(s,-CH3,3H),1.6-1.8(m,-CH2-,12H),1.62(s,-CH3,6H)

[0451] Compound (m0-15): 1H-NMR (DMSO-D6, 400MHz): δ(ppm)=5.63(s,-C=CH2,1H),5.38(s,-C=CH2,1H),4.08(s,-C H2-,4H),2.2(m,-CH2-,4H),1.83(s,-CH3,3H),1.6-1.8(m,-CH2-,12H),1.62(s,-CH3,6H)

[0452] <Manufacturing of polymer compounds> (Synthesis of polymer compound (A1-1)) 9.9 g of compound (m0-1), 5.0 g of compound (a10-1pre), and 1.4 g of azobis(isobutyrate)dimethyl (V-601) as a polymerization initiator were dissolved in 35 g of methyl ethyl ketone (MEK), heated to 80°C under a nitrogen atmosphere, and stirred for 6 hours. Then, 1.5 g of trifluoroacetic acid (TFA) and 50 g of t-butanol were added to the reaction mixture, and the mixture was stirred at 30°C for 18 hours. The resulting reaction mixture was added dropwise to 600 g of heptane. The resulting white solid was filtered, and 8.0 g of the target polymer compound (A1-1) was obtained by drying under reduced pressure for 24 hours.

[0453] [ka]

[0454] (Synthesis of polymer compounds (A1-2) to (A1-20)) Polymer compounds (A1-2) to (A1-20) were synthesized in the same manner as polymer compound (A1-1), except that the compounds used in the polymerization reaction were changed. The monomers used in the synthesis of polymer compounds (A1-2) to (A1-20) are shown below. [ka]

[0455] The polymer compounds (A1-1) to (A1-20) are shown below. In the formulas below, l, m, and n represent the composition ratio (molar ratio) of each constituent unit.

[0456] [ka]

[0457] [ka]

[0458] [ka]

[0459] [ka]

[0460] (Synthesis of comparative polymer compounds) Polymer compounds (A2-1) to (A2-3) were obtained using the same method as the synthesis of polymer compound (A1-1), except that the compounds used in the polymerization reaction were changed. The monomer compounds used in the synthesis of polymer compounds (A2-1) to (A2-3) are shown below.

[0461] [ka]

[0462] The obtained polymer compounds (A2-1) to (A2-3) are shown below. In the following formulas, l and m represent the composition ratio (molar ratio) of each constituent unit.

[0463] [ka]

[0464] For the obtained polymer compounds (A1-1) to (A1-20) and (A2-1) to (A2-3), the weight-average molecular weight (Mw) and molecular weight dispersion (Mw / Mn) were determined by GPC measurement (standard polystyrene equivalent). Furthermore, for the polymer compounds (A1-1) to (A1-20) and (A2-1) to (A2-3), the copolymerization composition ratio (the proportion (molar ratio) of each constituent unit in the structural formula) was determined by carbon-13 nuclear magnetic resonance spectroscopy (400 MHz, 13 The results were determined by 13C-NMR. The results are shown in Table 1.

[0465] [Table 1]

[0466] <Preparation of the resist composition> (Examples 1-22, Comparative Examples 1-3) Each example of a resist composition was prepared by mixing and dissolving the components shown in Tables 2 and 3.

[0467] [Table 2]

[0468] [Table 3]

[0469] In Tables 2 and 3, each abbreviation has the following meaning. The numbers in brackets [ ] represent the amount (parts by mass) of the ingredients. (A1-1)~(A1-22): The above polymer compounds (A1-1)~(A1-22). (A2-1)~(A2-3): The above-mentioned polymer compounds (A2-1)~(A2-3).

[0470] (B-1)~(B-2): An acid generator consisting of the following compounds (B-1)~(B-2).

[0471] [ka]

[0472] (D-1)~(D1-2): Acid diffusion control agents consisting of compounds represented by the following chemical formulas (D-1)~(D-2).

[0473] [ka]

[0474] (S-1): A mixed solvent of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 20 / 80 (mass ratio).

[0475] <Resist pattern formation> Steps to form a resist film: Each example of the resist composition was applied to an 8-inch silicon substrate treated with hexamethyldisilazane (HMDS) using a spinner, and a 60 nm thick resist film was formed by pre-baking (PAB) on a hot plate at 100°C for 60 seconds and drying.

[0476] The process of exposing the resist film: 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, and a contact hole pattern (CH pattern) with a target size of 46nm pitch width and 26nm hole diameter was created. Subsequently, a post-exposure heating (PEB) treatment was performed at 80°C for 60 seconds.

[0477] The process of developing the resist film after exposure: 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.). After that, a water rinse was performed with pure water for 15 seconds. As a result, a CH pattern with a pitch width of 46 nm and a hole diameter of 26 nm was formed.

[0478] [Evaluation of fine resolution] In the above-described <Formation of Resist Pattern>, the resolution at the optimal exposure dose (Eop) for CH pattern formation, specifically the hole diameter (nm) of the resolved pattern as the exposure dose is gradually reduced from the optimal exposure dose (Eop) to form the CH pattern, was determined using a scanning electron microscope S-9380 (Hitachi High-Technologies Corporation). The results are shown in Tables 4-5 as "Resolution (nm)".

[0479] [Evaluation of in-plane uniformity (CDU) of pattern dimensions] The CH pattern formed by the above <Resist Pattern Formation> was observed from above using a measuring SEM (Scanning Electron Microscope, accelerating voltage 500V, product name: CG5000, Hitachi High-Technologies Corporation), and the hole diameter (nm) of each hole was measured. Then, the value of three times the standard deviation (σ) calculated from the measurement results (3σ) was determined. The results are shown in Tables 4-5 as "CDU (nm)". The smaller the 3σ value obtained in this way, the higher the uniformity of the dimensions (CD) of the multiple holes formed in the resist film, meaning that the pattern roughness (CDU) is superior.

[0480] [Evaluation of exposure margin] For the formation of the CH pattern described above, the values ​​expressed by the following formula were determined when the exposure amount resulting in a hole width of 26 nm × 105% was defined as E(+) and the exposure amount resulting in a hole width of 26 nm × 95% was defined as E(-). The results are shown in Tables 4 and 5 as "5%EL(%)". The exposure margin obtained in this way means that the larger the value, the smaller the dimensional change due to the amount of exposure. 5%EL(%)={(E(+)-E(-)) / Eop}×100

[0481] [Table 4]

[0482] [Table 5]

[0483] As shown in Tables 4-5, the resist compositions of Examples 1-22 were confirmed to have good resolution, pattern roughness, and exposure margin. On the other hand, when using the resist compositions of Comparative Examples 1 to 3, the results were inferior in either resolution, pattern roughness, or exposure margin.

[0484] [Table 6]

[0485] [ka]

[0486] Table 6 summarizes the evaluation results, component (A), and its monomer composition for the resist compositions of Example 3, Example 13, and Comparative Examples 1-3 described above.

[0487] Comparison of Comparative Examples 1 and 2 with Comparative Example 3: Comparative Example 2, which used a monomer having two acid-dissociable groups, showed improved resolution compared to Comparative Example 3, but only slight improvements in pattern roughness and exposure margin. Comparative Example 1, which used monomer (m-1) in which the ester bond of monomer (m-3) used in Comparative Example 3 was changed to an amide bond, showed a significant improvement in pattern roughness and exposure margin compared to Comparative Example 3, but the resolution was slightly reduced.

[0488] Comparison of Example 13 and Comparative Example 2: Example 13, which used monomer (m0-13) obtained by changing the ester bond of monomer (m-2) in Comparative Example 2 to an amide bond, showed improved pattern roughness and exposure margin compared to Comparative Example 2.

[0489] Comparison of Example 3 and Comparative Example 1: Example 3, which used monomer (m0-3) with one more acid-dissociable group than monomer (m-1) in Comparative Example 1, showed improved resolution compared to Comparative Example 1.

[0490] From the comparisons between Comparative Examples 1 and 2 and Comparative Example 3, between Example 13 and Comparative Example 2, and between Example 3 and Comparative Example 1, it can be confirmed that the synergistic effect of having two acid-dissociable groups and the effect of having an amide bond significantly improved resolution, pattern roughness, and exposure margin.

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-m0). 【Chemistry 1】 [In the formula, W ０ represents a polymerizable group-containing group. X ０ represents a hydrogen atom, an alkyl group, or a group represented by *-L ０２ -COOR ０２ . * represents a bond bonded to the adjacent nitrogen atom. L ０１ and L ０２ each independently represent a linear or cyclic aliphatic hydrocarbon group which may have a substituent. R ０１ and R ０２ each independently represent an acid-dissociable group. n0 is 1 or 2. When n0 is 1, the X ０ is a group represented by *-L ０２ -COOR ０２ . When n0 is 2, the X ０ is a hydrogen atom or an alkyl group. When n0 is 2, the two R ０１ may be the same or different.]]

2. The resist composition according to claim 1, wherein the resin component (A1) has a constituent unit (a0-1) derived from a compound represented by the following general formula (a0-m0-1). 【Chemistry 2】 [In the formula, W ０１ X represents a polymerizable group-containing group. ０１ L represents a hydrogen atom or an alkyl group. ０１１ R represents a linear or cyclic aliphatic hydrocarbon group, which may have substituents. ０３ and R ０４ Each of these independently represents an acid-dissociating group.

3. The resist composition according to claim 1, wherein the resin component (A1) has a constituent unit (a0-2) derived from a compound represented by the following general formula (a0-m0-2). 【Transformation 3】 [In the formula, W ０２ L represents a polymerizable group-containing group. ０２１ and L ０２２ Each of these independently represents a linear or cyclic aliphatic hydrocarbon group, which may have substituents. ０５ and R ０６ Each of these independently represents an acid-dissociating group.

4. A method for forming a resist pattern, comprising the steps of: forming a resist film on a support using a resist composition according to any one of claims 1 to 3; exposing the resist film; and developing the exposed resist film to form a resist pattern.

5. A compound represented by the following general formula (a0-m0). 【Chemistry 4】 [In the formula, W ０ X represents a polymerizable group-containing group. ０ is a hydrogen atom, an alkyl group, or *-L ０２ - COOR ０２ This represents a group represented by . * represents a bond to an adjacent nitrogen atom. L ０１ and L ０２ Each of these independently represents a linear or cyclic aliphatic hydrocarbon group, which may have substituents. ０１ and R ０２ Each of these independently represents an acid-dissociable group. n0 is 1 or 2. When n0 is 1, the X ０ is, *-L ０２ - COOR ０２ The group is represented by . When n0 is 2, the X ０ is a hydrogen atom or an alkyl group. When n0 is 2, two R ０１ They may be the same or they may be different.

6. The compound according to claim 5, represented by the following general formula (a0-m0-1). 【Transformation 5】 [In the formula, W ０１ X represents a polymerizable group-containing group. ０１ L represents a hydrogen atom or an alkyl group. ０１１ R represents a linear or cyclic aliphatic hydrocarbon group, which may have substituents. ０３ and R ０４ Each of these independently represents an acid-dissociating group.

7. The compound according to claim 5, represented by the following general formula (a0-m0-2). 【Transformation 6】 [In the formula, W ０２ L represents a polymerizable group-containing group. ０２１ and L ０２２ Each of these independently represents a linear or cyclic aliphatic hydrocarbon group, which may have substituents. ０５ and R ０６ Each of these independently represents an acid-dissociating group.

8. A polymer compound having a structural unit derived from the compound described in any one of claims 5 to 7.

Images