Photoresist composition and photoresist pattern formation method

Abstract

A photoresist composition comprising a compound of general formula (d1-1) or a compound of general formula (d1-2) and a polymer compound (A01), wherein the polymer compound (A01) has a constitutive unit (a01) of general formula (a0-1), a constitutive unit (a02) of general formula (a0-2), and a constitutive unit (a03) of general formula (a0-3), wherein in formulas (a0-1) to (a0-3), Ra 01 is a cyclic group containing a lactone, such as a cyano group. Xaa 0 is a group that forms a monocyclic alicyclic hydrocarbon group together with Yaa 0, and Xab 0 is a group that forms a monocyclic alicyclic hydrocarbon group together with Yaab 0.

Description

[Technical Field]

[0001] This invention relates to photoresist composition and a method for forming photoresist patterns. This application claims priority based on Japanese Patent Application No. 2020-200268 filed on December 2, 2020, the contents of which are incorporated herein by reference. [Previous Technology]

[0002] In recent years, due to advancements in lithography technology, the miniaturization of patterns has been rapidly developing in the manufacturing of semiconductor devices or liquid crystal display devices. As a method of miniaturization, the wavelength of the exposure light source is generally shortened (high energy).

[0003] Photoresist materials require photolithography properties such as sensitivity to exposure light sources and resolution for reproducing fine-sized patterns. Conventionally, photoresist materials that meet such requirements have been chemically amplified photoresist compositions containing a substrate component whose solubility in a developing solution changes due to the action of acid and an acid-generating agent component that generates acid upon exposure.

[0004] In chemically amplified photoresist compositions, generally speaking, a resin having a plurality of constituent units is used to improve photolithography properties, etc. For example, Patent Document 1 describes a photoresist composition that combines a resin having a plurality of constituent units, such as those containing lactone groups, with a compound that generates an acid upon irradiation by active light or radiation. It also describes that with this photoresist composition, during immersion exposure, the collapse of the photoresist pattern and the deterioration of the outline are reduced, and dissolution into the immersion liquid is suppressed. [Prior Art Documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2009-271253 [Summary of the Invention]

[0006] [The problem that the invention aims to solve]

[0007] Recently, advancements in lithography technology and the expansion of its applications have led to a rapid miniaturization of patterns. However, if conventional photoresist compositions are used to form fine patterns (e.g., fine lines and gaps) on a substrate, the uniformity of the gap width (roughness reduction) within the pattern is still insufficient to meet requirements. Furthermore, resolution issues such as pattern collapse also arise, and the collapse margin is also inadequate. Moreover, the finer the pattern, the more likely the unexposed areas of the photoresist film will dissolve during development (developing film loss), resulting in a decrease in the amount of residual film in the pattern.

[0008] This invention was made in view of the above-mentioned circumstances. The objective is to provide a photoresist composition with good roughness reduction, collapse limit, and pattern residue, and a method for forming photoresist patterns using the photoresist composition. [Means for Solving the Problem]

[0009] In order to solve the above-mentioned problems, the present invention adopts the following structure. That is, the first state sample of the present invention is a photoresist composition, which is a photoresist composition that generates acid by exposure and whose solubility in the developing solution changes by the action of acid, comprising: a resin component (A1) whose solubility in the developing solution changes by the action of acid, and one or more compounds (D1) selected from the group consisting of compounds represented by the following general formula (d1-1) and compounds represented by the following general formula (d1-2), wherein the aforementioned resin component (A1) comprises a polymeric compound (A01) having a constituent unit (a01) represented by the following general formula (a0-1), a constituent unit (a02) represented by the following general formula (a0-2), and a constituent unit (a03) represented by the following general formula (a0-3);

[0010] [In the formula, Rd1 and Rd2 are each independently a cyclic group that may have substituents, a chain alkyl group that may have substituents, or a chain alkenyl group that may have substituents; however, in Rd2 in formula (d1-2), the carbon atom adjacent to the S atom is not bonded with a fluorine atom; m is an integer greater than or equal to 1, and Mm+ are each independently an m-valent organic cation];

[0011] [In formula (a0-1), R01 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms; Va01 is a divalent linkage; na01 is an integer from 0 to 2; Ra01 is a lactone-containing cyclic group having one or more substituents selected from the group consisting of halogen atoms, carboxyl groups, acetyls, nitro groups, and cyano groups; the aforementioned lactone-containing cyclic group may also have substituents other than those in the aforementioned group; In formula (a0-2), R02 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms; Va02 is a divalent linkage; na02 is an integer from 0 to 2; Ra021 and Ra022 are each independently a chain alkyl group; Yaa0 is a carbon atom; Xaa0 is a group that forms a monocyclic alicyclic hydrocarbon group together with Yaa0; some or all of the hydrogen atoms in this monocyclic alicyclic hydrocarbon group may be substituted. In formula (a0-3), R03 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms; Va03 is a divalent linkage; na03 is an integer from 0 to 2; Ra031 is a chain alkyl group; Yab0 is a carbon atom; Xab0 is a group that forms a monocyclic alicyclic hydrocarbon group together with Yab0; some or all of the hydrogen atoms in this monocyclic alicyclic hydrocarbon group may be substituted.

[0012] The second aspect of the present invention is a method for forming a photoresist pattern, comprising: a step of forming a photoresist film on a support using the photoresist composition of the first aspect; a step of exposing the photoresist film; and a step of developing the exposed photoresist film to form a photoresist pattern. [Effects of the Invention]

[0013] According to the present invention, a photoresist composition with good roughness reduction, collapse limit and pattern residual film, and a photoresist pattern forming method using the photoresist composition can be provided.

Implementation Method

[0014] [Form of the invention]

[0015] In this specification and the claims of this application, "aliphatic" is a concept relative to aromatic, defined as a group, compound, etc., that does not possess aromaticity. "Alkyl" unless otherwise specified includes linear, branched, and cyclic monovalent saturated hydrocarbon groups. The same applies to alkyl groups in alkoxy groups. "Dialkyl" unless otherwise specified 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 constitutes a polymer compound (resin, polymer, copolymer). When stated as "may have substituents," it includes both the case of a monovalent group replacing a hydrogen atom (-H) and the case of a divalent group replacing a methylene group (-CH2-). "Exposure" encompasses all forms of radiation exposure.

[0016] An "acid-decomposable group" is a group whose structure, at least a portion of the bonds, can be broken by the action of an acid, thus possessing acid-decomposability. Examples of acid-decomposable groups whose polarity increases by the action of an acid include groups that decompose by the action of an acid to produce polar groups. Examples of polar groups include carboxyl, hydroxyl, amino, and sulfonyl (-SO3H). Specifically, examples of acid-decomposable groups include groups whose aforementioned polar groups are protected by acid-dissociating groups (e.g., groups in which the hydrogen atoms of an OH-containing polar group are protected by an acid-dissociating group).

[0017] The term "acid-dissociable group" refers to (i) a group whose bonds with adjacent atoms can be broken by the action of an acid, or (ii) a group whose bonds can be broken by a partial bond breakage by an acid, and which can further break bonds with adjacent atoms through a decarbonation reaction. The acid-dissociable group constituting the acid-dissociable group must be a lower polarity group than the polar group generated by its dissociation. Therefore, when the acid-dissociable group dissociates by an acid, a higher polarity group is generated, thus increasing the overall polarity. As a result, the overall polarity of component (A1) increases. By increasing polarity, the solubility in the developing solution changes accordingly. When the developing solution is alkaline, the solubility increases; when the developing solution is organic, the solubility decreases.

[0018] "Substrate component" is an organic compound with film-forming ability. Organic compounds used as substrate components are broadly classified into non-polymers and polymers. Non-polymers typically use compounds with a molecular weight of 500 or more but less than 4000. When referred to as "low molecular weight compound," it indicates a non-polymer with a molecular weight of 500 or more but less than 4000. Polymers typically use compounds with a molecular weight of 1000 or more. When referred to as "resin," "high molecular weight compound," or "polymer," it indicates a polymer with a molecular weight of 1000 or more. The molecular weight of the polymer is the weight-average molecular weight converted from polystyrene using GPC (gel permeation chromatography).

[0019] "Derived constituent unit" refers to a constituent unit formed by the breaking of multiple bonds between carbon atoms, such as vinyl double bonds. "Acrylate" refers to an acrylate in which the hydrogen atom of the carbon atom bonded at the α-position can be replaced by a substituent. The substituent (Rαx) replacing the hydrogen atom of the carbon atom bonded at the α-position is an atom or group other than hydrogen. It also includes isoconic acid diesters in which the substituent (Rαx) is replaced by a substituent containing an ester bond, or α-hydroxy acrylates in which the substituent (Rαx) is replaced by a hydroxyalkyl group or a group that modifies its hydroxyl group. Furthermore, unless otherwise specified, the carbon atom at the α-position of an acrylate is the carbon atom bonded to the carbonyl group of acrylic acid. Hereinafter, acrylates in which the hydrogen atom of the carbon atom bonded at the α-position is replaced by a substituent are sometimes referred to as α-substituted acrylates.

[0020] "Derivative" refers to a compound in which the hydrogen atom at the α-position is replaced by other substituents such as alkyl groups or halogenated alkyl groups, and such derivatives. Examples of such derivatives include compounds in which the hydrogen atom at the α-position of the target compound is replaced by an organogroup; and compounds in which the hydrogen atom at the α-position of the target compound is replaced by a substituent other than a hydroxyl group. Furthermore, unless otherwise specified, the α-position refers to the first carbon atom adjacent to the functional group. Examples of substituents for the hydrogen atom at the α-position of substituted hydroxystyrene include those similar to Rαx.

[0021] In this specification and the scope of this application, depending on the structure represented by the chemical formula, if an asymmetric carbon is present, either an enantiomer or a diastereomer may be present. In such cases, each isomer is represented by a single chemical formula. These isomers may be used alone or as mixtures.

[0022] (Photoresist composition) The photoresist composition of this embodiment generates acid through exposure, and its solubility in the developing solution changes due to the action of the acid. The photoresist composition contains: a substrate component (A) whose solubility in the developing solution changes due to the action of the acid (hereinafter also referred to as "(A) component"), and one or more compounds (D1) selected from the group consisting of compounds represented by general formula (d1-1) and compounds represented by general formula (d1-2) (hereinafter also referred to as "compound (D1)").

[0023] When a photoresist film is formed using the photoresist composition of this embodiment and the photoresist film is selectively exposed, acid is generated in the exposed portion of the photoresist film. Due to the action of the acid, the solubility in the developing solution of component (A) changes. On the other hand, in the unexposed portion of the photoresist film, since the solubility in the developing solution of component (A) does not change, the difference in solubility in the developing solution occurs between the exposed and unexposed portions of the photoresist film.

[0024] The photoresist composition of this embodiment can be either a positive photoresist composition or a negative photoresist composition. Furthermore, the photoresist composition of this embodiment can be used in an alkaline developing process where an alkaline developing solution is used in the developing process during photoresist pattern formation, or in a solvent developing process where an organic developing solution is used in the developing process. That is, the photoresist composition of this embodiment is a "positive photoresist composition for alkaline developing process" for forming a positive photoresist pattern in an alkaline developing process, or a "negative photoresist composition for solvent developing process" for forming a negative photoresist pattern in a solvent developing process.

[0025] <(A) Component> In the photoresist composition of this embodiment, the (A) component contains a resin component (A1) whose solubility in the developer changes due to the action of acid (hereinafter also referred to as "(A1) component"). The aforementioned resin component (A1) comprises a polymeric compound (A01) having a constituent unit (a01) shown in the following general formula (a0-1), a constituent unit (a02) shown in the following general formula (a0-2), and a constituent unit (a03) shown in the following general formula (a0-3). As the (A) component, at least the (A1) component is used, and at least one of other polymeric compounds and low molecular weight compounds may also be used together with the (A1) component.

[0026] In the photoresist composition of this embodiment, component (A) may be used alone or in combination with two or more components.

[0027] ・Regarding component (A1), component (A1) has constituent unit (a01), constituent unit (a02) and constituent unit (a03).

[0028] ≪Construment (a01)≫ The constituent unit (a01) is a constituent unit derived from the compound represented by the following general formula (a0-1).

[0029] [In formula (a0-1), R01 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms; Va01 is a divalent linkage; na01 is an integer from 0 to 2; Ra01 is a lactone-containing cyclic group having one or more substituents selected from the group consisting of halogen atoms, carboxyl groups, acetyls, nitro groups, and cyano groups; the aforementioned lactone-containing cyclic group may also have substituents other than those in the aforementioned group].

[0030] In the above general formula (a0-1), R01 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. Preferably, the alkyl group having 1 to 5 carbon atoms in R01 is a straight-chain or branched alkyl group having 1 to 5 carbon atoms; specifically, examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tributyl, pentyl, isopentyl, neopentyl, etc. Preferably, the halogenated alkyl group having 1 to 5 carbon atoms in R01 is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are replaced by halogen atoms. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., and particularly fluorine atoms. Preferably, R01 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms; from the perspective of industrial availability, it is more preferably a hydrogen atom or a methyl group, especially methyl.

[0031] In the above general formula (a0-1), Va01 is a divalent hydrocarbon group that may have an ether bond. The divalent hydrocarbon group in Va01 may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0032] The aliphatic hydrocarbon group of the divalent hydrocarbon group in VaO1 can be saturated or unsaturated, but saturation is generally preferred. More specifically, examples of such aliphatic hydrocarbon groups include straight-chain or branched aliphatic hydrocarbon groups or aliphatic hydrocarbon groups containing rings in their structure.

[0033] The number of carbon atoms in the straight-chain aliphatic hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, particularly preferably 1 to 4, and most preferably 1 to 3. Specifically, examples of the straight-chain aliphatic hydrocarbon group include methylene [-CH2-], ethyl [-(CH2)2-], trimethylene [-(CH2)3-], tetramethylene [-(CH2)4-], and pentamethylene [-(CH2)5-]. The number of carbon atoms in the branched aliphatic hydrocarbon group is preferably 2 to 10, more preferably 3 to 6, particularly preferably 3 or 4, and most preferably 3. Specifically, examples of branched aliphatic hydrocarbon groups include alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkyl ethyl groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyl trimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkyl tetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. Preferably, the alkyl group in the alkyl alkyl group is a straight-chain alkyl group having 1 to 5 carbon atoms.

[0034] Examples of aliphatic hydrocarbon groups containing a ring in this structure include alicyclic hydrocarbon groups (groups with two hydrogen atoms removed from an aliphatic hydrocarbon ring), alicyclic hydrocarbon groups bonded to the end of a straight-chain or branched aliphatic hydrocarbon group, and alicyclic hydrocarbon groups intermediate in the middle of a straight-chain or branched aliphatic hydrocarbon group. Examples of straight-chain or branched aliphatic hydrocarbon groups include those identical to the straight-chain or branched aliphatic hydrocarbon groups. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12. The alicyclic hydrocarbon group can be polycyclic or monocyclic. For monocyclic alicyclic hydrocarbon groups, it is preferable to have two hydrogen atoms removed from a monocyclic alkane. The monocyclic alkane preferably has 3 to 6 carbon atoms; specifically, cyclopentane and cyclohexane are examples. The polycyclic alicyclic hydrocarbon group is preferably a group that has two hydrogen atoms removed from a polycyclic alkane. The polycyclic alkane is preferably one with 7 to 12 carbon atoms. Examples of such polycyclic alkane include adamantane, norcamphene, isocamphene, tricyclodecane, and tetracyclododecane.

[0035] The aromatic hydrocarbon group, which is a divalent hydrocarbon group in VaO1, is a hydrocarbon group having an aromatic ring. The number of carbon atoms in this aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, this number of carbon atoms does not include the number of carbon atoms in the substituents. Specifically, examples of the aromatic ring in this aromatic hydrocarbon group include aromatic hydrocarbon rings of benzene, biphenyl, fentanyl, naphthalene, onion, phenanthrene, etc.; and aromatic heterocycles in which a portion of the carbon atoms constituting the aromatic hydrocarbon ring are replaced by heteroatoms. Examples of heteroatoms in the aromatic heterocycle include oxygen atoms, sulfur atoms, nitrogen atoms, etc. Specifically, examples of this aromatic hydrocarbon group include a group (aryl) from which two hydrogen atoms have been removed from the aromatic hydrocarbon ring; and a group (aryl) from which one hydrogen atom has been removed from the aromatic hydrocarbon ring, wherein one hydrogen atom is replaced by an alkyl group (e.g., a group from which one hydrogen atom is further removed from an aryl group of benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.). The alkyl group (the alkyl chain in the aryl alkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2, and particularly preferably 1.

[0036] In the above general formula (a0-1), na01 is an integer from 0 to 2, preferably 0 or 1, and more preferably 0.

[0037] In the above general formula (a0-1), Ra01 is a lactone-containing cyclic group having one or more substituents selected from the group consisting of halogen atoms, carboxyl groups, acetoyl groups, nitro groups and cyano groups (hereinafter also referred to as "lactone-containing cyclic group having cyano groups, etc".

[0038] "A cyclic group containing a lactone" refers to a cyclic group whose ring skeleton contains a ring including -OC (=O)- (lactone ring). The lactone ring is considered as the first ring; when only the lactone ring is present, it is called a monocyclic group; when it has other ring structures, it is called a polycyclic group regardless of its structure. A cyclic group containing a lactone can be either a monocyclic group or a polycyclic group.

[0039] As a preferred example of a cyclic group containing lactone such as a cyano group in Ra01, the group shown in the following general formula (Ra0-1) can be cited.

[0040] [In the formula, Ra012 and Ra013 are each independently a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, an alkoxy group, or an alkylthio group, or Ra012 and Ra013 can be bonded to each other to form an alkyl group with 1 to 6 carbon atoms containing oxygen or sulfur atoms, an ether bond, or a thioether bond. X011 is a halogen atom, a carboxyl group, an acetyl group, a nitro group, or a cyano group. Ra011 is an alkyl group with 1 to 6 carbon atoms containing halogen atoms, a hydroxyl portion that can be protected by a protecting group and may contain a hydroxyalkyl group with 1 to 6 carbon atoms containing halogen atoms, a carboxyl group that can form a salt, or a substituted oxycarbonyl group. p01 is an integer from 0 to 8, and q01 represents an integer from 1 to 9. However, p01 + q01 ≦ 9. When there are more than two X011s, the complex X011s can be the same or different from each other. When there are more than two Ra011s, the complex Ra011s can be the same or different from each other.] When Ra012 and Ra013 are bonded together to form an alkyl group with 1 to 6 carbon atoms that may contain oxygen or sulfur atoms, X011 and Ra011 can each independently exist as substituents replacing the hydrogen atoms of the aforementioned alkyl group with 1 to 6 carbon atoms. * indicates a bond to an oxygen atom in the aforementioned formula (a0-1).

[0041] In the above general formula (Ra0-1), Ra012 and Ra013 are each independently hydrogen atoms, alkyl, alkoxy or alkylthio groups with 1 to 5 carbon atoms, or Ra012 and Ra013 can be bonded to each other to form alkyl groups with 1 to 6 carbon atoms, ether bonds or thioether bonds that may contain oxygen atoms or sulfur atoms.

[0042] The alkyl group having 1 to 5 carbon atoms is preferably a straight-chain or branched alkyl group, specifically, examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tributyl, pentyl, isopentyl, neopentyl, etc. The alkoxy group having 1 to 5 carbon atoms is preferably a straight-chain or branched alkoxy group, specifically, examples include groups in which the alkyl group listed in Ra012 and Ra013 is bonded to an oxygen atom (-O-). The alkylthio group having 1 to 5 carbon atoms is preferably one having 1 to 4 carbon atoms, specifically, examples include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, tributylthio, etc.

[0043] The alkyl group having 1 to 6 carbon atoms formed by the mutual bonding of Ra012 and Ra013 is preferably a straight-chain or branched alkyl group, and examples include methylene, ethyl alkyl, trimethylene, and propyl alkyl. Specific examples of the alkyl group containing oxygen or sulfur atoms include groups with -O- or -S- atoms at the end of the alkyl group or between carbon atoms, such as -O-CH2-, -CH2-O-CH2-, -S-CH2-, and -CH2-S-CH2-. The group formed by the mutual bonding of Ra012 and Ra013 is preferably an alkyl group having 1 to 6 carbon atoms or -O-, more preferably an alkyl group having 1 to 6 carbon atoms, particularly preferably an alkyl group having 1 to 3 carbon atoms, and especially preferably methylene.

[0044] Preferably, Ra012 and Ra013 are mutually bonded to form an alkyl group having 1 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms is more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methylene group.

[0045] In the above general formula (Ra0-1), Ra011 represents an alkyl group that may have 1 to 6 carbon atoms with halogen atoms, a hydroxyl group that may be protected by a protecting group and may have 1 to 6 carbon atoms with halogen atoms, a carboxyl group that may form a salt, or a substituted oxygen carbonyl group.

[0046] Examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, dibutyl, tributyl, pentyl, and hexyl. Among these, alkyl groups having 1 to 5 carbon atoms are preferred, more preferably alkyl groups having 1 to 4 carbon atoms, especially preferably alkyl groups having 1 to 3 carbon atoms, particularly preferably methyl or ethyl, and most preferably methyl. The alkyl group having 1 to 6 carbon atoms may or may not have a halogen atom. The halogen atom is preferably a fluorine atom or a chlorine atom, and more preferably a fluorine atom. Examples of alkyl groups having 1 to 6 carbon atoms and containing a halogen atom include chloroalkyl groups such as chloromethyl; and fluoroalkyl groups such as trifluoromethyl, 2,2,2-trifluoroethyl, and pentafluoroethyl (preferably fluoroalkyl groups having 1 to 3 carbon atoms).

[0047] Examples of hydroxyalkyl groups having 1 to 6 carbon atoms include hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, and 6-hydroxyhexyl. These hydroxyalkyl groups having 1 to 6 carbon atoms may or may not have a halogen atom. The halogen atom is preferably a fluorine atom. Examples of hydroxyalkyl groups having 1 to 6 carbon atoms and containing a halogen atom include difluorohydroxymethyl, 1,1-difluoro-2-hydroxyethyl, 2,2-difluoro-2-hydroxyethyl, and 1,1,2,2-tetrafluoro-2-hydroxyethyl. These hydroxyalkyl groups having 1 to 6 carbon atoms preferably have 1 to 3 carbon atoms, more preferably 1 or 2 carbon atoms, and especially preferably 1 carbon atom. The hydroxyalkyl group having 1 to 6 carbon atoms may or may not have its hydroxyl portion protected by a protecting group. Examples of protecting groups that protect the hydroxyl moiety include methyl, methoxymethyl, and other groups that can form ether or acetal bonds with the oxygen atom constituting the hydroxyl group; and acetyl, benzoyl, and other groups that can form ester bonds with the oxygen atom constituting the hydroxyl group.

[0048] The salt-forming carboxyl group is selected from the group consisting of carboxyl groups and salt-forming carboxyl groups (salts of carboxyl groups). Examples of salt-forming carboxyl groups (salts of carboxyl groups) include alkali metal salts of carboxyl groups, alkaline earth metal salts of carboxyl groups, and transition metal salts of carboxyl groups.

[0049] As the substituted oxygen carbonyl group, examples include alkoxy carbonyl groups with 1 to 4 carbon atoms bonded to carbonyl groups (specifically, alkoxy carbonyl groups such as methoxy carbonyl, ethoxy carbonyl, isopropyloxy carbonyl, n-propoxy carbonyl; olefinic carbonyl groups such as ethyleneoxy carbonyl, allyloxy carbonyl); cycloalkoxy carbonyl groups such as cyclohexyloxy carbonyl; aryloxy carbonyl groups such as phenoxy carbonyl; etc.

[0050] In the above general formula (Ra0-1), X011 represents a halogen atom, a carboxyl group, a cellulose group, a nitro group, or a cyano group. The halogen atom is preferably a fluorine atom. The cellulose group is preferably a cellulose group with 1 to 3 carbon atoms; specific examples include methylcellulose, acetylcellulose, and propionic acid.

[0051] In the above general formula (Ra0-1), X011 is one of the above, preferably cyano.

[0052] In the above general formula (Ra0-1), p01 is an integer from 0 to 8. p01 is preferably an integer from 0 to 6, more preferably an integer from 0 to 3, even more preferably 0 or 1, and especially preferably 0. In the above general formula (Ra0-1), q01 is an integer from 1 to 9. However, p01 + q01 ≦ 9. q01 is preferably an integer from 1 to 5, more preferably 1 or 2, and even more preferably 1. When p01 is an integer from 2 to 8, and there are more than two Ra011s, the complex Ra011s can be the same or different from each other. When q01 is an integer from 2 to 9, and there are more than two X011s, the complex X011s can be the same or different from each other.

[0053] When Ra012 and Ra013 are bonded together to form an alkyl group with 1 to 6 carbon atoms that may contain oxygen or sulfur atoms, X011 and Ra011 can each exist independently as substituents that replace the hydrogen atoms of the aforementioned alkyl group with 1 to 6 carbon atoms.

[0054] As a cyclic group containing lactone such as a cyano group in Ra01, as a specific example of a group other than the group shown in the above general formula (Ra0-1), examples can be given in the group shown in the general formulas (a2-r-1) to (a2-r-7) described below, in which at least one of the two Ra'21s is substituted with a halogen atom, a carboxyl group, a cellulose group, a nitro group or a cyano group; as a substituent in the group shown in the general formulas (a2-r-1) to (a2-r-7) described below, examples can be given in the group having one or more substituents selected from the group consisting of a halogen atom, a carboxyl group, a cellulose group, a nitro group and a cyano group.

[0055] The constituent unit (a01) is preferably the constituent unit shown in the following general formula (a01-1).

[0056] [In formula (a01-1), R01 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms; Va01 is a divalent linker; na01 is an integer from 0 to 2; Ra1 and Ra2 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group, or an alkylthio group, or Ra1 and Ra2 can be bonded to each other to form an alkyl group having 1 to 6 carbon atoms containing oxygen atoms or sulfur atoms, an ether bond, or a thioether bond; Ra'01 is a halogen atom, an alkyl group having 1 to 6 carbon atoms containing halogen atoms, a hydroxyl group that can be protected by a protecting group and has 1 to 6 carbon atoms containing halogen atoms, a carboxyl group that can form a salt, or a substituted oxygen carbonyl group; p0 is an integer from 0 to 8; when two or more Ra'01 are present, the complex Ra'01 can be the same or different from each other; q0 is an integer from 1 to 9].

[0057] R01, Va01, and na01 in the above general formula (a01-1) are each the same as R01, Va01, and na01 in the above general formula (a0-1). Ra1 and Ra2 in the above general formula (a01-1) can be the same as Ra012 and Ra013 in the above general formula (Ra0-1). The alkyl group having 1 to 6 carbon atoms, the hydroxyl group having 1 to 6 carbon atoms, the hydroxyalkyl group having 1 to 6 carbon atoms, the carboxyl group that can form a salt, or the substituted oxycarbonyl group in Ra'01 of the above general formula (a01-1) can be the same as Ra011 in the above general formula (Ra0-1).

[0058] In the above general formula (a01-1), p0 is an integer from 0 to 8, preferably an integer from 0 to 3, more preferably 0 or 1, and even more preferably 0.

[0059] In the above general formula (a01-1), q0 is an integer from 1 to 9, preferably an integer from 1 to 3, more preferably 1 or 2, and even more preferably 1.

[0060] The constituent unit (a01) is preferably the constituent unit shown in the following general formula (a01-1-1).

[0061] [In formula (a01-1-1), R01 is a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a haloalkyl group with 1 to 5 carbon atoms; Va01 is a divalent linkage group; na01 is an integer from 0 to 2; q00 is an integer from 1 to 3].

[0062] R01, Va01 and na01 in the above general formula (a01-1-1) are the same as R01, Va01 and na01 in the above general formula (a0-1).

[0063] In the above general formula (a01-1-1), q00 is an integer from 1 to 3, preferably 1 or 2, and more preferably 1.

[0064] The following shows suitable specific examples of the constituent unit (a01). In the following formulas, Rα is a hydrogen atom, a methyl group, or a trifluoromethyl group. nα is an integer from 0 to 2, preferably 0 or 1. Ac represents an acetyl group. X represents a halogen atom, a carboxyl group, an acetyl group, a nitro group, or a cyano group, preferably a cyano group.

[0065]

[0066]

[0067]

[0068] The constituent unit (a01) is among those described above, preferably a constituent unit shown in any of the above formulas (a01-1a-1) to (a01-1a-18), and more preferably a constituent unit shown in the above formula (a01-1a-1).

[0069] The constituent unit (a01) of component (A1) may be one type or two or more types. The proportion of the constituent unit (a01) in component (A1) relative to the total (100 mol%) of all constituent units constituting component (A1) is preferably 20 mol% to 70 mol%, more preferably 30 mol% to 60 mol%, even more preferably 40 mol% to 60 mol%, and particularly preferably 45 mol% to 55 mol%. By setting the proportion of constituent unit (a01) to the lower limit of the above-mentioned preferred range, the roughness reduction performance can be further improved by appropriately adjusting the solubility during development. Furthermore, if the proportion of constituent unit (a01) is below the upper limit of the above-mentioned preferred range, a balance with other constituent units can be achieved.

[0070] ≪Construment (a02)≫ The constituent unit (a02) is a constituent unit derived from the compound represented by the following general formula (a0-2).

[0071] [In formula (a0-2), R02 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms; Va02 is a divalent linkage group; na02 is an integer from 0 to 2; Ra021 and Ra022 are each independently a chain alkyl group; Yaa0 is a carbon atom; Xaa0 is a group that forms a monocyclic alicyclic hydrocarbon group together with Yaa0; some or all of the hydrogen atoms in this monocyclic alicyclic hydrocarbon group may be substituted].

[0072] In the above general formula (a0-2), RO2 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms, and examples can be made that are the same as RO1 in the above general formula (a0-1). In the above general formula (a0-2), VaO2 is a divalent linker, and examples can be made that are the same as VaO1 in the above general formula (a0-1).

[0073] In the above general formula (a0-2), na02 is an integer from 0 to 2, preferably 0 or 1, and more preferably 0.

[0074] In the above general formula (a0-2), Ra021 and Ra022 are each independently a chain alkyl group. The chain alkyl group is preferably a straight-chain or branched alkyl group having 1 to 5 carbon atoms. Specifically, suitable examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tributyl, pentyl, isopentyl, and neopentyl.

[0075] In the above general formula (a0-2), the total number of carbon atoms of the chain alkyl groups in Ra021 and Ra022 is preferably 2 to 8, more preferably 2 to 6, and even more preferably 2 to 4. In the above general formula (a0-2), Ra021 and Ra022 are specifically preferably methyl or ethyl.

[0076] In the above general formula (a0-2), Xaa0 is a monocyclic alicyclic hydrocarbon group that forms a single ring together with Yaa0. Preferably, this monocyclic alicyclic hydrocarbon group is a group formed by removing one or more hydrogen atoms from a monocyclic alkane. Preferably, this monocyclic alkane has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, particularly preferably 5 or 6 carbon atoms, and especially preferably 6 carbon atoms. Specifically, this monocyclic alkane is preferably cyclopentane or cyclohexane, and more preferably cyclohexane.

[0077] The monocyclic alicyclic hydrocarbon system formed by XaaO and YaaO together may have substituents. Examples of such substituents include methyl, ethyl, propyl, hydroxyl, hydroxyalkyl, carboxyl, halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), alkoxy (methoxy, ethoxy, propoxy, butoxy, etc.), acetyl, alkoxycarbonyl, alkylcarbonyloxy, etc.

[0078] The following shows suitable specific examples of the constituent unit (a02). In the following formulas, Rα is a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0079]

[0080] The constituent unit (a02) is among those described above, and is preferably a constituent unit shown in any of the above formulas (a02-1a-1) to (a02-1a-3).

[0081] The (A1) component may have one or more constituent units (a02). The proportion of the constituent unit (a02) in the (A1) component, relative to the total (100 mol%) of all constituent units constituting the (A1) component, is preferably 10 mol% to 60 mol%, more preferably 20 mol% to 60 mol%, even more preferably 20 mol% to 50 mol%, and particularly preferably 35 mol% to 45 mol%. By setting the proportion of the constituent unit (a02) to the lower limit of the above-mentioned preferred range, the dissolution of the unexposed portion of the photoresist film caused by imaging can be further suppressed. Furthermore, the lithography properties, such as roughness reduction, are improved. Also, if the proportion of the constituent unit (a02) is below the upper limit of the above-mentioned preferred range, a balance with other constituent units can be achieved.

[0082] ≪Construment (a03)≫ The constituent unit (a03) is a constituent unit derived from the compound represented by the following general formula (a0-3).

[0083] [In formula (a0-3), R03 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms; Va03 is a divalent linkage group; na03 is an integer from 0 to 2; Ra031 is a chain alkyl group; Yab0 is a carbon atom; Xab0 is a group that forms a monocyclic alicyclic hydrocarbon group together with Yab0; some or all of the hydrogen atoms in this monocyclic alicyclic hydrocarbon group may be replaced].

[0084] In the above general formula (a0-3), R03 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms, and examples can be made that are the same as R01 in the above general formula (a0-1). In the above general formula (a0-3), VaO3 is a divalent linker, and examples can be made that are the same as VaO1 in the above general formula (a0-1).

[0085] In the above general formula (a0-3), na03 is an integer from 0 to 2, preferably 0 or 1, and more preferably 0.

[0086] In the above general formula (a0-3), Ra031 is a chain alkyl group. The chain alkyl group is preferably a straight-chain or branched alkyl group having 1 to 5 carbon atoms. Specifically, suitable examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tributyl, pentyl, isopentyl, and neopentyl.

[0087] In the above general formula (a0-3), Ra031 is one of the above, and from the viewpoint of reducing roughness and improving the collapse limit, it is preferably methyl or ethyl, and from the viewpoint of high sensitivity, it is preferably isopropyl.

[0088] In the above general formula (a0-3), Xab0 is a group that forms a monocyclic alicyclic hydrocarbon group together with Yabo. Preferably, this monocyclic alicyclic hydrocarbon group is a group formed by removing two or more hydrogen atoms from a monocyclic alkane. Preferably, this monocyclic alkane has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, particularly preferably 5 or 6 carbon atoms, and especially preferably 5 carbon atoms. Specifically, this monocyclic alkane is preferably cyclopentane or cyclohexane, and more preferably cyclopentane.

[0089] The monocyclic alicyclic hydrocarbon system formed by XabO and YabO together may have substituents. Examples of such substituents include methyl, ethyl, propyl, hydroxyl, hydroxyalkyl, carboxyl, halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), alkoxy (methoxy, ethoxy, propoxy, butoxy, etc.), acetyl, alkoxycarbonyl, alkylcarbonyloxy, etc.

[0090] The following shows suitable specific examples of the constituent unit (a03). In the following formulas, Rα is a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0091]

[0092]

[0093] The constituent unit (a03) is among those described above, preferably a constituent unit shown in any of the above formulas (a03-1a-1) to (a03-1a-7), and more preferably a constituent unit shown in any of the above formulas (a03-1a-1) to (a03-1a-3).

[0094] The (A1) component may have one or more constituent units (a03). The proportion of the constituent unit (a03) in the (A1) component, relative to the total number of all constituent units constituting the (A1) component (100 mol%), is preferably 1 mol% to 50 mol%, more preferably 5 mol% to 30 mol%, even more preferably 5 mol% to 20 mol%, and particularly preferably 5 mol% to 15 mol%. By setting the proportion of the constituent unit (a03) to the lower limit of the above-mentioned preferred range, the deprotection reactivity can be improved. Furthermore, if the proportion of the constituent unit (a03) is below the upper limit of the above-mentioned preferred range, a balance with other constituent units can be achieved.

[0095] <Other constituent units> (A1) In addition to the constituent units (a01), (a02) and (a03) mentioned above, the component may have other constituent units as needed. Other constituent units include, for example, a constituent unit (a1) containing an acid-decomposable group whose polarity increases due to the action of an acid (excluding those equivalent to constituent units (a01), (a02), or (a03)); a constituent unit (a2) containing a cyclic group containing a lactone, a cyclic group containing -SO2-, or a cyclic group containing a carbonate (excluding those equivalent to constituent unit (a01), the aforementioned constituent unit (a02), constituent unit (a03), or constituent unit (a1)); a constituent unit (a3) ​​containing an aliphatic hydrocarbon group containing a polar group (excluding those equivalent to constituent units (a01), (a02), (a03), (a1), or the aforementioned constituent unit (a2)); a constituent unit (a4) containing an aliphatic cyclic group that is non-dissociable with an acid; a constituent unit derived from styrene or styrene derivatives; and a constituent unit derived from hydroxystyrene or hydroxystyrene derivatives.

[0096] ≪Construment (a1)≫ Construment (a1) is a constitutive unit containing an acid-decomposing group whose polarity increases through the action of an acid. However, those equivalent to constitutive unit (a01), constitutive unit (a02), or constitutive unit (a03) are excluded.

[0097] As an acid-dissociating group, examples of proposers of acid-dissociating groups for base resins used in chemically amplified photoresist compositions to date can be cited. Specifically, examples of proposers of acid-dissociating groups for base resins used in chemically amplified photoresist compositions include "acetal-type acid-dissociating groups", "tertiary alkyl ester-type acid-dissociating groups", and "tertiary alkoxycarbonyl acid-dissociating groups" as described below.

[0098] Acetal type acid dissociation group: As an acid dissociation group that protects the carboxyl or hydroxyl group in the aforementioned polar group, for example, the acid dissociation group shown in the following general formula (a1-r-1) (hereinafter also referred to as "acetal type acid dissociation group").

[0099] [In the formula, Ra'1 and Ra'2 are hydrogen atoms or alkyl groups, Ra'3 is a hydrocarbon group, and Ra'3 can bond with either Ra'1 or Ra'2 to form a ring].

[0100] In formula (a1-r-1), at least one of Ra'1 and Ra'2 is preferably a hydrogen atom, and more preferably both are hydrogen atoms. When Ra'1 or Ra'2 is an alkyl group, the alkyl group can be the same as those listed in the description of α-substituted acrylates above as substituents that can be bonded to the carbon atom at the α-position, preferably an alkyl group having 1 to 5 carbon atoms. Specifically, linear or branched alkyl groups are preferred. More specifically, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tributyl, pentyl, isopentyl, neopentyl, etc. are preferred, especially methyl or ethyl, and particularly preferably methyl.

[0101] In formula (a1-r-1), the hydrocarbon group of Ra'3 can be a straight-chain or branched alkyl or cyclic hydrocarbon group. The straight-chain alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and particularly preferably 1 or 2 carbon atoms. Specifically, methyl, ethyl, n-propyl, n-butyl, n-pentyl, etc., can be included. Among these, methyl, ethyl, or n-butyl is preferred, and methyl or ethyl is even more preferred.

[0102] The branched alkyl group preferably has 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms, and specifically, isopropyl, isobutyl, tributyl, isopentyl, neopentyl, 1,1-diethylpropyl, 2,2-dimethylbutyl, etc., preferably isopropyl.

[0103] When Ra'3 becomes a cyclic hydrocarbon group, the hydrocarbon group can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and it can also be a polycyclic group or a monocyclic group. As a monocyclic aliphatic hydrocarbon group, it is preferred to be a group that has removed one hydrogen atom from a monocyclic alkane. As a monocyclic alkane, it is preferred to have 3 to 6 carbon atoms, specifically, cyclopentane, cyclohexane, etc. As a polycyclic aliphatic hydrocarbon group, it is preferred to be a group that has removed one hydrogen atom from a polycyclic alkane, and the polycyclic alkane is preferably a group that has 7 to 12 carbon atoms, specifically, adamantane, norcamphene, isocamphene, tricyclodecane, tetracyclododecane, etc.

[0104] When the cyclic hydrocarbon group of Ra'3 is an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. There is no particular limitation as long as the aromatic ring is a cyclic conjugated system having 4n+2 π electrons; it can be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, particularly preferably 6 to 15, and especially preferably 6 to 12. Specifically, examples of aromatic rings include aromatic hydrocarbon rings of benzene, naphthalene, onion, phenanthrene, etc.; and aromatic heterocycles in which a portion of the carbon atoms constituting the aforementioned aromatic hydrocarbon rings are replaced by heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, nitrogen atoms, etc. Specifically, examples of aromatic heterocycles include pyridine rings, thiophene rings, etc. Specifically, the aromatic hydrocarbon group in Ra'3 can be exemplified by a group (aryl or heteroaryl) that has one hydrogen atom removed from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle; a group that has one hydrogen atom removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, benzoylene, etc.); or a group in which one hydrogen atom of the aforementioned aromatic hydrocarbon ring or aromatic heterocycle is replaced by an alkyl group (e.g., arylalkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.). The alkyl group bonded to the aforementioned aromatic hydrocarbon ring or aromatic heterocycle preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

[0105] The cyclic hydrocarbon group in Ra'3 may have substituents. Examples of such substituents include -RP1, -RP2-O-RP1, -RP2-CO-RP1, -RP2-CO-ORP1, -RP2-O-CO-RP1, -RP2-OH, -RP2-CN, or -RP2-COOH (hereinafter, these substituents are collectively referred to as "Rax5"). Here, RP1 is a monovalent chain saturated hydrocarbon group with 1 to 10 carbon atoms, a monovalent aliphatic cyclic saturated hydrocarbon group with 3 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group with 6 to 30 carbon atoms. RP2 is a single bond, a divalent chain saturated hydrocarbon group with 1 to 10 carbon atoms, a divalent aliphatic cyclic saturated hydrocarbon group with 3 to 20 carbon atoms, or a divalent aromatic hydrocarbon group with 6 to 30 carbon atoms. However, some or all of the hydrogen atoms in the chain saturated hydrocarbon group, aliphatic cyclic saturated hydrocarbon group, and aromatic hydrocarbon group of RP1 and RP2 can be replaced by fluorine atoms. The aforementioned aliphatic cyclic hydrocarbon group may have one or more of the above-mentioned substituents, or it may have one or more of the above-mentioned substituents. Examples of monovalent chain saturated hydrocarbon groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl. Examples of monocyclic aliphatic cyclic saturated hydrocarbon groups with 3 to 20 carbon atoms include monocyclic aliphatic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and cyclododecyl; and polycyclic aliphatic saturated hydrocarbon groups such as bicyclic [2.2.2]octyl, tricyclic [5.2.1.02,6]decyl, tricyclic [3.3.1.13,7]decyl, tetracyclic [6.2.1.13,6.02,7]dodecyl, and adamantyl. Examples of monovalent aromatic hydrocarbon groups with 6 to 30 carbon atoms include groups formed by removing one hydrogen atom from the aromatic hydrocarbon rings of benzene, biphenyl, fentanyl, naphthalene, anthracene, and phenanthrene.

[0106] When Ra'3 forms a ring by bonding with any one of Ra'1 or Ra'2, the cyclic group is preferably a 4-7 member ring, and more preferably a 4-6 member ring. Specific examples of the cyclic group include tetrahydropyranyl and tetrahydrofuranyl.

[0107] Tertiary alkyl ester type acid-dissociative group: As an acid-dissociative group that protects the carboxyl group in the above-mentioned polar group, examples of acid-dissociative groups represented by the following general formula (a1-r-2) can be cited. Furthermore, among the acid-dissociative groups represented by the following formula (a1-r-2), those composed of alkyl groups are sometimes referred to hereinafter for convenience as "tertiary alkyl ester type acid-dissociative groups".

[0108] [In the formula, Ra'4~Ra'6 are each a hydrocarbon group, and Ra'5 and Ra'6 can bond together to form a ring].

[0109] Examples of the hydrocarbon group in Ra'4 include straight-chain or branched alkyl groups, chain or cyclic alkenyl groups, or cyclic hydrocarbon groups. Examples of the straight-chain or branched alkyl groups or cyclic hydrocarbon groups (monocyclic aliphatic hydrocarbon groups, polycyclic aliphatic hydrocarbon groups, aromatic hydrocarbon groups) in Ra'4 are the same as those in Ra'3 described above. The chain or cyclic alkenyl groups in Ra'4 are preferably alkenyl groups having 2 to 10 carbon atoms. Examples of the hydrocarbon groups in Ra'5 and Ra'6 are the same as those in Ra'3 described above.

[0110] When Ra'5 and Ra'6 are bonded to each other to form a ring, the groups represented by the following general formula (a1-r2-1), the following general formula (a1-r2-2), and the following general formula (a1-r2-3) can be suitably cited. On the other hand, when Ra'4 to Ra'6 are not bonded to each other and are independent hydrocarbon groups, the group represented by the following general formula (a1-r2-4) can be suitably cited.

[0111] [In formula (a1-r2-1), Ra'10 represents a straight-chain or branched alkyl group with 1 to 12 carbon atoms that can be partially replaced by a halogen atom or a heteroatom-containing group; Ra'11 represents a group that forms an aliphatic cyclic group together with the carbon atom bonded to Ra'10; in formula (a1-r2-2), Ya is a carbon atom; Xa is a group that forms a cyclic hydrocarbon group together with Ya; some or all of the hydrogen atoms in this cyclic hydrocarbon group can be replaced; Ra101 to Ra103 are each independently a hydrogen atom, a monovalent chain saturated hydrocarbon group with 1 to 10 carbon atoms, or...] A monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms; one or all of the hydrogen atoms in this chain-like saturated hydrocarbon group and the aliphatic cyclic saturated hydrocarbon group may be substituted; two or more of Ra101 to Ra103 may be bonded together to form a cyclic structure; in formula (a1-r2-3), Yaa is a carbon atom; Xaa is a group that forms an aliphatic cyclic group together with Yaa; Ra104 is an aromatic hydrocarbon group that may have substituents; in formula (a1-r2-4), Ra'12 and Ra'13 each independently represent a monovalent chain-like saturated hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. One or all of the hydrogen atoms in this chain-like saturated hydrocarbon group may be substituted; Ra'14 is a hydrocarbon group that may have substituents; * indicates a bond.

[0112] In the above formula (a1-r2-1), Ra'10 is a straight-chain or branched alkyl group with 1 to 12 carbon atoms that can be replaced by a halogen atom or a heteroatom-containing group.

[0113] The straight-chain alkyl group in Ra'10 has 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, and particularly preferably 1 to 5 carbon atoms. As for the branched alkyl group in Ra'10, examples similar to those in Ra'3 mentioned above can be cited.

[0114] The alkyl group in Ra'10 may be partially replaced by a halogen atom or a heteroatom-containing group. For example, one of the hydrogen atoms constituting the alkyl group may be partially replaced by a halogen atom or a heteroatom-containing group. Also, one of the carbon atoms constituting the alkyl group (such as methylene) may be partially replaced by a heteroatom-containing group. Examples of heteroatoms mentioned 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.

[0115] In formula (a1-r2-1), Ra'11 (an aliphatic cyclic group formed together with the carbon atoms bonded to Ra'10) is preferably an aliphatic hydrocarbon group (alicyclic hydrocarbon group) listed as a monocyclic or polycyclic group of Ra'3 in formula (a1-r-1). Among them, a monocyclic alicyclic hydrocarbon group is preferred, and more specifically, cyclopentyl or cyclohexyl is more preferred, especially cyclopentyl.

[0116] In formula (a1-r2-2), the cyclic hydrocarbon group formed by Xa and Ya together can be a group that further removes one or more hydrogen atoms from the cyclic monovalent hydrocarbon group (aliphatic hydrocarbon group) in Ra'3 of the aforementioned formula (a1-r-1). The cyclic hydrocarbon group formed by Xa and Ya together may have substituents. As such substituents, the same substituents that can be present in the cyclic hydrocarbon group in Ra'3 mentioned above can be cited. In formula (a1-r2-2), the monovalent chain saturated hydrocarbon group with 1 to 10 carbon atoms in Ra101 to Ra103 can be, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, etc. Examples of monocyclic aliphatic cyclic saturated hydrocarbon groups with 3 to 20 carbon atoms in Ra101 to Ra103 include monocyclic aliphatic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and cyclododecyl; and polycyclic aliphatic saturated hydrocarbon groups such as bicyclic [2.2.2]octyl, tricyclic [5.2.1.02,6]decyl, tricyclic [3.3.1.13,7]decyl, tetracyclic [6.2.1.13,6.02,7]dodecyl, and adamantyl. From the viewpoint of ease of synthesis, Ra101 to Ra103 are preferably monovalent chain saturated hydrocarbon groups with 1 to 10 carbon atoms, especially hydrogen atoms, methyl, or ethyl groups, and particularly preferably hydrogen atoms.

[0117] Substituents that are present in the chain-like saturated hydrocarbon groups or aliphatic cyclic saturated hydrocarbon groups shown in Ra101 to Ra103 above can be, for example, groups similar to Rax5 above.

[0118] Examples of groups containing carbon-carbon double bonds that are formed by two or more interlinked bonds of Ra101 to Ra103 include cyclopentenyl, cyclohexenyl, methylcyclopentenyl, methylcyclohexene, cyclopentylene, and cyclohexylenecyclovinyl. Among these, cyclopentenyl, cyclohexene, and cyclopentylene are preferred from the viewpoint of ease of synthesis.

[0119] In formula (a1-r2-3), the aliphatic cyclic group formed by Xaa and Yaa together is preferably an aliphatic hydrocarbon group listed as a monocyclic or polycyclic group of Ra'3 in formula (a1-r-1). In formula (a1-r2-3), the aromatic hydrocarbon group of Ra104 can be a group in which one or more hydrogen atoms have been removed from an aromatic hydrocarbon ring having 5 to 30 carbon atoms. Among them, Ra104 is preferably a group in which one or more hydrogen atoms have been removed from an aromatic hydrocarbon ring having 6 to 15 carbon atoms, more preferably a group in which one or more hydrogen atoms have been removed from benzene, naphthalene, onion or phenanthrene, even more preferably a group in which one or more hydrogen atoms have been removed from benzene, naphthalene or onion, particularly preferably a group in which one or more hydrogen atoms have been removed from benzene or naphthalene, and most preferably a group in which one or more hydrogen atoms have been removed from benzene.

[0120] Substituents that Ra104 in formula (a1-r2-3) may have include, for example, methyl, ethyl, propyl, hydroxyl, carboxyl, halogen atom, alkoxy (methoxy, ethoxy, propoxy, butoxy, etc.), alkoxy carbonyl, etc.

[0121] In formula (a1-r2-4), Ra'12 and Ra'13 each independently represent a monovalent chain saturated hydrocarbon group or a hydrogen atom having 1 to 10 carbon atoms. Examples of monovalent chain saturated hydrocarbon groups having 1 to 10 carbon atoms in Ra'12 and Ra'13 are those identical to those in Ra101 to Ra103 described above. Some or all of the hydrogen atoms in this chain saturated hydrocarbon group may be substituted. Among Ra'12 and Ra'13, hydrogen atoms and alkyl groups having 1 to 5 carbon atoms are preferred, more preferably alkyl groups having 1 to 5 carbon atoms, especially methyl or ethyl, and particularly preferably methyl. When the chain saturated hydrocarbon groups represented by Ra'12 and Ra'13 are substituted, examples of substituents are those identical to those in Rax5 described above.

[0122] In formula (a1-r2-4), Ra'14 is a hydrocarbon group that may have substituents. Examples of hydrocarbon groups in Ra'14 include straight-chain or branched alkyl groups or cyclic hydrocarbon groups.

[0123] The linear alkyl group in Ra'14 preferably has 1 to 5 carbon atoms, more preferably 1 to 4, and even more preferably 1 or 2. Specifically, examples include methyl, ethyl, n-propyl, n-butyl, and n-pentyl. Among these, methyl, ethyl, or n-butyl is preferred, and methyl or ethyl is even more preferred.

[0124] The branched alkyl group in Ra'14 preferably has 3 to 10 carbon atoms, more preferably 3 to 5. Specifically, examples include isopropyl, isobutyl, tributyl, isopentyl, neopentyl, 1,1-diethylpropyl, 2,2-dimethylbutyl, etc., with isopropyl being the most preferred.

[0125] When Ra'14 becomes a cyclic hydrocarbon group, the hydrocarbon group can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and it can also be a polycyclic group or a monocyclic group. As a monocyclic aliphatic hydrocarbon group, it is preferred to be a group that has removed one hydrogen atom from a monocyclic alkane. As a monocyclic alkane, it is preferred to have 3 to 6 carbon atoms, specifically, cyclopentane, cyclohexane, etc. As a polycyclic aliphatic hydrocarbon group, it is preferred to be a group that has removed one hydrogen atom from a polycyclic alkane, and as a polycyclic alkane, it is preferred to have 7 to 12 carbon atoms, specifically, adamantane, norcamphene, isocamphene, tricyclodecane, tetracyclododecane, etc.

[0126] As an aromatic hydrocarbon group in Ra'14, examples can be the same as those in Ra104. Ra'14 is preferably a group having one or more hydrogen atoms removed from an aromatic hydrocarbon ring having 6 to 15 carbon atoms, more preferably a group having one or more hydrogen atoms removed from benzene, naphthalene, anthracene, or phenanthrene, even more preferably a group having one or more hydrogen atoms removed from benzene, naphthalene, or anthracene, particularly preferably a group having one or more hydrogen atoms removed from naphthalene or anthracene, and most preferably a group having one or more hydrogen atoms removed from naphthalene. As for substituents that Ra'14 may have, examples can be the same as those that Ra104 may have.

[0127] When Ra'14 in formula (a1-r2-4) is a naphthyl group, the bond position with the tertiary carbon atom in the aforementioned formula (a1-r2-4) can be either the 1st or 2nd position of the naphthyl group. When Ra'14 in formula (a1-r2-4) is an anthracene group, the bond position with the tertiary carbon atom in the aforementioned formula (a1-r2-4) can be either the 1st, 2nd, or 9th position of the anthracene group.

[0128] The following are specific examples of the basis shown in the aforementioned formula (a1-r2-1).

[0129]

[0130]

[0131]

[0132] The following are specific examples of the basis shown in the aforementioned formula (a1-r2-2).

[0133]

[0134]

[0135]

[0136] The following are specific examples of the basis shown in the aforementioned formula (a1-r2-3).

[0137]

[0138] The following are specific examples of the basis shown in the aforementioned formula (a1-r2-4).

[0139]

[0140] Tri-alkoxycarbonyl acid dissociation group: As an acid dissociation group that protects the hydroxyl group in the aforementioned polar group, for example, the acid dissociation group shown in the following general formula (a1-r-3) can be cited (hereinafter sometimes referred to as "tri-alkoxycarbonyl acid dissociation group" for convenience).

[0141] [In the formula, Ra'7 to Ra'9 are each alkyl groups].

[0142] In formula (a1-r-3), Ra'7 to Ra'9 are preferably alkyl groups having 1 to 5 carbon atoms, more preferably alkyl groups having 1 to 3 carbon atoms. Furthermore, the total number of carbon atoms of each alkyl group is preferably 3 to 7, more preferably 3 to 5, and most preferably 3 to 4.

[0143] Examples of constituent units (a1) include acrylates derived from carbon atoms bonded to the α-position whose hydrogen atoms can be replaced by substituents; acrylamide derived from a constituent unit; a constituent unit derived from hydroxystyrene or hydroxystyrene derivatives in which at least a portion of the hydrogen atoms in the hydroxyl group is protected by a substituent containing the aforementioned acid-degrading group; and a constituent unit derived from vinylbenzoic acid or vinylbenzoic acid derivatives in which at least a portion of the hydrogen atoms in the -C(=O)-OH group is protected by a substituent containing the aforementioned acid-degrading group.

[0144] The following shows specific examples of the constituent unit (a1). In the following formulas, Rα represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152] (A1) The constituent unit (a1) may be one type or two or more types. When the constituent unit (A1) has a constituent unit (a1), the proportion of the constituent unit (a1) in the constituent unit (A1) relative to the total of all constituent units constituting the constituent unit (100 mol%) is preferably 1 to 50 mol%, more preferably 1 to 40 mol%.

[0153] Regarding the constituent unit (a2): The component (A1) may further have a constituent unit (a2) containing a cyclic group containing lactone, a cyclic group containing -SO2-, or a cyclic group containing carbonate (however, those equivalent to constituent unit (a01), the aforementioned constituent unit (a02), constituent unit (a03), or constituent unit (a1) are excluded). The cyclic group containing lactone, the cyclic group containing -SO2-, or the cyclic group containing carbonate of the constituent unit (a2) is effective in improving the adhesion of the photoresist film to the substrate when the component (A1) is used to form a photoresist film. Furthermore, due to the presence of the constituent unit (a2), for example, by appropriately adjusting the acid diffusion length, the adhesion of the photoresist film to the substrate is improved, and the solubility during imaging is appropriately adjusted, resulting in better photolithography properties.

[0154] There is no particular limitation on the lactone-containing cyclic group in the constitutive unit (a2), and any one of them can be used. Specifically, groups represented by the following general formulas (a2-r-1) to (a2-r-7) can be cited.

[0155] [In the formula, Ra'21 are each independently a hydrogen atom, alkyl, alkoxy, halogen atom, haloalkyl, hydroxyl, -COOR”, -OC(=O)R”, hydroxyalkyl or cyano; R” is a hydrogen atom, alkyl, cyclic group containing lactone, cyclic group containing carbonate or cyclic group containing -SO2-; A” is an alkyl group with 1 to 5 carbon atoms, oxygen atom or sulfur atom that may contain oxygen atom (-O-) or sulfur atom (-S-), n' is an integer from 0 to 2, and m' is 0 or 1].

[0156] In the aforementioned general formulas (a2-r-1) to (a2-r-7), the alkyl group in Ra'21 is preferably an alkyl group having 1 to 6 carbon atoms. This alkyl group is preferably linear or branched. Specifically, examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tributyl, pentyl, isopentyl, neopentyl, and hexyl. Among these, methyl or ethyl is preferred, and methyl is particularly preferred. The alkoxy group in Ra'21 is preferably an alkoxy group having 1 to 6 carbon atoms. This alkoxy group is preferably linear or branched. Specifically, examples include groups in which the alkyl group listed above in Ra'21 is linked to an oxygen atom (-O-). The halogen atom in Ra'21 is preferably a fluorine atom. The halogenated alkyl group in Ra'21 is a group in which one or all of the hydrogen atoms of the alkyl group in Ra'21 are replaced by the aforementioned halogen atom. The alkyl halide is preferably a fluorinated alkyl group, and more preferably a perfluoroalkyl group.

[0157] In Ra'21, in "-COOR" and "-OC(=O)R", "R" is a hydrogen atom, an alkyl group, a cyclic group containing an lactone, a cyclic group containing a carbonate, or a cyclic group containing "-SO2-". The alkyl group in "R" can be linear, branched, or cyclic, and the number of carbon atoms is preferably 1 to 15. When "R" is a linear or branched alkyl group, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, and particularly preferably methyl or ethyl. When "R" is a cyclic alkyl group, the number of carbon atoms is preferably 3 to 15, more preferably 4 to 12, and most preferably 5 to 10. Specifically, examples include groups from monocyclic alkanes that can be substituted with fluorine atoms or fluorinated alkyl groups or that can be unsubstituted, and groups from polycyclic alkanes such as bicyclic alkanes, tricyclic alkanes, and tetracyclic alkanes that have had one or more hydrogen atoms removed. More specifically, examples include groups that have removed one or more hydrogen atoms from monocyclic alkanes such as cyclopentane and cyclohexane; and groups that have removed one or more hydrogen atoms from polycyclic alkanes such as adamantane, norcamphene, isocamphene, tricyclodecane, and tetracyclododecane. As for the lactone-containing cyclic group in "R", examples include those identical to the groups represented by the aforementioned general formulas (a2-r-1) to (a2-r-7). As for the carbonate-containing cyclic group in "R", similar to the carbonate-containing cyclic groups described later, examples include those identical to the groups represented by the general formulas (ax3-r-1) to (ax3-r-3). As for the -SO2- cyclic group in R”, similar to the -SO2- cyclic groups described later, specifically, groups represented by general formulas (a5-r-1) to (a5-r-4) can be cited. As for the hydroxyalkyl group in Ra’21, it is preferably one with 1 to 6 carbon atoms, specifically, groups in the aforementioned Ra’21 in which at least one hydrogen atom of the alkyl group is replaced by a hydroxyl group can be cited.

[0158] In the aforementioned general formulas (a2-r-2), (a2-r-3), and (a2-r-5), the alkyl group having 1 to 5 carbon atoms in A” is preferably a straight-chain or branched alkyl group, such as methylene, ethyl alkyl, n-propyl alkyl, and isopropyl alkyl. When the alkyl group contains an oxygen atom or a sulfur atom, examples include groups with -O- or -S- atoms at the end of the aforementioned alkyl group or between carbon atoms, such as O-CH2-, -CH2-O-CH2-, -S-CH2-, and -CH2-S-CH2-. As A”, it is preferably an alkyl group having 1 to 5 carbon atoms or -O-, more preferably an alkyl group having 1 to 5 carbon atoms, and most preferably methylene.

[0159] The following are specific examples of the bases represented by the general formulas (a2-r-1) to (a2-r-7).

[0160]

[0161]

[0162] "A cyclic group containing -SO2-" refers to a cyclic group whose ring skeleton contains a ring containing -SO2-. Specifically, a cyclic group in which the sulfur atom (S) in -SO2- forms part of the ring skeleton of the cyclic group. The ring containing -SO2- in the ring skeleton is counted as the first ring. When there is only this ring, it is called a monocyclic group. When there are other ring structures, it is called a polycyclic group regardless of its structure. A cyclic group containing -SO2- can be a monocyclic group or a polycyclic group. Cyclic groups containing -SO2- are particularly preferred, especially cyclic groups in which -O-SO2- is contained in the ring skeleton, that is, cyclic groups in which -OS- in -O-SO2- forms part of the sultone ring in the ring skeleton. More specifically, groups represented by the following general formulas (a5-r-1) to (a5-r-4) can be cited as cyclic groups containing -SO2-.

[0163] [In the formula, Ra'51 are each independently a hydrogen atom, alkyl, alkoxy, halogen atom, haloalkyl, hydroxyl, -COOR”, -OC(=O)R”, hydroxyalkyl or cyano; R” is a hydrogen atom, alkyl, cyclic group containing lactone, cyclic group containing carbonate or cyclic group containing -SO2-; A” is an alkyl group, oxygen atom or sulfur atom with 1 to 5 carbon atoms that may contain oxygen atom or sulfur atom, and n' is an integer from 0 to 2].

[0164] In the aforementioned general formulas (a5-r-1) to (a5-r-2), A” is the same as A” in the aforementioned general formulas (a2-r-2), (a2-r-3), and (a2-r-5). Examples of alkyl groups, alkoxy groups, halogen atoms, alkyl halides, -COOR”, -OC(=O)R”, and hydroxyalkyl groups in Ra'51 are the same as those listed in the description of Ra'21 in the aforementioned general formulas (a2-r-1) to (a2-r-7). Specific examples of groups represented by general formulas (a5-r-1) to (a5-r-4) are listed below. “Ac” in the formula represents acetyl.

[0165]

[0166]

[0167]

[0168] "Cyclic group containing carbonate rings" refers to a cyclic group containing a ring (carbonate ring) with -OC (=O)-O- in its ring skeleton. Counting the carbonate ring as the first ring, a group with only a carbonate ring is called a monocyclic group, and a group with other ring structures is called a polycyclic group regardless of its structure. A cyclic group containing carbonate rings can be either a monocyclic group or a polycyclic group. There is no particular limitation on the type of cyclic group containing carbonate rings, and any type can be used. Specifically, groups represented by the following general formulas (ax3-r-1) to (ax3-r-3) can be cited as examples.

[0169] [In the formula, Ra'x31 are each independently a hydrogen atom, alkyl, alkoxy, halogen atom, haloalkyl, hydroxyl, -COOR”, -OC(=O)R”, hydroxyalkyl or cyano; R” is a hydrogen atom, alkyl, cyclic group containing lactone, cyclic group containing carbonate or cyclic group containing -SO2-; A” is an alkyl group with 1 to 5 carbon atoms that may contain oxygen or sulfur atoms, oxygen or sulfur atoms, p' is an integer from 0 to 3, and q' is 0 or 1].

[0170] In the aforementioned general formulas (ax3-r-2) to (ax3-r-3), A” is the same as A” in the aforementioned general formulas (a2-r-2), (a2-r-3), and (a2-r-5). As for the alkyl, alkoxy, halogen atom, haloalkyl, -COOR”, -OC(=O)R”, and hydroxyalkyl in Ra'31, examples can be given that each is the same as those listed in the description of Ra'21 in the aforementioned general formulas (a2-r-1) to (a2-r-7). Specific examples of the groups represented by the general formulas (ax3-r-1) to (ax3-r-3) are given below.

[0171]

[0172] (A1) The constituent unit (a2) may be one type or two or more types. When the constituent unit (A1) has a constituent unit (a2), the proportion of the constituent unit (a2) relative to the total (100 mol%) of all constituent units constituting the constituent unit (A1) is preferably 1 to 50 mol%, more preferably 1 to 40 mol%.

[0173] Regarding the constituent unit (a3): Component (A1) may further have a constituent unit (a3) ​​containing an aliphatic hydrocarbon group with a polar group (however, excluding those equivalent to constituent units (a01), (a02), (a03), (a1), or the aforementioned constituent unit (a2)). By having a constituent unit (a3) ​​in component (A1), the hydrophilicity of component (A) is increased, which helps to improve the resolution. Furthermore, the acid diffusion length can be appropriately adjusted.

[0174] Examples of polar groups include hydroxyl, cyano, carboxyl, and hydroxyalkyl groups in which one hydrogen atom is partially replaced by a fluorine atom, with hydroxyl being particularly preferred. Examples of aliphatic hydrocarbon groups include straight-chain or branched hydrocarbon groups (preferably alkyl groups) having 1 to 10 carbon atoms or cyclic aliphatic hydrocarbon groups (cyclic groups). The cyclic group can be monocyclic or polycyclic, and can be appropriately selected from many proposers, for example, in resins used as photoresist compositions for ArF excimer lasers.

[0175] When the cyclic group is a monocyclic group, the number of carbon atoms is preferably 3 to 10. More preferably, it is a constituent unit derived from an acrylate, wherein the acrylate comprises an aliphatic monocyclic group containing a hydroxyalkyl group in which one of the hydrogen atoms of a hydroxyl, cyano, carboxyl, or alkyl group is partially replaced by a fluorine atom. Examples of such monocyclic groups include groups that have removed two or more hydrogen atoms from a monocyclic alkane. Specifically, examples include groups that have removed two or more hydrogen atoms from monocyclic alkanes such as cyclopentane, cyclohexane, and cyclooctane. Among these monocyclic groups, groups that have removed two or more hydrogen atoms from cyclopentane and groups that have removed two or more hydrogen atoms from cyclohexane are more industrially suitable.

[0176] When the cyclic group is a polycyclic group, the number of carbon atoms in the polycyclic group is preferably 7 to 30. More preferably, it is a constituent unit derived from an acrylate, wherein the acrylate comprises an aliphatic polycyclic group containing a hydroxyl group, a cyano group, a carboxyl group, or an alkyl group, one of whose hydrogen atoms are partially replaced by fluorine atoms. Examples of such polycyclic groups include groups from bicyclic alkanes, tricyclic alkanes, tetracyclic alkanes, etc., with two or more hydrogen atoms removed. Specifically, examples include groups from polycyclic alkanes such as adamantane, norcamphene, isobenzane, tricyclodecane, tetracyclododecane, etc., with two or more hydrogen atoms removed. Among these polycyclic groups, groups with two or more hydrogen atoms removed from adamantane, groups with two or more hydrogen atoms removed from norcamphene, and groups with two or more hydrogen atoms removed from tetracyclododecane are more industrially suitable.

[0177] As a constitutive unit (a3), there is no particular limitation as long as it contains an aliphatic hydrocarbon group with a polar group, and any unit can be used. As a constitutive unit (a3), it is a constitutive unit derived from an acrylate in which the hydrogen atom of the carbon atom bonded to the α-position can be replaced by a substituent, and preferably a constitutive unit containing an aliphatic hydrocarbon group with a polar group. As a constitutive unit (a3), when the hydrocarbon group in the aliphatic hydrocarbon group containing a polar group is a straight-chain or branched hydrocarbon group with 1 to 10 carbon atoms, it is preferably a constitutive unit derived from hydroxyethyl acrylate of acrylic acid. Furthermore, as a constitutive unit (a3), when the hydrocarbon group in the aliphatic hydrocarbon group containing a polar group is a polycyclic group, the constitutive units shown in formula (a3-1), formula (a3-2), and formula (a3-3) are preferred; when it is a monocyclic group, the constitutive unit shown in formula (a3-4) is preferred.

[0178] [In the formula, R is the same as above, j is an integer from 1 to 3, k is an integer from 1 to 3, t' is an integer from 1 to 3, l is an integer from 0 to 5, and s is an integer from 1 to 3].

[0179] In formula (a3-1), j is preferably 1 or 2, more preferably 1. When j is 2, the hydroxyl group is preferably bonded to the 3- or 5-position of the adamantyl alkyl group. When j is 1, the hydroxyl group is preferably bonded to the 3-position of the adamantyl alkyl group. When j is 1, it is particularly preferably that the hydroxyl group is bonded to the 3-position of the adamantyl alkyl group.

[0180] In formula (a3-2), k is preferably 1. The cyano group is preferably bonded to the 5th or 6th position of the norcamphene group.

[0181] In formula (a3-3), t' is preferably 1; l is preferably 1; s is preferably 1. These are preferably achieved by bonding a 2-norkenyl or 3-norkenyl group to the end of the carboxyl group of the acrylic acid. The fluorinated alkyl alcohol is preferably bonded at the 5 or 6 position of the norkenyl group.

[0182] In formula (a3-4), t' is preferably 1 or 2. l is preferably 0 or 1. s is preferably 1. The fluorinated alkyl alcohol is preferably bonded to the 3 or 5 position of the cyclohexyl group.

[0183] The (A1) component may have one or more constituent units (a3). When the (A1) component has constituent units (a3), the proportion of constituent units (a3) ​​relative to the total (100 mol%) of all constituent units constituting the (A1) component is preferably 1 to 30 mol%, more preferably 2 to 25 mol%, and even more preferably 5 to 20 mol%. By setting the proportion of constituent units (a3) ​​above the preferred lower limit, the effect of containing constituent units (a3) ​​can be fully obtained through the aforementioned effect. If it is below the preferred upper limit, a balance with other constituent units can be achieved, and various lithography properties become better.

[0184] Regarding the constituent unit (a4): The (A1) component may further have a constituent unit (a4) containing an acid-non-dissociative aliphatic cyclic group. By having the constituent unit (a4) in the (A1) component, the dry etching resistance of the formed photoresist pattern is improved. Furthermore, the hydrophobicity of the (A) component is increased. The improvement in hydrophobicity is particularly helpful in improving resolution and photoresist pattern shape during solvent imaging processes. The "acid-non-dissociative cyclic group" in the constituent unit (a4) is a cyclic group that remains in the constituent unit as is, even when acid is generated in the photoresist composition by exposure (for example, when acid is generated from a constituent unit that generates acid by exposure or from the (B) component), it does not dissociate during the reaction of the acid.

[0185] As a constitutive unit (a4), it is preferably a constitutive unit derived from an acrylate containing an acid-non-dissociable aliphatic cyclic group. This cyclic group can be any of the commonly known resin components used in photoresist compositions for ArF excimer lasers, KrF excimer lasers (preferably ArF excimer lasers), etc. From the perspective of industrial availability, this cyclic group is particularly preferably selected from at least one of tricyclodecyl, adamantyl, tetracyclododecyl, isocamphenyl, and norcamphenyl. These polycyclic groups may have a straight-chain or branched alkyl group having 1 to 5 carbon atoms as a substituent. Specifically, as a constitutive unit (a4), examples can be shown of constitutive units represented by the following general formulas (a4-1) to (a4-7).

[0186] [In the formula, Rα is the same as above].

[0187] (A1) The constituent unit (a4) may be one type or two or more types. When the (A1) constituent unit has a constituent unit (a4), the proportion of the constituent unit (a4) relative to the total (100 mol%) of all constituent units constituting the (A1) constituent unit is preferably 1 to 40 mol%, more preferably 5 to 20 mol%. By setting the proportion of the constituent unit (a4) above the preferred lower limit, the effect of containing the constituent unit (a4) can be fully obtained. On the other hand, by setting it below the preferred upper limit, it is easy to achieve a balance with other constituent units.

[0188] The (A1) component contained in the photoresist composition may be used alone or in combination with two or more. The (A1) component includes a polymeric compound (A01) having a repeating structure of a constituent unit (a01), a constituent unit (a02) and a constituent unit (a03), and preferably the (A1) component is a polymeric compound (A011) composed of a repeating structure of a constituent unit (a01), a constituent unit (a02) and a constituent unit (a03).

[0189] The proportion of the constituent units (a01) in the polymer compound (A01) relative to the total number of all constituent units constituting the (A1) component (100 mol%) is preferably 20 mol% or more and 70 mol% or less, more preferably 30 mol% or more and 60 mol% or less, even more preferably 40 mol% or more and 60 mol% or less, and particularly preferably 45 mol% or more and 55 mol% or less. The proportion of the constituent units (a02) in the polymer compound (A01) relative to the total number of all constituent units constituting the (A1) component (100 mol%) is preferably 10 mol% or more and 60 mol% or less, more preferably 20 mol% or more and 60 mol% or less, even more preferably 20 mol% or more and 50 mol% or less, and particularly preferably 35 mol% or more and 45 mol% or less. The proportion of the constituent unit (a03) in the polymer compound (A01) relative to the total (100 mol%) of all constituent units constituting the (A1) component is preferably 1 mol% or more and 50 mol% or less, more preferably 5 mol% or more and 30 mol% or less, even more preferably 5 mol% or more and 20 mol% or less, and particularly preferably 5 mol% or more and 15 mol% or less.

[0190] The molar ratio (constituent unit (a03):constituent unit (a02)) of the content of the constituent unit (a03) in the polymer compound (A01) is preferably 10:90 to 90:10, more preferably 10:90 to 60:40, even more preferably 10:90 to 50:50, and particularly preferably 10:90 to 40:60.

[0191] The molar ratio of the content of the constituent unit (a01) in the polymer compound (A01) to the total content of the constituent units (a02) and (a03) (constituent unit (a01): constituent unit (a02) and constituent unit (a03)) is preferably 80:20 to 20:80, more preferably 70:30 to 30:70, and even more preferably 60:40 to 40:60.

[0192] The (A1) component can be manufactured by dissolving the monomers of each derived constituent unit in a polymerization solvent, and adding, for example, a free radical polymerization initiator such as azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyrate (e.g., V-601) to the solvent. Alternatively, the (A1) component can be manufactured by dissolving the monomers of the derived constituent unit (a01), the monomers of the derived constituent unit (a02), the monomers of the derived constituent unit (a03), and, as needed, the monomers of constituent units other than those constituent units, in a polymerization solvent, and adding, as described above, a free radical polymerization initiator to the solvent. Furthermore, during polymerization, for example, a -C(CF3)2-OH group can be introduced at the end by using a chain transfer agent such as HS-CH2-CH2-CH2-C(CF3)2-OH. Thus, copolymers of hydroxyalkyl groups in which one of the hydrogen atoms of an alkyl group is partially replaced by fluorine atoms can effectively reduce imaging defects or reduce LER (line edge roughness: unevenness of the sidewalls of a line).

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

[0194] ・Regarding component (A2), the photoresist composition of this embodiment is component (A), and may be used in conjunction with a substrate component (hereinafter referred to as "component (A2)") whose solubility in the developer changes due to the action of acid, which is not equivalent to component (A1) mentioned above. There are no particular limitations on component (A2), and it may be selected arbitrarily from the majority of known substrate components used as chemical amplification photoresist compositions. Component (A2) may be a single polymeric compound or a low-molecular-weight compound, or it may be used in combination of two or more.

[0195] Relative to the total mass of component (A), the proportion of component (A1) in component (A) is preferably 25% by mass or more, more preferably 50% by mass or more, especially preferably 75% by mass or more, and may also be 100% by mass. If the proportion is 25% by mass or more, it is easy to form photoresist patterns with excellent photolithography characteristics such as high sensitivity, resolution, and improved roughness.

[0196] In the photoresist composition of this embodiment, the content of component (A) can be adjusted according to the desired photoresist film thickness, etc.

[0197] <Compound (D1)> In addition to component (A), the photoresist composition of this embodiment further contains compound (D1). Compound (D1) is one or more compounds selected from the group consisting of compounds shown in general formula (d1-1) and compounds shown in general formula (d1-2) below, and acts as, for example, as a quencher (acid diffusion control agent) for capturing acid generated by exposure in the photoresist composition.

[0198] [In the formula, Rd1 and Rd2 are each independently a cyclic group that may have substituents, a chain alkyl group that may have substituents, or a chain alkenyl group that may have substituents; however, in Rd2 of formula (d1-2), the carbon atom adjacent to the S atom is not bonded to a fluorine atom; m is an integer greater than or equal to 1, and Mm+ are each independently an m-valent organic cation].

[0199] {(d1-1) component} ・・In the anionic formula (d1-1), Rd1 is a cyclic group that may have substituents, a chain alkyl group that may have substituents, or a chain alkenyl group that may have substituents.

[0200] Cyclic group that may have substituents: The cyclic group is preferably a cyclic hydrocarbon group, which may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group that is not aromatic. Furthermore, the aliphatic hydrocarbon group may be saturated or unsaturated, but is usually preferred to be saturated.

[0201] The aromatic hydrocarbon group is a hydrocarbon group having an aromatic ring. The number of carbon atoms in the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, this number of carbon atoms does not include the number of carbon atoms in the substituents. Specifically, examples of the aromatic ring in the aromatic hydrocarbon group include benzene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic heterocycles in which a portion of the carbon atoms constituting such aromatic rings are replaced by heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specifically, examples of such aromatic hydrocarbon groups include groups with one hydrogen atom removed from the aforementioned aromatic ring (aryl: for example, phenyl, naphthyl, etc.), and groups in which one hydrogen atom of the aforementioned aromatic ring is replaced by an alkyl group (for example, arylalkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.). The aforementioned alkyl group (the alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2, and particularly preferably 1.

[0202] Examples of the cyclic aliphatic hydrocarbon group include aliphatic hydrocarbon groups containing a ring in their structure. Examples of aliphatic hydrocarbon groups containing a ring in their structure include alicyclic hydrocarbon groups (groups with one hydrogen atom removed from an aliphatic hydrocarbon ring), alicyclic hydrocarbon groups bonded to the end of a straight-chain or branched aliphatic hydrocarbon group, and alicyclic hydrocarbon groups intermediate in the middle of a straight-chain or branched aliphatic hydrocarbon group. The aforementioned alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12. The aforementioned alicyclic hydrocarbon group can be a polycyclic group or a monocyclic group. As a monocyclic alicyclic hydrocarbon group, it is preferable to have one or more hydrogen atoms removed from a monocyclic alkane. As for the monocyclic alkane, it is preferable to have 3 to 6 carbon atoms; specifically, cyclopentane and cyclohexane are examples. The polycyclic alicyclic hydrocarbon group is preferably a group that has removed one or more hydrogen atoms from the polycyclic alkane, and the polycyclic alkane preferably has 7 to 30 carbon atoms. Among them, the polycyclic alkane is more preferably a polycyclic alkane with a polycyclic skeleton that has a cross-linked ring system such as adamantane, norcamphene, isocamphene, tricyclodecane, tetracyclododecane, etc.; or a polycyclic alkane with a polycyclic skeleton that has a condensed ring system such as a cyclic group with a steroid skeleton.

[0203] Cyclic hydrocarbon groups, such as heterocycles, may contain heteroatoms. Specifically, examples include cyclic groups containing lactones represented by the aforementioned general formulas (a2-r-1) to (a2-r-7), cyclic groups containing -SO2- represented by the aforementioned general formulas (a5-r-1) to (a5-r-4), and other heterocyclic groups represented by the following chemical formulas (r-hr-1) to (r-hr-16). * indicates a bond.

[0204]

[0205] Substituents in the cyclic group of Rd1 can include, for example, alkyl, alkoxy, halogen atom, haloalkyl, hydroxy, carbonyl, nitro, etc.

[0206] The chain alkyl group may have substituents: The chain alkyl group of Rd1 may be either straight-chain or branched. As a straight-chain alkyl group, the preferred number of carbons is 1 to 20, more preferably 1 to 15, and most preferably 1 to 10. As a branched alkyl group, the preferred number of carbons is 3 to 20, more preferably 3 to 15, and most preferably 3 to 10. Specifically, examples include 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, etc.

[0207] The chain alkenyl group may have substituents: The chain alkenyl group of Rd1 may be either linear or branched, preferably having 2 to 10 carbon atoms, more preferably 2 to 5, particularly preferably 2 to 4, and especially preferably 3. Examples of linear alkenyl groups include vinyl, allyl, and butynyl. Examples of branched alkenyl groups include 1-methylvinyl, 2-methylvinyl, 1-methylpropenyl, and 2-methylpropenyl. Among the above, linear alkenyl groups are preferred, more preferably vinyl or allyl, and especially preferably vinyl.

[0208] Substituents in the chain alkyl or alkenyl groups of Rd1 include, for example, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, nitro groups, amino groups, etc.

[0209] Among these, Rd1 is preferably an aromatic hydrocarbon group that may have substituents, an aliphatic cyclic group that may have substituents, or a chain alkyl group that may have substituents. Examples of substituents that may be present in such groups include hydroxyl, oxy, alkyl, aryl, fluorine atom, fluorinated alkyl, lactone-containing cyclic groups represented by the above general formulas (a2-r-1) to (a2-r-7), ether bonds, ester bonds, or combinations thereof. When an ether bond or ester bond is included as a substituent, it may be an alkyl group. In this case, a linking group represented by the following general formulas (y-al-1) to (y-al-7) is preferred. Furthermore, when the substituent has a linker represented by each of the following general formulas (y-al-1) to (y-al-7), the bond between the substituent and Rd1 in the general formula (d1-1) is V'101 in the following general formulas (y-al-1) to (y-al-7).

[0210] [In the formula, V'101 is a single bond or an alkyl group with 1 to 5 carbon atoms, and V'102 is a divalent saturated hydrocarbon group with 1 to 30 carbon atoms].

[0211] The divalent saturated hydrocarbon group in V'102 is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and even more preferably an alkyl group having 1 to 5 carbon atoms.

[0212] The alkyl group in V'101 and V'102 can be a straight-chain alkyl group or a branched alkyl group, preferably a straight-chain alkyl group. Specifically, examples of alkyl groups in V'101 and V'102 include methylene [-CH2-]; alkyl methylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkyl ethyl groups such as ... Alkyl tetramethylene groups such as -CH2CH(CH3)CH2CH2-; pentamethylene groups such as [-CH2CH2CH2CH2CH2-]. Furthermore, one of the methylene groups in the aforementioned alkyl groups in V'101 or V'102 may be replaced by a divalent aliphatic cyclic group having 5 to 10 carbon atoms. This aliphatic cyclic group is preferably a divalent group formed by further removing one hydrogen atom from the cyclic aliphatic hydrocarbon group (monocyclic aliphatic hydrocarbon group, polycyclic aliphatic hydrocarbon group) of Ra'3 in the aforementioned formula (a1-r-1), and more preferably an alkylcyclohexyl, 1,5-alkyl adamantyl, or 2,6-alkyl adamantyl.

[0213] Among the aromatic hydrocarbon groups in Rd1, phenyl, naphthyl, and polycyclic structures including a bicyclic octane skeleton (polycyclic structures consisting of a bicyclic octane skeleton and other ring structures) are suitable examples. Among the aliphatic cyclic groups in Rd1, groups that have removed one or more hydrogen atoms from polycyclic alkanes such as adamantane, norcamphene, isocamphene, tricyclic decane, and tetracyclic dodecane are more preferred. Among the chain alkyl groups in Rd1, the number of carbon atoms is preferably 1 to 10. Specifically, straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl are suitable examples; 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 are also suitable examples.

[0214] When the aforementioned chain alkyl group has a fluorine atom or 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 atoms. Examples of atoms other than fluorine atoms include oxygen atoms, sulfur atoms, and nitrogen atoms.

[0215] The following shows a preferred example of the anionic portion of the (d1-1) component.

[0216]

[0217] ・・In the above general formula (d1-1) for the cation part, Mm+ is an m-valent organic cation. Among them, strontium cation and iodonium cation are preferred. m is an integer of 1 or more.

[0218] As a preferred cation portion ((Mm+)1 / m), examples include organic cations represented by the following general formulas (ca-1) to (ca-5).

[0219] [In the formula, R201~R207 and R211~R212 each independently represent aryl, alkyl or alkenyl groups that may have substituents; R201~R203, R206~R207, R211~R212 may be bonded to each other to form a ring together with the sulfur atom in the formula; R208~R209 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; R210 is an aryl group that may have substituents, an alkyl group that may have substituents, an alkenyl group that may have substituents or a cyclic group containing -SO2- that may have substituents; L201 represents -C(=O)- or -C(=O)-O-; Y201 each independently represents an aryl, alkyl or alkenyl group; x is 1 or 2; W201 represents a (x+1) valence linker group].

[0220] In the above general formulas (ca-1) to (ca-5), the aryl groups in R201 to R207 and R211 to R212 can be unsubstituted aryl groups with 6 to 20 carbon atoms, preferably phenyl or naphthyl. The alkyl groups in R201 to R207 and R211 to R212 are chain-like or cyclic alkyl groups, preferably with 1 to 30 carbon atoms. The alkenyl groups in R201 to R207 and R211 to R212 preferably have 2 to 10 carbon atoms. Substituents that can be present in R201 to R207 and R210 to R212 can be, for example, 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).

[0221] [In the formula, R'201 are each independently a hydrogen atom, a cyclic group that may have substituents, a chain alkyl group that may have substituents, or a chain alkenyl group that may have substituents].

[0222] As for the cyclic group, the chain alkyl group, and the chain alkenyl group that may have substituents in R'201, examples can be the same as the cyclic group, the chain alkyl group, and the chain alkenyl group that may have substituents in Rd1 of the above general formula (d1-1).

[0223] In addition to the cyclic group, the chain alkyl group or the chain alkenyl group that may have a substituent in R'201, the same acid dissociative group as shown in the above formula (a1-r-2) may also be mentioned.

[0224] Wherein, R'201 is preferably a cyclic group that may have substituents, and more preferably a cyclic hydrocarbon group that may have substituents. More specifically, for example, it is preferably phenyl, naphthyl, a group that has removed one or more hydrogen atoms from a polycyclic alkane; a cyclic group containing lactone represented by each of the aforementioned general formulas (a2-r-1) to (a2-r-7); a cyclic group containing -SO2- represented by each of the aforementioned general formulas (a5-r-1) to (a5-r-4), etc.

[0225] In the above general formulas (ca-1) to (ca-5), when R201 to R203, R206 to R207, and R211 to R212 are bonded to each other to form a ring together with the sulfur atom in the formula, they can be bonded through heteroatoms such as sulfur atoms, oxygen atoms, and nitrogen atoms, or functional groups such as carbonyl groups, -SO-, -SO2-, -SO3-, -COO-, -CONH-, or -N(RN)- (where RN is an alkyl group having 1 to 5 carbon atoms). As the formed ring, the ring skeleton contains one ring containing the sulfur atom in the formula, preferably a 3 to 10-membered ring, and more preferably a 5 to 7-membered ring. Specific examples of the rings formed include thiophene rings, thiazole rings, thianthene rings, benzothiophene rings, dibenzothiophene rings, 9H-thioxanthene rings, thioxanone rings, thianthene rings, phenanthrene rings, tetrahydrothiophene rings, and tetrahydrothiaranthion rings.

[0226] R208 to R209 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. When they are alkyl groups, they can bond with each other to form a ring.

[0227] R210 is an aryl group that may have substituents, an alkyl group that may have substituents, an alkenyl group that may have substituents, or a cyclic group containing -SO2- that may have substituents. Examples of the aryl group in R210 include unsubstituted aryl groups having 6 to 20 carbon atoms, preferably phenyl or naphthyl. The alkyl group in R210 is a chain or cyclic alkyl group, preferably having 1 to 30 carbon atoms. The alkenyl group in R210 preferably has 2 to 10 carbon atoms. The cyclic group containing -SO2- that may have substituents in R210 is preferably a "polycyclic group containing -SO2-", more preferably a group represented by the above general formula (a5-r-1).

[0228] Y201 each independently represents an aryl, alkyl, or alkenyl group. Examples of aryl groups in Y201 include groups that have one hydrogen atom removed from an aryl group exemplified as an aromatic hydrocarbon group in the above-described Yax0. Examples of alkyl and alkenyl groups in Y201 include groups that have one hydrogen atom removed from a group exemplified as a chain alkyl or chain alkenyl group in the above-described R'201.

[0229] In the aforementioned formula (ca-4), x is 1 or 2. W201 is (x+1) valence, that is, a divalent or trivalent linkage. As the divalent linkage in W201, it is preferably a divalent hydrocarbon group that may have substituents, such as a divalent hydrocarbon group that may have substituents, similar to Ya21 in the above general formula (a2-1). The divalent linkage in W201 can be any of straight-chain, branched, or cyclic, preferably cyclic. Among them, it is preferably a group with two carbonyl groups combined at both ends of the aryl group. Examples of aryl groups include phenyl, naphthyl, etc., with phenyl being particularly preferred. As the trivalent linkage in W201, examples include a group that removes one hydrogen atom from the divalent linkage in W201, or a group that further bonds the aforementioned divalent linkage to the aforementioned divalent linkage. As a trivalent linker in W201, it is preferably a group with two carbonyl groups bonded to an aryl group.

[0230] The following shows suitable cations represented by the above general formula (ca-1).

[0231]

[0232]

[0233] [In the formula, g2 and g3 represent the number of repetitions, g2 is an integer from 0 to 20, and g3 is an integer from 0 to 20].

[0234]

[0235]

[0236] [In the formula, R”201 is a hydrogen atom or a substituent, and the same substituents as those listed above as possible substituents that R201~R207 and R210~R212 can be included as such substituents].

[0237]

[0238]

[0239]

[0240] Specifically, suitable cations represented by the above general formula (ca-2) include diphenyliodonium cation, bis(4-tert-butylphenyl)iodonium cation, etc.

[0241] As a suitable cation represented by the above general formula (ca-3), specifically, cations represented by the following formulas (ca-3-1) to (ca-3-6) can be cited.

[0242]

[0243] As a suitable cation represented by the above general formula (ca-4), specifically, cations represented by the following formulas (ca-4-1) to (ca-4-2) can be cited.

[0244]

[0245] As a suitable cation represented by the above general formula (ca-5), specifically, cations represented by the following general formulas (ca-5-1) to (ca-5-3) can be cited.

[0246]

[0247] In the above general formula (d1-1), Mm+ refers to the above-mentioned cation, preferably the cation shown in the above general formula (ca-1). The (d1-1) component can be used alone or in combination of two or more.

[0248] {(d1-2) Components} ・・Anionic Section In the above general formula (d1-2), Rd2 can be a cyclic group that may have substituents, a chain alkyl group that may have substituents, or a chain alkenyl group that may have substituents, such as R'201 mentioned above. However, in Rd2, the carbon atom adjacent to the S atom is not bonded to a fluorine atom (not substituted by fluorine). Therefore, the anion of the (d1-2) component becomes a moderately weak acid anion, enhancing its quenching ability.

[0249] In the above general formula (d1-2), Rd2 is one of the above, preferably a chain alkyl group that may have substituents or an aliphatic cyclic group that may have substituents, and more preferably an aliphatic cyclic group that may have substituents.

[0250] The chain alkyl group preferably has 1 to 10 carbon atoms, more preferably 3 to 10. The aliphatic cyclic group is more preferably a group (which may have substituents) that has removed one or more hydrogen atoms from adamantane, norcamphene, isocamphene, tricyclodecane, tetracyclododecane, etc.; or a group that has removed one or more hydrogen atoms from camphor, etc. The hydrocarbon group of Rd2 may have substituents, and examples of substituents are those that may have the same substituents as those that may have the hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, chain alkyl group) in Rd1 of the above general formula (d1-1). Furthermore, when the substituent has a linking base represented by each of the above general formulas (y-al-1) to (y-al-7), the one bonded to Rd1 in formula (d1-1) in the above general formulas (y-al-1) to (y-al-7) is V'101 in the above general formulas (y-al-1) to (y-al-7).

[0251] The anionic portion of component (d1-2) is among those described above, and is preferably an anion represented by the following general formula (an-d1-2).

[0252] [In the formula, Ld11 is an alkyl group that may have substituents; Yd11 represents a single bond or a divalent linkage containing an oxygen atom; Rd11 represents an alicyclic hydrocarbon group that may have substituents; however, Ld11, Yd11 and Rd11 do not contain halogen atoms].

[0253] In the above general formula (an-d1-2), Ld11 represents an alkyl group that may have substituents. The aforementioned alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, even more preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms. The aforementioned alkyl group may be linear or branched. Specific examples of alkyl groups in Ld11 include methylene [-CH2-]; alkyl methylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkyl ethyl groups such as ... Alkyl tetramethylenes such as -CH2CH(CH3)CH2CH2-; pentamethylenes such as [-CH2CH2CH2CH2CH2-].

[0254] The alkyl group in Ld11 may or may not have substituents, but it is preferred that it does not have substituents. Examples of substituents that may be present in the alkyl group of Ld11 include alkoxy, hydroxy, carbonyl, nitro, and amino groups.

[0255] The alkyl group of Ld11 is preferably a straight-chain alkyl group having 1 to 5 carbons, more preferably a straight-chain alkyl group having 1 to 3 carbons, and even more preferably methylene or ethyl alkyl group.

[0256] In the above general formula (an-d1-2), Yd11 represents a single bond or a divalent linkage containing an oxygen atom. When Yd11 is a divalent linkage containing an oxygen atom, Yd11 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 linkages containing oxygen atoms include oxygen atoms (ether bond: -O-), ester bond (-C(=O)-O-), oxycarbonyl (-OC(=O)-), amide bond (-C(=O)-NH-), carbonyl (-C(=O)-), carbonate bond (-OC(=O)-O-), etc., which are non-hydrocarbon linkages containing oxygen atoms; combinations of these non-hydrocarbon linkages containing oxygen atoms with alkyl groups, etc. In this combination, a sulfonyl group (-SO2-) can be further linked.

[0257] More specifically, the binding bases containing oxygen atoms in Yd11 can be suitably represented by the binding bases represented by the above general formulas (y-al-1) to (y-al-7). Furthermore, when Yd11 in the above general formula (an-d1-2) is a binding base represented by the above general formulas (y-al-1) to (y-al-7), the bonded to Rd11 in the above formula (an-d1-2) is V'101 in the above general formulas (y-al-1) to (y-al-7).

[0258] As Yd11, it is preferably a divalent linker containing an ester bond, a divalent linker containing an oxygen carbonyl group, or a single bond, and more preferably a divalent linker containing an ester bond or a divalent linker containing an oxygen carbonyl group. Specifically, as Yd11, it is preferably a linker shown in the above general formula (y-al-1) or (y-al-3).

[0259] In the aforementioned formula (an-d1-2), Rd11 represents an alicyclic hydrocarbon group that may have substituents. Examples of alicyclic hydrocarbon groups in Rd11 include those listed as alicyclic hydrocarbon groups in Rd1. Preferably, the alicyclic hydrocarbon group in Rd11 is a polycyclic alicyclic hydrocarbon group, more preferably a group consisting of a polycyclic alkane with a polycyclic skeleton having one or more hydrogen atoms removed (cross-linked cyclic alicyclic hydrocarbon group), or a lactone-containing cyclic group as shown in the aforementioned general formula (a2-r-7), a group consisting of adamantane or norbornene having one or more hydrogen atoms removed, or a lactone-containing cyclic group as shown in the aforementioned general formula (a2-r-7). Preferably, the substituent is an alkyl or carbonyl group.

[0260] The following shows specific examples of the anionic portion of the (d1-2) component.

[0261]

[0262]

[0263] The anionic portion of the (d1-2) component is preferably an anion represented by the above chemical formulas (an-d12-1) to (an-d12-14) and (an-d12-18) to (an-d12-21), and more preferably an anion represented by the above chemical formulas (an-d12-10) or (an-d12-14).

[0264] ・・In the cation part formula (d1-2), Mm+ is an m-valent organic cation, the same as Mm+ in the general formula (d1-1) above. Component (d1-2) can be used alone or in combination of two or more.

[0265] (d1-2) is one of the above, preferably a compound represented by the following general formula (d1-2-1) (hereinafter also referred to as "(d1-2-1) component").

[0266]

[0267] The anionic component of component (d1-2-1) is the same as the anion represented by the above general formula (an-d1-2). The cation component of component (d1-2-1) is the same as the cation represented by the above general formula (ca-1).

[0268] The compound (D1) is among those described above, preferably the compound represented by the general formula (d1-2), and more preferably the compound represented by the general formula (d1-2-1).

[0269] The following shows a suitable specific example of compound (D1).

[0270]

[0271] As compound (D1), among the above, it is preferably the compound represented by each of the above formulas (D1-1) to (D1-3), and more preferably the compound represented by the above formulas (D1-1) or (D1-2).

[0272] The content of compound (D1) in the photoresist composition of this embodiment is preferably 3 to 20 parts by mass relative to 100 parts by mass of component (A1), and more preferably 5 to 15 parts by mass. As long as the content of compound (D1) is above or above the aforementioned preferred lower limit, it is particularly easy to obtain good lithography properties and good photoresist pattern shape. On the other hand, if it is below or below the aforementioned preferred upper limit, good sensitivity can be maintained.

[0273] Method for manufacturing compound (D1): There is no particular limitation on the method for manufacturing component (d1-1), and it can be manufactured by a well-known method. Also, there is no particular limitation on the method for manufacturing component (d1-2), and it can be manufactured in the same manner as described in US Publication No. 2012-0149916.

[0274] <Other Components> In addition to component (A) and compound (D1) mentioned above, the photoresist composition system of this embodiment may further contain other components. Examples of other components include component (B), component (D) (except for compound (D1)), component (E), component (F), and component (S) shown below.

[0275] ≪Acid Generating Agent Component (B)≫ The photoresist composition of this embodiment may further contain an acid generating agent component (B) that generates acid by exposure (hereinafter referred to as "(B) component"). There are no particular limitations on the (B) component, and acid generating agents proposed for use in chemically amplified photoresist compositions to date may be used. Examples of such acid generating agents include onium salt acid generating agents such as iodonium salts or strontium salts, oxime sulfonate acid generating agents; dialkyl or diarylsulfonyldiazomethane, poly(disulfonyl)diazomethane, and other diazomethane acid generating agents; nitrobenzyl sulfonate acid generating agents, imino sulfonate acid generating agents, disulfonate acid generating agents, and many others.

[0276] For example, compounds represented by general formula (b-1) (hereinafter also referred to as "(b-1) component"), compounds represented by general formula (b-2) (hereinafter also referred to as "(b-2) component") or compounds represented by general formula (b-3) (hereinafter also referred to as "(b-3) component") can be used as onium salt acid generating agents.

[0277] [In the formula, R101 and R104 to R108 are each independently a cyclic group that may have substituents, a chain alkyl group that may have substituents, or a chain alkenyl group that may have substituents; R104 and R105 may be bonded to each other to form a ring structure; R102 is a fluorinated alkyl group or a fluorine atom with 1 to 5 carbon atoms; Y101 is a divalent linker group containing an oxygen atom or a single bond; V101 to V103 are each independently a single bond, an alkyl group, or a fluorinated alkyl group; L101 to L102 are each independently a single bond or an oxygen atom; L103 to L105 are each independently a single bond, -CO-, or -SO2-; m is an integer greater than or equal to 1, and M'm+ is an m-valent onium cation].

[0278] {Anionic part} ・(b-1) In the anionic formula (b-1) of the component, R101 is a cyclic group that may have substituents, a chain alkyl group that may have substituents, or a chain alkenyl group that may have substituents.

[0279] Cyclic group that may have substituents: The cyclic group is preferably a cyclic hydrocarbon group, which may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group that is not aromatic. Furthermore, the aliphatic hydrocarbon group may be saturated or unsaturated, but is usually preferred to be saturated.

[0280] The aromatic hydrocarbon group in R101 is a hydrocarbon group having an aromatic ring. The number of carbon atoms in this aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, this number of carbon atoms does not include the number of carbon atoms in the substituents. Specifically, examples of the aromatic ring in the aromatic hydrocarbon group of R101 include benzene, naphthalene, onion, phenanthrene, biphenyl, or aromatic heterocycles in which a portion of the carbon atoms constituting such aromatic rings is replaced by heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specifically, the aromatic hydrocarbon group in R101 can be a group in which one hydrogen atom is removed from the aforementioned aromatic ring (aryl: for example, phenyl, naphthyl, etc.), or a group in which one hydrogen atom of the aforementioned aromatic ring is replaced by an alkyl group (for example, arylalkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.). The aforementioned alkyl group (the alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2, and particularly preferably 1.

[0281] Examples of cyclic aliphatic hydrocarbon groups in R101 include aliphatic hydrocarbon groups that contain a ring in their structure. Examples of aliphatic hydrocarbon groups containing a ring in their structure include alicyclic hydrocarbon groups (groups with one hydrogen atom removed from an aliphatic hydrocarbon ring), alicyclic hydrocarbon groups bonded to the end of a straight-chain or branched aliphatic hydrocarbon group, and alicyclic hydrocarbon groups intermediate in the middle of a straight-chain or branched aliphatic hydrocarbon group. Preferably, the aforementioned alicyclic hydrocarbon group has 3 to 20 carbon atoms, more preferably 3 to 12. The aforementioned alicyclic hydrocarbon group can be a polycyclic group or a monocyclic group. Preferably, the monocyclic alicyclic hydrocarbon group is a group with one or more hydrogen atoms removed from a monocyclic alkane. Preferably, the monocyclic alkane has 3 to 6 carbon atoms; specifically, cyclopentane and cyclohexane are examples. The polycyclic alicyclic hydrocarbon group is preferably a group that has removed one or more hydrogen atoms from a polycyclic alkane, and the polycyclic alkane preferably has 7 to 30 carbon atoms. More preferably, the polycyclic alkane is a polycyclic alkane with a polycyclic skeleton that has a cross-linked ring system, such as adamantane, norcamphene, isocamphene, tricyclodecane, or tetracyclododecane; or a polycyclic alkane with a polycyclic skeleton that has a condensed ring system, such as a cyclic group with a steroid skeleton.

[0282] Among them, the cyclic aliphatic hydrocarbon group in R101 is preferably a group that has removed one or more hydrogen atoms from a monocyclic alkane or polycyclic alkane, more preferably a group that has removed one hydrogen atom from a polycyclic alkane, especially adamantyl or norbornel, and most preferably adamantyl.

[0283] A straight-chain aliphatic hydrocarbon group that can be bonded to an alicyclic hydrocarbon group, preferably having 1 to 10 carbon atoms, more preferably 1 to 6, particularly preferably 1 to 4, and most preferably 1 to 3. As a straight-chain aliphatic hydrocarbon group, it is preferably a straight-chain alkyl group, specifically, examples include methylene [-CH2-], ethyl [-(CH2)2-], trimethylene [-(CH2)3-], tetramethylene [-(CH2)4-], pentamethylene [-(CH2)5-], etc., which are branched aliphatic hydrocarbon groups that can be bonded to an alicyclic hydrocarbon group, preferably having 2 to 10 carbon atoms, more preferably 3 to 6, particularly preferably 3 or 4, and most preferably 3. As a branched aliphatic hydrocarbon group, it is preferred to be a branched alkyl group. Specifically, examples include alkyl methylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkyl ethyl groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyl trimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkyl tetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The alkyl group in the alkyl group is preferably a straight-chain alkyl group having 1 to 5 carbon atoms.

[0284] Furthermore, the cyclic hydrocarbon group in R101 may also contain heteroatoms, such as heterocycles. Specifically, examples include cyclic groups containing lactones represented by the aforementioned general formulas (a2-r-1) to (a2-r-7), cyclic groups containing -SO2- represented by the aforementioned general formulas (a5-r-1) to (a5-r-4), and other heterocyclic groups represented by the aforementioned chemical formulas (r-hr-1) to (r-hr-16).

[0285] Examples of substituents in the cyclic group of R101 include alkyl, alkoxy, halogen atom, alkyl halide, hydroxyl, carbonyl, and nitro groups. The alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, most preferably methyl, ethyl, propyl, n-butyl, or tributyl. The alkoxy group is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, or tributoxy, most preferably methoxy or ethoxy. Examples of halogen atoms in the substituent include fluorine, chlorine, bromine, and iodine atoms, most preferably fluorine. Examples of alkyl halide groups are alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, or tributyl, where some or all of the hydrogen atoms are replaced by the aforementioned halogen atoms. The carbonyl group in the substituent is a methylene (-CH2-) group that substitutes for the cyclic hydrocarbon group.

[0286] The cyclic hydrocarbon group in R101 may include a condensed cyclic group of a condensed ring formed by the condensation of an aliphatic hydrocarbon ring and an aromatic ring. Examples of the aforementioned condensed ring include polycyclic alkanes with a polycyclic skeleton in a cross-linked ring system, such as those condensed with one or more aromatic rings. Specific examples of the aforementioned cross-linked polycyclic alkanes include bicyclic alkanes such as bicyclo[2.2.1]heptane (norbornene) and bicyclo[2.2.2]octane. The aforementioned condensed cyclic group is preferably a group containing a condensed ring of two or three aromatic rings condensed in a bicyclic alkanes, and more preferably a group containing a condensed cyclic group of two or three aromatic rings condensed in bicyclo[2.2.2]octane. Specific examples of the condensed cyclic group in R101 include those shown in the following formulas (r-br-1) to (r-br-2). In the formula, * represents the Y101 bond in formula (b-1).

[0287]

[0288] Examples of substituents that may be present in the condensed cyclic group of R101 include alkyl, alkoxy, halogen atom, alkyl halide, hydroxyl, carbonyl, nitro, aromatic hydrocarbon group, and alicyclic hydrocarbon group. Examples of alkyl, alkoxy, halogen atom, and alkyl halide substituents in the aforementioned condensed cyclic group are the same as those listed as substituents in the cyclic group of R101. Examples of aromatic hydrocarbon groups that may be substituents in the aforementioned condensed cyclic group include groups with one hydrogen atom removed from the aromatic ring (aryl: for example, phenyl, naphthyl, etc.), groups with one hydrogen atom of the aforementioned aromatic ring replaced by an alkyl group (for example, benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc., arylalkyl groups), and heterocyclic groups represented by each of the above formulas (r-hr-1) to (r-hr-6). Examples of alicyclic hydrocarbon groups that can be used as substituents for the aforementioned condensed cyclic groups include groups that have had one hydrogen atom removed from monocyclic alkanes such as cyclopentane and cyclohexane; groups that have had one hydrogen atom removed from polycyclic alkanes such as adamantane, norcamphene, isocamphene, tricyclodecane, and tetracyclododecane; cyclic groups containing lactones represented by the aforementioned general formulas (a2-r-1) to (a2-r-7); cyclic groups containing -SO2- represented by the aforementioned general formulas (a5-r-1) to (a5-r-4); and heterocyclic groups represented by the aforementioned formulas (r-hr-7) to (r-hr-16).

[0289] A chain alkyl group that may have substituents: As R101, the chain alkyl group may be either straight-chain or branched. As a straight-chain alkyl group, it is preferred to have 1 to 20 carbon atoms, more preferably 1 to 15, and most preferably 1 to 10. As a branched alkyl group, it is preferred to have 3 to 20 carbon atoms, more preferably 3 to 15, and most preferably 3 to 10. Specifically, examples include 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, etc.

[0290] The chain alkenyl group may have substituents: The chain alkenyl group as R101 may be either linear or branched, preferably having 2 to 10 carbon atoms, more preferably 2 to 5, particularly preferably 2 to 4, and especially preferably 3. Examples of linear alkenyl groups include vinyl, allyl, and butynyl. Examples of branched alkenyl groups include 1-methylvinyl, 2-methylvinyl, 1-methylpropenyl, and 2-methylpropenyl. Among the above, linear alkenyl groups are preferred, more preferably vinyl or allyl, and especially preferably vinyl.

[0291] Substituents in the chain alkyl or alkenyl groups of R101 can be, for example, alkoxy groups, halogen atoms, halogenated alkyl groups, hydroxyl groups, carbonyl groups, nitro groups, amino groups, and cyclic groups in the above-mentioned R101.

[0292] Of the above, R101 is preferably a cyclic group that may have substituents, and more preferably a cyclic hydrocarbon group that may have substituents. More specifically, it is preferably a group from which one or more hydrogen atoms have been removed from phenyl, naphthyl, or polycyclic alkyl groups; cyclic groups containing lactones represented by the aforementioned general formulas (a2-r-1) to (a2-r-7); and cyclic groups containing -SO2- represented by the aforementioned general formulas (a5-r-1) to (a5-r-4), etc.

[0293] In formula (b-1), Y101 is a single bond or a divalent linkage containing an oxygen atom. When Y101 is a divalent linkage containing an oxygen atom, it may contain atoms other than oxygen atoms. Examples of atoms other than oxygen atoms include carbon atoms, hydrogen atoms, sulfur atoms, and nitrogen atoms. Examples of divalent linkages containing oxygen atoms include non-hydrocarbon linkages containing oxygen atoms 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-); combinations of these non-hydrocarbon linkages containing oxygen atoms with alkyl groups, etc. In such combinations, sulfonyl groups (-SO2-) may be further linked. As a divalent linker containing an oxygen atom, examples include the linkers represented by the above general formulas (y-al-1) to (y-al-7). Furthermore, in the above general formulas (y-al-1) to (y-al-7), the linker bonded to R101 in formula (b-1) is V'101 in the following general formulas (y-al-1) to (y-al-7).

[0294] As Y101, it is preferably a divalent linker containing an ester bond or a divalent linker containing an ether bond, and more preferably a linker represented by each of the above formulas (y-al-1) to (y-al-5).

[0295] In formula (b-1), V101 is a single bond, an alkyl group, or a fluorinated alkyl group. Preferably, the alkyl group or fluorinated alkyl group in V101 has 1 to 4 carbon atoms. Examples of fluorinated alkyl groups in V101 include groups in which some or all of the hydrogen atoms of the alkyl group in V101 are replaced by fluorine atoms. Preferably, V101 is a single bond or a fluorinated alkyl group having 1 to 4 carbon atoms.

[0296] In formula (b-1), R102 is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. R102 is preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and more preferably a fluorine atom.

[0297] As a specific example of the anionic part shown in the aforementioned formula (b-1), when Y101 is a single bond, fluorinated alkyl sulfonate anions such as trifluoromethane sulfonate anion or perfluorobutane sulfonate anion can be cited; when Y101 is a divalent linker containing an oxygen atom, anions shown in any of the following formulas (an-1) to (an-3) can be cited.

[0298] [In the formula, R”101 is an aliphatic cyclic group that may have substituents, a monovalent heterocyclic group represented by each of the above chemical formulas (r-hr-1) to (r-hr-6), a condensed cyclic group represented by the aforementioned formula (r-br-1) or (r-br-2), or a chain alkyl group that may have substituents; R”102 is an aliphatic cyclic group that may have substituents, a condensed cyclic group represented by the aforementioned formula (r-br-1) or (r-br-2), or a group represented by the aforementioned general formulas (a2-r-1), (a2-r-3) to (a2-r-7). Each of the above-mentioned general formulas (a5-r-1) to (a5-r-4) represents a cyclic group containing lactone, or a cyclic group containing -SO2-. R”103 is an aromatic cyclic group, an aliphatic cyclic group, or a chain alkenyl group that may have substituents. V”101 is a single bond, an alkyl group with 1 to 4 carbon atoms, or a fluorinated alkyl group with 1 to 4 carbon atoms. R102 is a fluorine atom or a fluorinated alkyl group with 1 to 5 carbon atoms. v” is an integer from 0 to 3, q” is an integer from 0 to 20, and n” is 0 or 1.

[0299] The aliphatic cyclic groups that may have substituents, such as R”101, R”102 and R”103, are preferably the groups exemplified as the cyclic aliphatic hydrocarbon group in R101 of the aforementioned formula (b-1). As the aforementioned substituents, those that are the same as the substituents that can replace the cyclic aliphatic hydrocarbon group in R101 of the aforementioned formula (b-1) can be cited.

[0300] The aromatic cyclic group that may have a substituent in R”103 is preferably the aromatic hydrocarbon group exemplified as the cyclic hydrocarbon group in R101 of the aforementioned formula (b-1). As the aforementioned substituent, the same substituent as that which may replace the aromatic hydrocarbon group in R101 of the aforementioned formula (b-1) can be cited.

[0301] The chain alkyl group that may have substituents in R”101 is preferably the group exemplified as the chain alkyl group in R101 of the aforementioned formula (b-1). The chain alkenyl group that may have substituents in R”103 is preferably the group exemplified as the chain alkenyl group in R101 of the aforementioned formula (b-1).

[0302] ・In the anionic formula (b-2) of component (b-2), R104 and R105 are each independently a cyclic group that may have substituents, a chain alkyl group that may have substituents, or a chain alkenyl group that may have substituents, and each can be the same as R101 in formula (b-1). However, R104 and R105 can also be bonded to each other to form a ring. R104 and R105 are preferably chain alkyl groups that may have substituents, more preferably straight-chain or branched alkyl groups, or straight-chain or branched fluorinated alkyl groups. The number of carbon atoms in the chain alkyl group is preferably 1 to 10, more preferably 1 to 7, and even more preferably 1 to 3. The fewer carbon atoms in the chain alkyl group of R104 and R105 within the above-mentioned range, the better, based on reasons such as good solubility in photoresist solvents. Furthermore, the more hydrogen atoms replaced by fluorine atoms in the chain alkyl groups of R104 and R105, the stronger the acid, and the better, due to the improved transparency to high-energy light or electron beams below 250 nm. The proportion of fluorine atoms in the aforementioned chain alkyl groups, 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 replaced by fluorine atoms. In formula (b-2), V102 and V103 are each independently a single bond, an alkyl group, or a fluorinated alkyl group, and examples of each can be the same as V101 in formula (b-1). In formula (b-2), L101 and L102 are each independently a single bond or an oxygen atom.

[0303] ・In the anionic formula (b-3) of component (b-3), R106 to R108 are each independently a cyclic group that may have substituents, a chain alkyl group that may have substituents, or a chain alkenyl group that may have substituents, and each can be the same as R101 in formula (b-1). In formula (b-3), L103 to L105 are each independently a single bond, -CO-, or -SO2-.

[0304] In the above, the anionic portion of component (B) is preferably the anion in component (b-1). Preferably, it is an anion represented by any of the above general formulas (an-1) to (an-3), more preferably an anion represented by any of general formulas (an-1) or (an-2), and most preferably an anion represented by general formula (an-2).

[0305] {Cation Section} In the aforementioned formulas (b-1), (b-2), and (b-3), M'm+ represents an m-valent ononium cation. Preferably, it is a strontium cation or an iodonium cation. m is an integer greater than or equal to 1.

[0306] As a preferred cation portion ((M'm+)1 / m), examples can be organic cations represented by the above general formulas (ca-1) to (ca-5), with the cation represented by the above general formula (ca-1) being more preferred.

[0307] In the photoresist composition of this embodiment, component (B) can be used alone or in combination with two or more components. When the photoresist composition contains component (B), the content of component (B) in the photoresist composition is preferably less than 50 parts by mass relative to 100 parts by mass of component (A1), more preferably 5 to 40 parts by mass, and even more preferably 8 to 20 parts by mass. By setting the content of component (B) within the above range, a pattern can be sufficiently formed. Furthermore, when the components of the photoresist composition are dissolved in an organic solvent, a homogeneous solution is easily obtained, and the photoresist composition exhibits good storage stability and is therefore more suitable.

[0308] ≪Alkali Component (D)≫ The photoresist composition of this embodiment may further contain an alkaline component ((D) component) other than a compound (D1) that captures (i.e., controls the diffusion of acid) generated by exposure. The (D) component acts as a quencher (acid diffusion control agent) that captures acid generated by exposure in the photoresist composition. Examples of (D) components include photodisintegrating alkali (D3) (hereinafter referred to as "(D3) component") that loses its acid diffusion control function by decomposition upon exposure, and nitrogen-containing organic compounds (D2) (hereinafter referred to as "(D2) component") that are not equivalent to the (D3) component.

[0309] ・Regarding the (D3) component: When forming a photoresist pattern, the contrast between the exposed and unexposed areas of the photoresist film can be further improved by using a photoresist composition containing the (D3) component. There are no particular limitations on the (D3) component, as long as it decomposes upon exposure and loses its acid diffusion control, but it is preferably a compound represented by the following general formula (d1-3) (hereinafter referred to as "(d1-3) component"). Since the (d1-3) component decomposes in the exposed area of ​​the photoresist film and loses its acid diffusion control (alkalinity), it does not act as a quenching agent, but acts as a quenching agent in the unexposed area of ​​the photoresist film.

[0310] [In the formula, Rd3 and Rd4 are each independently a cyclic group that may have substituents, a chain alkyl group that may have substituents, or a chain alkenyl group that may have substituents; Yd1 is a single bond or a divalent linked group; m is an integer greater than or equal to 1, and Mm+ is an m-valent organic cation].

[0311] {(d1-3) Components} ・・In the anionic formula (d1-3), Rd3 is a cyclic group that may have substituents, a chain alkyl group that may have substituents, or a chain alkenyl group that may have substituents. Examples include those similar to R'201 mentioned above, but preferably a cyclic group, chain alkyl group, or chain alkenyl group containing fluorine atoms. Among these, a fluorinated alkyl group is preferred, and more preferably the same as the fluorinated alkyl group of Rd1 mentioned above.

[0312] In formula (d1-3), Rd4 is a cyclic group that may have substituents, a chain alkyl group that may have substituents, or a chain alkenyl group that may have substituents, and examples are similar to those of R'201 mentioned above. Preferably, it is an alkyl group, alkoxy group, alkenyl group, or cyclic group that may have substituents. The alkyl group in Rd4 is preferably a straight-chain or branched alkyl group having 1 to 5 carbon atoms, specifically, examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tributyl, pentyl, isopentyl, neopentyl, etc. A portion of the hydrogen atom of the alkyl group in Rd4 may be replaced by a hydroxyl group, cyano group, etc. The alkoxy group in Rd4 is preferably an alkoxy group having 1 to 5 carbon atoms, specifically, examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and tributoxy. Preferably, it is methoxy or ethoxy.

[0313] The alkenyl group in Rd4 can be the same as that in R'201, preferably vinyl, propenyl (allyl), 1-methylpropenyl, or 2-methylpropenyl. These groups may further have an alkyl group having 1 to 5 carbon atoms or a haloalkyl group having 1 to 5 carbon atoms as a substituent.

[0314] The cyclic group in Rd4 can be the same as the cyclic group in R'201 mentioned above. Preferably, it is an alicyclic group with one or more hydrogen atoms removed from cycloalkanes such as cyclopentane, cyclohexane, adamantane, norcamphene, isocamphene, tricyclodecane, and tetracyclododecane, or an aromatic group such as phenyl or naphthyl. When Rd4 is an alicyclic group, the photoresist composition dissolves well in organic solvents, resulting in better lithography properties. Furthermore, when Rd4 is an aromatic group, the photoresist composition exhibits excellent light absorption efficiency and improved sensitivity or lithography properties in lithography using EUV or similar exposure light sources.

[0315] In formula (d1-3), Yd1 is a single bond or a divalent linkage. There is no particular limitation on the divalent linkage in Yd1, but examples include divalent hydrocarbon groups (aliphatic hydrocarbon groups, aromatic hydrocarbon groups) that may have substituents, and divalent linkage groups containing heteroatoms. Examples of these are the same as those listed in the description of the divalent linkage in Ya21 of formula (a2-1) above, including divalent hydrocarbon groups that may have substituents and divalent linkage groups containing heteroatoms. Yd1 is preferably a carbonyl group, an ester bond, an amide bond, an alkyl group, or a combination thereof. As an alkyl group, it is more preferably a straight-chain or branched alkyl group, and especially preferably a methylene or ethyl group.

[0316] The following shows a preferred example of the anionic portion of the (d1-3) components.

[0317]

[0318]

[0319] .. In the cation part formula (d1-3), Mm+ is an m-valent organic cation. Specifically, examples can be given of organic cations represented by the above general formulas (ca-1) to (ca-5). The (d1-3) component can be used alone or in combination of two or more.

[0320] (D3) Component can be used alone or in combination of two or more. When the photoresist composition contains (D3) component, the content of (D3) component is preferably 0.5 to 20 parts by mass relative to 100 parts by mass of (A1) component, more preferably 1 to 15 parts by mass.

[0321] (D3) Manufacturing method: Furthermore, the manufacturing method of components (d1-3) is not particularly limited, for example, it can be manufactured in the same way as the method described in US2012-0149916.

[0322] ・Regarding component (D2), as component (D), it may contain a nitrogen-containing organic compound component (hereinafter referred to as "component (D2)") that is not equivalent to component (D3) described above. As component (D2), there are no particular limitations as long as it functions as an acid diffusion control agent and is not equivalent to component (D3), and well-known components may be used at will. Among these, aliphatic amines are preferred, and secondary aliphatic amines or tertiary aliphatic amines are particularly preferred. Aliphatic amines are amines having one or more aliphatic groups, and the aliphatic group preferably has 1 to 12 carbon atoms. Examples of aliphatic amines include amines (alkylamines or alkylolamines) or cyclic amines in which at least one hydrogen atom of ammonia NH3 is replaced by an alkyl or hydroxyalkyl group having 12 or fewer carbon atoms. Specific examples of alkylamines and alkylolamines 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 alkylolamines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octylamine, and tri-octylamine. Among these, trialkylamines having 5 to 10 carbon atoms are more preferred, and tri-n-pentylamine or tri-octylamine are particularly preferred.

[0323] As a cyclic amine, examples include heterocyclic compounds containing a nitrogen atom as a heteroatom. Such heterocyclic compounds can be monocyclic (aliphatic monocyclic amines) or polycyclic (aliphatic polycyclic amines). Specifically, examples of aliphatic monocyclic amines include piperidine and piperidine. For aliphatic polycyclic amines, those with a preferred carbon number of 6 to 10 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.

[0324] Other aliphatic amines include triethanolamine (2-methoxymethoxyethyl)amine, triethanolamine {2-(2-methoxyethoxy)ethyl}amine, triethanolamine {2-(2-methoxyethoxymethoxy)ethyl}amine, triethanolamine {2-(1-methoxyethoxy)ethyl}amine, triethanolamine {2-(1-ethoxyethoxy)ethyl}amine, triethanolamine {2-(1-ethoxypropoxy)ethyl}amine, triethanolamine [2-{2-(2-hydroxyethoxy)ethoxy}ethyl]amine, triethanolamine triacetate, etc., with triethanolamine triacetate being preferred.

[0325] Furthermore, aromatic amines may also be used as component (D2). Examples of aromatic amines include 4-dimethylaminepyridine, pyrrole, indole, pyrazole, imidazole or derivatives thereof, tribenzylamine, 2,6-diisopropylaniline, N-tert-butoxycarbonylpyrrolidine, etc.

[0326] Component (D2) can be used alone or in combination of two or more. When the photoresist composition contains component (D2), the content of component (D2) in the photoresist composition is usually in the range of 0.01 to 5 parts by mass relative to 100 parts by mass of component (A1). By setting it within the above range, the shape of the photoresist pattern and its stability over time are improved.

[0327] ≪At least one compound (E) selected from the group consisting of organic carboxylic acids and phosphorus oxyacids and their derivatives≫ In the photoresist composition of this embodiment, for the purpose of preventing sensitivity degradation or improving the shape of the photoresist pattern and the stability over time, at least one compound (E) selected from the group consisting of organic carboxylic acids and phosphorus oxyacids and their derivatives (hereinafter referred to as "(E) component") may be included as an optional component. As an organic carboxylic acid, acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, etc. are preferred. As a phosphorus oxyacid, phosphoric acid, phosphonic acid, hypophosphonic acid, etc. are possible examples, among which phosphonic acid is particularly preferred. As a derivative of phosphorus oxyacid, esters in which the hydrogen atoms of the above-mentioned oxyacid are replaced by hydrocarbon groups are possible examples, and as the aforementioned hydrocarbon group, alkyl groups having 1 to 5 carbon atoms, aryl groups having 6 to 15 carbon atoms, etc. are possible examples. Examples of phosphoric acid derivatives include dibutyl phosphate, diphenyl phosphate, and other phosphate esters. Examples of phosphonic acid derivatives include dimethyl phosphonate, dibutyl phosphonate, phenylphosphonic acid, diphenyl phosphonate, dibenzyl phosphonate, and other phosphonate esters. Examples of hypophosphonic acid derivatives include hypophosphonate esters or phenylhydantoin. In the photoresist composition of this embodiment, component (E) may be used alone or in combination with two or more components. When the photoresist composition contains component (E), the content of component (E) is typically in the range of 0.01 to 5 parts by mass relative to 100 parts by mass of component (A1).

[0328] ≪Fluorine Additive Component (F)≫ The photoresist composition of this embodiment may contain a fluorine additive component (hereinafter referred to as "(F) component") in order to impart water repellency to the photoresist film or to improve the photolithography properties. As the (F) component, for example, fluorine-containing polymeric compounds described in Japanese Patent Application Publication No. 2010-002870, Japanese Patent Application Publication No. 2010-032994, Japanese Patent Application Publication No. 2010-277043, Japanese Patent Application Publication No. 2011-13569, and Japanese Patent Application Publication No. 2011-128226 may be used. More specifically, polymers having the constituent unit (f1) shown in the following general formula (f1-1) may be cited as the (F) component. The polymer is preferably a homopolymer composed solely of the constituent unit (f1) shown in formula (f1-1); a copolymer of the constituent unit (f1) and the aforementioned constituent unit (a1); or a copolymer of the constituent unit (f1) and a constituent unit derived from acrylic acid or methacrylic acid with the aforementioned constituent unit (a1). Here, the aforementioned constituent unit (a1) copolymerized with the constituent unit (f1) is preferably a constituent unit derived from 1-ethyl-1-cyclooctyl (meth)acrylate or a constituent unit derived from 1-methyl-1-adamantyl (meth)acrylate.

[0329] [In the formula, R is the same as above, Rf102 and Rf103 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or a alkyl halide having 1 to 5 carbon atoms, and Rf102 and Rf103 may be the same or different; nf1 is an integer from 0 to 5, and Rf101 is an organic group containing a fluorine atom].

[0330] In formula (f1-1), the R group at the carbon atom bonded to the α-position is the same as described above. R is preferably a hydrogen atom or a methyl group. In formula (f1-1), the halogen atom of Rf102 and Rf103 is preferably a fluorine atom. As the alkyl group of Rf102 and Rf103 having 1 to 5 carbon atoms, examples can be made that are the same as the alkyl group of R having 1 to 5 carbon atoms described above, preferably methyl or ethyl. As the alkyl halide of Rf102 and Rf103 having 1 to 5 carbon atoms, specifically, examples can be groups in which part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are replaced by halogen atoms. As the halogen atom, it is preferably a fluorine atom. Among them, as Rf102 and Rf103, it is preferably a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom, a fluorine atom, a methyl group, or an ethyl group. In formula (f1-1), nf1 is an integer from 0 to 5, preferably an integer from 0 to 3, and even more preferably 1 or 2.

[0331] In formula (f1-1), Rf101 is an organic group containing a fluorine atom, preferably a hydrocarbon group containing a fluorine atom. The hydrocarbon group containing a fluorine atom can be linear, branched, or cyclic, preferably with 1 to 20 carbon atoms, more preferably with 1 to 15 carbon atoms, and especially preferably with 1 to 10 carbon atoms. Furthermore, the hydrocarbon group containing a fluorine atom is preferably in which at least 25% of the hydrogen atoms are fluorinated, more preferably at least 50%, and especially preferably at least 60%, as this improves the hydrophobicity of the photoresist film during immersion exposure. Rf101 is more preferably a fluorinated hydrocarbon group with 1 to 6 carbon atoms, and especially preferably trifluoromethyl, -CH2-CF3, -CH2-CF2-CF3, -CH(CF3)2, -CH2-CH2-CF3, or -CH2-CH2-CF2-CF2-CF2-CF3.

[0332] (F) The weight average molecular weight (Mw) of the component (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 photoresist solvents when used as a photoresist; if it is above the lower limit of this range, the photoresist film has good water repellency. The dispersion (Mw / Mn) of the component (F) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.0 to 2.5.

[0333] In the photoresist composition of this embodiment, the (F) component may be used alone or in combination with two or more components. When the photoresist composition contains the (F) component, the content of the (F) component is usually used in a ratio of 0.5 to 10 parts by mass relative to 100 parts by mass of the (A1) component.

[0334] ≪Organic Solvent Component (S)≫ The photoresist composition system of this embodiment can be manufactured by dissolving the photoresist material in an organic solvent component (hereinafter referred to as "(S) component"). As the (S) component, it is acceptable as long as it can dissolve all the components used to form a homogeneous solution, and any well-known solvent conventionally used as a solvent for chemically amplified photoresist compositions can be appropriately selected. As component (S), examples include lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl n-pentanone, methyl isopentanone, and 2-heptanone; polyols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; compounds containing ester bonds such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; and polyol derivatives containing ether bonds such as monopropyl ethers, monoethyl ethers, monopropyl ethers, monobutyl ethers, etc., of the aforementioned polyols or compounds containing ester bonds. [Among these, the preferred type is...] The solvents include propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME); cyclic ethers such as dialkylene; esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, etc.; aromatic organic solvents such as benzyl ether, ethyl benzyl ether, tolyl methyl ether, diphenyl ether, bibenzyl ether, phenethyl ether, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, isopropyltoluene, mesitylene, etc.; and dimethyl sulfoxide (DMSO). In the photoresist composition of this embodiment, component (S) can be used alone or as a mixed solvent of two or more. Among them, PGMEA, PGME, γ-butyrolactone, EL, and cyclohexanone are preferred.

[0335] Furthermore, as component (S), a mixed solvent of PGMEA and a polar solvent is also preferred. The mixing ratio (mass ratio) can be appropriately determined by considering the compatibility of PGMEA and the polar solvent, but is preferably in the range of 1:9 to 9:1, more preferably in the range of 2:8 to 8:2. More specifically, when EL or cyclohexanone is mixed as a polar solvent, the mass ratio of PGMEA:EL or cyclohexanone is preferably 1:9 to 9:1, more preferably 2:8 to 8:2. Also, when PGME is mixed as a polar solvent, the mass ratio of PGMEA:PGME is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, and even more preferably 3:7 to 7:3. Furthermore, a mixed solvent of PGMEA and PGME with cyclohexanone is also preferred. Additionally, as component (S), a mixed solvent of at least one selected from PGMEA and EL with γ-butyrolactone is also preferred. At this point, the preferred mixing ratio of the former to the latter is 70:30 to 95:5. The amount of component (S) used is not particularly limited, and should be appropriately set according to the coating thickness, based on the concentration required for coating onto a substrate, etc. Generally, component (S) is used with a solid content concentration of 0.1 to 20% by mass, preferably within the range of 0.2 to 15% by mass.

[0336] In the photoresist composition of this embodiment, additives with miscibility may be added as desired, such as additional resins, dissolution inhibitors, plasticizers, stabilizers, colorants, halo inhibitors, dyes, etc., for improving the performance of the photoresist film.

[0337] The photoresist composition of this embodiment can remove impurities after dissolving the aforementioned photoresist material in component (S) using a polyimide porous membrane, a polyamide-imide porous membrane, or the like. For example, a filter made of a polyimide porous membrane, a filter made of a polyamide-imide porous membrane, or a filter made of both polyimide porous membranes can be used to filter the photoresist composition. Examples of the aforementioned polyimide porous membranes and polyamide-imide porous membranes include those described in Japanese Patent Application Publication No. 2016-155121.

[0338] The photoresist composition of this embodiment described above contains a polymer compound (A01) and a compound (D1) having the aforementioned constituent units (a01), (a02), and (a03). The polymer compound (A01) has constituent units (a01), which allows for appropriate adjustment of its solubility in the developing solution. Furthermore, the polymer compound (A01) contains two types of constituent units (constituent units (a02) and (a03)) that both have acid-dissociating groups, thereby improving deprotection reactivity and suppressing the dissolution of unexposed portions of the photoresist film caused by developing. In addition, the presence of compound (D1) further enhances the contrast between exposed and unexposed portions. Through the synergistic effect of these combinations, the photoresist composition of this embodiment improves roughness reduction, collapse limits, and pattern residue.

[0339] The photoresist composition of this embodiment is particularly useful for forming sparse patterns with a linewidth to gap width ratio.

[0340] (Photoresist Pattern Forming Method) The photoresist pattern forming method of the second aspect of the present invention is a method comprising the following steps: forming a photoresist film on a support using the photoresist composition of the first aspect of the present invention described above; exposing the aforementioned photoresist film; and developing the exposed photoresist film to form a photoresist pattern. As one embodiment of this photoresist pattern forming method, for example, a photoresist pattern forming method performed as follows can be cited.

[0341] First, the photoresist composition of the above embodiment is coated onto a support using a spin coater or similar equipment. For example, it is baked at a temperature of 80–150°C for 40–120 seconds, preferably 60–90 seconds (post-coating baking (PAB)) to form a photoresist film. Next, the photoresist film is selectively exposed using an exposure apparatus such as an electron line drawing apparatus or an ArF exposure apparatus, either by exposure through a mask (mask pattern) or by direct electron line irradiation without exposure through the mask pattern. Then, it is baked at a temperature of 80–150°C for 40–120 seconds, preferably 60–90 seconds (post-exposure baking (PEB)). Finally, the aforementioned photoresist film is developed. In an alkaline development process, an alkaline developer is used; in a solvent development process, a developer containing an organic solvent (organic developer) is used.

[0342] After development, a rinsing process is preferably performed. In alkaline development processes, rinsing with pure water is preferred; in solvent development processes, rinsing with a rinsing solution containing an organic solvent is preferred. In solvent development processes, after the aforementioned development or rinsing process, a supercritical fluid can also be used to remove the developer or rinsing solution adhering to the pattern. After development or rinsing, drying is performed. Alternatively, depending on the circumstances, a baking process (post-baking) can be performed after the aforementioned development process. In this way, a photoresist pattern can be formed.

[0343] There are no particular limitations on the support body; conventional materials can be used, such as substrates for electronic components, or substrates on which specific wiring patterns are formed. More specifically, examples include metal substrates such as silicon wafers, copper, chromium, iron, and aluminum, or glass substrates. Materials for the wiring patterns can be, for example, copper, aluminum, nickel, and gold. Furthermore, the support body can also be a substrate on which inorganic and / or organic films are formed. Examples of inorganic films include inorganic antireflective films (inorganic BARC). Examples of organic films include organic antireflective films (organic BARC) or organic films such as the lower organic film in multilayer photoresist processes. Here, the so-called multilayer photoresist method refers to a method in which at least one organic film (lower organic film) and at least one photoresist film (upper photoresist film) are deposited on a substrate. The photoresist pattern formed on the upper photoresist film is used as a mask to pattern the lower organic film. This method is considered capable of forming patterns with high aspect ratios. In other words, according to the multilayer photoresist method, since the required thickness can be ensured by the lower organic film, the photoresist film can be thinned, and fine patterns with high aspect ratios can be formed. The multilayer photoresist method is basically divided into: a two-layer structure forming an upper photoresist film and a lower organic film (2-layer photoresist method); and a three-layer or more multilayer structure having one or more intermediate layers (such as metal thin films) between the upper photoresist film and the lower organic film (3-layer photoresist method).

[0344] There are no particular limitations on the wavelength used for exposure; radiation from ArF excimer lasers, KrF excimer lasers, F2 excimer lasers, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-rays, soft X-rays, etc., can be used. The aforementioned photoresist composition is highly useful as a KrF excimer laser, ArF excimer laser, EB, or EUV, and even more useful as an ArF excimer laser.

[0345] The exposure method for the photoresist film can be ordinary exposure (dry exposure) performed in an inert gas such as air or nitrogen, or liquid immersion lithography, but liquid immersion lithography is preferred. Liquid immersion lithography is an exposure method in which the space between the photoresist film and the lens at the lowest position of the exposure apparatus is filled with a solvent (immersion medium) having a refractive index greater than that of air, and exposure is performed in this state (immersion exposure). As for the immersion medium, it is preferably a solvent having a refractive index greater than that of air and less than that of the photoresist film being exposed. As for the refractive index of the solvent, there are no other limitations as long as it is within the aforementioned range. Examples of solvents having a refractive index greater than that of air and less than that of the aforementioned photoresist film include water, fluorine-based inert liquids, silicon-based solvents, and hydrocarbon-based solvents. Specific examples of fluorine-based inert liquids include liquids with fluorine compounds as the main component, such as C3HCl2F5, C4F9OCH3, C4F9OC2H5, and C5H3F7, with a boiling point preferably of 70–180°C, and more preferably 80–160°C. When a fluorine-based inert liquid has a boiling point within the above range, the medium used for immersion can be easily removed after exposure, making it preferable. As a fluorine-based inert liquid, perfluoroalkane compounds in which all hydrogen atoms of the alkyl group are replaced by fluorine atoms are particularly preferred. Specifically, perfluoroalkane compounds include perfluoroalkyl ether compounds and perfluoroalkylamine compounds. Furthermore, specifically, perfluoro(2-butyltetrahydrofuran) (boiling point 102°C) can be cited as a perfluoroalkyl ether compound, and perfluorotributylamine (boiling point 174°C) can be cited as a perfluoroalkylamine compound. From the perspectives of cost, safety, environmental issues, and versatility, water is more suitable as a liquid immersion medium.

[0346] Examples of alkaline developing solutions used in alkaline developing processes include 0.1–10% by mass tetramethylammonium hydroxide (TMAH) aqueous solutions. For organic developing solutions used in solvent developing processes, the organic solvent can be any solvent capable of dissolving component (A) (component (A) before exposure), and can be appropriately selected from well-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. Ketone solvents are organic solvents whose structure contains CC(=O)-C. Ester solvents are organic solvents whose structure contains CC(=O)-OC. Alcohol solvents are organic solvents whose structure contains an alcoholic hydroxyl group. "Alcoholic hydroxyl group" refers to a hydroxyl group bonded to a carbon atom of an aliphatic hydrocarbon group. Nitrile solvents are organic solvents whose structure contains a nitrile group. Acrylamine solvents are organic solvents whose structure contains acetamine groups. Ether solvents are organic solvents whose structure contains COC. Among organic solvents, there are also organic solvents whose structure contains a plurality of functional groups having the characteristics of the solvents described above, but in that case, they are equivalent to solvents containing any one of the functional groups possessed by that organic solvent. For example, diethylene glycol monomethyl ether is equivalent to either alcohol solvents or ether solvents in the above classification. Hydrocarbon solvents are composed of hydrocarbons that can be halogenated and are hydrocarbon solvents without substituents other than halogen atoms. As a halogen atom, a fluorine atom is preferred. Among the organic solvents contained in organic developing solutions, polar solvents are preferred, and ketone solvents, ester solvents, nitrile solvents, etc. are more preferred.

[0347] Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexyl ketone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetoacetone, acetone-based acetone, ionone, diacetone alcohol, acetoethanol, acetophenone, methyl naphthyl ketone, isophorone, propenyl carbonate, γ-butyrolactone, and methylpentyl ketone (2-heptanone). Among these, methylpentyl ketone (2-heptanone) is preferred as a ketone solvent.

[0348] Examples of ester-based solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxy, ethyl ethoxy, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate. Acetates, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate Esters, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, etc. Among these, butyl acetate is preferred as an ester solvent.

[0349] As a nitrile solvent, examples include acetonitrile, propionitrile, valerate, and butyronitrile.

[0350] Well-known additives may be incorporated into the organic developing solution as needed. Examples of such additives include surfactants. There are no particular limitations on the surfactant; for example, ionic or nonionic fluorinated and / or silicone surfactants may be used. Nonionic surfactants are preferred, more preferably nonionic fluorinated or silicone surfactants. When incorporating a surfactant, the amount incorporated is typically 0.001–5% by mass relative to the total amount of the organic developing solution, preferably 0.005–2% by mass, and even more preferably 0.01–0.5% by mass.

[0351] The developing system can be implemented by well-known developing methods, such as: immersing the support in the developing solution for a certain time (immersion method), piling the developing solution on the surface of the support by surface tension and letting it stand for a certain time (coating method), spraying the developing solution onto the surface of the support (spraying method), and continuously dispensing the developing solution onto the support rotating at a certain speed while scanning the developing solution nozzle at a certain speed (dynamic distribution method), etc.

[0352] The organic solvent contained in the rinsing solution used for rinsing after developing in the solvent-based developing process may, for example, be selected from the organic solvents listed above used as organic developing solutions, preferably those that are difficult to dissolve photoresist patterns. Typically, at least one solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is used. Among these, at least one solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, and amide solvents is preferred; more preferably, at least one solvent selected from alcohol solvents and ester solvents is preferred; and most preferably, an alcohol solvent is used. The alcohol solvent used in the rinsing solution is preferably a monohydric alcohol having 6 to 8 carbon atoms, and the monohydric alcohol may be linear, branched, or cyclic. Specifically, examples include 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, and benzyl alcohol. Among these, 1-hexanol, 2-heptanol, and 2-hexanol are preferred, and 1-hexanol and 2-hexanol are even more preferred. Any one of these organic solvents can be used alone, or two or more can be used in combination. Furthermore, it can be used in combination with other organic solvents mentioned above or with water. However, considering the imaging characteristics, the amount of water added to the rinsing solution relative to the total amount of the rinsing solution is preferably 30% by mass or less, more preferably 10% by mass or less, particularly preferably 5% by mass or less, and especially preferably 3% by mass or less. Well-known additives can be added to the rinsing solution as needed. Examples of such additives include surfactants. The surfactant can be any of the same types mentioned above, preferably a nonionic surfactant, more preferably a nonionic fluorinated surfactant or a nonionic silicone surfactant. When a surfactant is incorporated, its dosage relative to the total amount of the rinsing solution is typically 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass.

[0353] The rinsing treatment (cleaning treatment) using rinsing fluid can be carried out by well-known rinsing methods. Examples of such rinsing treatment methods include: continuously dispensing rinsing fluid onto a support rotating at a certain speed (spin coating method), immersing the support in rinsing fluid for a certain time (immersion method), and spraying rinsing fluid onto the surface of the support (spraying method).

[0354] According to the photoresist pattern forming method of this embodiment described above, since the above-described photoresist composition is used, a photoresist pattern with good roughness reduction, collapse limit, and pattern residue can be formed. Furthermore, according to the photoresist pattern forming method of this embodiment, the roughness reduction, collapse limit, and pattern residue are particularly excellent in the formation of sparsely spaced patterns. [Example]

[0355] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

[0356] <Preparation of Polymer Compounds> The polymer compounds (A1-1) to (A1-11) and (A2-1) to (A2-6) used in this embodiment were obtained by free radical polymerization using monomers capable of deriving the constituent units of each polymer compound at a specified molar ratio. For each obtained polymer compound, the weight average molecular weight (Mw) and molecular weight dispersion (Mw / Mn) were determined by GPC measurement (conversion to standard polystyrene). Furthermore, for each obtained polymer compound, the copolymerization composition ratio (the proportion of each constituent unit in the structural formula (molar ratio)) was determined by carbon-13 nuclear magnetic resonance spectroscopy (600MHz_13C-NMR).

[0357]

[0358] Polymer (A1-1): Weight average molecular weight (Mw) 6900, molecular weight dispersion (Mw / Mn) 1.57, l / m / n = 50 / 10 / 40. Polymer (A1-2): Weight average molecular weight (Mw) 7000, molecular weight dispersion (Mw / Mn) 1.60, l / m / n = 50 / 10 / 40. Polymer (A1-3): Weight average molecular weight (Mw) 7200, molecular weight dispersion (Mw / Mn) 1.61, l / m / n = 50 / 10 / 40. Polymer (A1-4): Weight average molecular weight (Mw) 7100, molecular weight dispersion (Mw / Mn) 1.67, l / m / n = 50 / 10 / 40.

[0359]

[0360] Polymer compound (A1-5): Weight average molecular weight (Mw) 7000, molecular weight dispersion (Mw / Mn) 1.63, l / m / n = 50 / 10 / 40. Polymer compound (A1-6): Weight average molecular weight (Mw) 6800, molecular weight dispersion (Mw / Mn) 1.59, l / m / n = 50 / 10 / 40. Polymer compound (A1-7): Weight average molecular weight (Mw) 6600, molecular weight dispersion (Mw / Mn) 1.58, l / m / n = 50 / 10 / 40. Polymer compound (A1-8): Weight average molecular weight (Mw) 6900, molecular weight dispersion (Mw / Mn) 1.62, l / m / n = 50 / 10 / 40.

[0361]

[0362] Polymer (A1-9): Weight average molecular weight (Mw) 7200, molecular weight dispersion (Mw / Mn) 1.66, l / m / n = 50 / 10 / 40. Polymer (A1-10): Weight average molecular weight (Mw) 7000, molecular weight dispersion (Mw / Mn) 1.59, l / m / n = 50 / 25 / 25. Polymer (A1-11): Weight average molecular weight (Mw) 6800, molecular weight dispersion (Mw / Mn) 1.58, l / m / n = 50 / 40 / 10. Polymers (A1-1), (A1-10), and (A1-11) have the same constituent units, but the ratios of these units differ.

[0363]

[0364] Polymer (A2-1): Weight average molecular weight (Mw) 7000, molecular weight dispersion (Mw / Mn) 1.64, l / m / n = 50 / 10 / 40. Polymer (A2-2): Weight average molecular weight (Mw) 6800, molecular weight dispersion (Mw / Mn) 1.50, l / m / n = 50 / 10 / 40. Polymer (A2-3): Weight average molecular weight (Mw) 6800, molecular weight dispersion (Mw / Mn) 1.53, l / m / n = 50 / 10 / 40. Polymer (A2-4): Weight average molecular weight (Mw) 8000, molecular weight dispersion (Mw / Mn) 1.50, l / m / n = 50 / 10 / 40. Polymer compound (A2-5): Weight average molecular weight (Mw) 7500, molecular weight dispersion (Mw / Mn) 1.60, l / m / n = 50 / 10 / 40. Polymer compound (A2-6): Weight average molecular weight (Mw) 7200, molecular weight dispersion (Mw / Mn) 1.61, l / m / n = 50 / 10 / 40.

[0365] <Preparation of photoresist composition> (Examples 1-17, Comparative Examples 1-8) Photoresist compositions of each example were prepared by mixing and dissolving the components shown in Tables 1 and 2.

[0366]

[0367]

[0368] In Tables 1 and 2, each abbreviation symbol has the following meaning. The value in [ ] is the amount of admixture (parts by mass). (A1)-1~(A1)-11: The above-mentioned polymeric compounds (A1-1)~(A1-11). (A2)-1~(A2)-6: The above-mentioned polymeric compounds (A2-1)~(A2-6). (B)-1: An acid-producing agent composed of the compound represented by the following chemical formula (B-1). (B)-2: An acid-producing agent composed of the compound represented by the following chemical formula (B-2).

[0369]

[0370] (D1)-1~(D1)-6: Acid diffusion control agents composed of compounds represented by the following chemical formulas (D1-1)~(D1-6). (D2)-1: Tri-n-octylamine. (S)-1: A mixed solvent of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether / cyclohexanone = 60 / 10 / 30 (mass ratio).

[0371]

[0372] <Formation of Photoresist Pattern> Using a spinner, an organic antireflective film composition (trade name: ARC29A, manufactured by BULWER Scientific Corporation) was coated onto a 12-inch silicon wafer. It was then dried by baking at 205°C for 60 seconds on a hot plate to form an organic antireflective film with a thickness of 98 nm. Using a spinner, photoresist compositions of various examples were coated onto the aforementioned antireflective film, and a pre-baking (PAB) treatment was performed at 130°C for 60 seconds on a hot plate, followed by drying to form photoresist films with a thickness of 80 nm. Next, using a spinner, a top coating was coated onto the photoresist film, and a baking treatment was performed at 90°C for 60 seconds on a hot plate to form a top coating film with a thickness of 35 nm. Next, the aforementioned photoresist film was selectively irradiated with an ArF excimer laser (193 nm) through a photomask (6% halftone) using an NXT1900Gi immersion ArF exposure apparatus [ASML; NA (numerical aperture) = 1.35, Dipole 90X, Sigma (in / out = 0.80 / 0.97) TE-pol, immersion medium: ultrapure water]. Then, a PEB treatment was performed at 90°C for 60 seconds. Subsequently, alkaline development was performed at 23°C with a 2.38% by mass TMAH aqueous solution (trade name: NMD-3, Tokyo Ohka Kogyo Co., Ltd.), followed by a 15-second water rinse with pure water and spin-drying. As a result, line and gap patterns (hereinafter referred to as LS patterns) with a linewidth of 30 nm and a spacing of 90 nm (mask size 40 nm) were formed.

[0373] [Evaluation of the optimal exposure (Eop)] The optimal exposure Eop (mJ / cm2) for the target size LS pattern formed by the above <formation of photoresist pattern> is determined and displayed as "Eop (mJ / cm2)" in Table 3.

[0374] [Evaluation of LWR (Line Width Roughness)] For the LS pattern formed by the above <Formation of Photoresist Pattern>, the 3σ value representing the LWR scale is determined. It is displayed as "LWR (nm)" in Table 3. "3σ" is the value of three times the standard deviation (σ) obtained by measuring the line position at 400 points along the length of the line using a length-measuring SEM (scanning electron microscope, accelerating voltage 500V, trade name: CG5000, manufactured by Hitachi High Technology Co., Ltd.). The smaller the value of 3σ, the smaller the roughness of the line sidewall, and the more uniform the width of the LS pattern can be obtained.

[0375] [Evaluation of Collapse Margin] Determine the optimal exposure value Eop for forming the target-sized LS pattern using the above <Formation of Photoresist Pattern>. Then, while gradually increasing the exposure value from the aforementioned optimal exposure value Eop to form the LS pattern, use a length-measuring SEM (scanning electron microscope, accelerating voltage 500V, trade name: CG5000, manufactured by Hitachi High Technology Corporation) to determine the minimum size of the pattern that can be resolved without collapsing. This is shown as the "collapse margin (nm)" in Table 3.

[0376] [Evaluation of Pattern Residual Film] For the LS pattern formed by the above <Formation of Photoresist Pattern>, cross-sectional observation was performed using a length-measuring SEM (scanning electron microscope, trade name: SU8000, manufactured by Hitachi High Technology Co., Ltd.) to measure the pattern residual film, and the following criteria were used for evaluation. These are shown in Table 3 as "pattern residual film". A: Pattern residual film exceeds 70nm but is below 80nm B: Pattern residual film is 60nm to 70nm C: Pattern residual film is less than 60nm

[0377]

[0378] As shown in Table 3, compared with the photoresist composition of the comparative example, the photoresist composition of the embodiment has good sensitivity, roughness reduction and collapse limit, and can form photoresist patterns with a large amount of residual film.

Claims

1. A photoresist composition that generates acid upon exposure and whose solubility in a developing solution changes due to the action of the acid, comprising: a resin component (A1) whose solubility in a developing solution changes due to the action of the acid, and one or more compounds (D1) selected from the group consisting of compounds represented by the following general formula (d1-1) and compounds represented by the following general formula (d1-2), wherein the content of the aforementioned compound (D1) is 3 to 20 parts by mass relative to 100 parts by mass of the aforementioned resin component (A1), and the aforementioned resin component (A1) comprises a polymeric compound (A01) consisting only of a constituent unit (a01) represented by the following general formula (a0-1), a constituent unit (a02) represented by the following general formula (a0-2), and a constituent unit (a03) represented by the following general formula (a0-3). [In the formula, Rd1 and Rd2 are each independently a cyclic group that may have substituents, a chain alkyl group that may have substituents, or a chain alkenyl group that may have substituents; however, in Rd2 in formula (d1-2), the carbon atom adjacent to the S atom is not bonded with a fluorine atom; m is an integer of 1 or more, and Mm+ are each independently an m-valent organic cation]; [In formula (a0-1), R01 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms; Va01 is a divalent linked group; na01 is an integer of 0 to 2; Ra01 is a lactone-containing cyclic group having one or more substituents selected from the group consisting of halogen atoms, carboxyl groups, acetyls, nitro groups, and cyano groups; the aforementioned lactone-containing cyclic group may also have substituents other than those in the aforementioned group;] In formula (a0-2), R02 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms; Va02 is a divalent linkage; na02 is an integer from 0 to 2; Ra021 and Ra022 are each independently a chain alkyl group; Yaa0 is a carbon atom; Xaa0 is a group that forms a monocyclic alicyclic hydrocarbon group together with Yaa0; some or all of the hydrogen atoms in this monocyclic alicyclic hydrocarbon group may be substituted. In formula (a0-3), R03 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms; Va03 is a divalent linkage; na03 is an integer from 0 to 2; Ra031 is a chain alkyl group; Yab0 is a carbon atom; Xab0 is a group that forms a monocyclic alicyclic hydrocarbon group together with Yab0; some or all of the hydrogen atoms in this monocyclic alicyclic hydrocarbon group may be substituted.

2. The photoresist composition of claim 1, wherein the aforementioned constituent unit (a01) is a constituent unit represented by the following general formula (a01-1); [In formula (a01-1), R01 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms; Va01 is a divalent linker; na01 is an integer from 0 to 2; Ra1 and Ra2 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group, or an alkylthio group, or Ra1 and Ra2 can be bonded to each other to form an alkyl group having 1 to 6 carbon atoms containing oxygen atoms or sulfur atoms, an ether bond, or a thioether bond; Ra'01 is a halogen atom, an alkyl group having 1 to 6 carbon atoms containing halogen atoms, a hydroxyl group that can be protected by a protecting group and has 1 to 6 carbon atoms containing halogen atoms, a carboxyl group that can form a salt, or a substituted oxycarbonyl group; p0 is an integer from 0 to 8; when two or more Ra'01 are present, the complex Ra'01 can be the same or different from each other; q0 is an integer from 1 to 9].

3. The photoresist composition of claim 1, wherein the aforementioned constitutive unit (a01) is a constitutive unit represented by the following general formula (a01-1-1); [in formula (a01-1-1), R01 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms; Va01 is a divalent linkage group; na01 is an integer from 0 to 2; q00 is an integer from 1 to 3].

4. The photoresist composition of claim 1, wherein the aforementioned compound (D1) contains the compound represented by the aforementioned general formula (d1-2).

5. The photoresist composition of claim 1, wherein the molar ratio of the content of the constituent unit (a01) of the aforementioned polymer compound (A01) to the total content of the constituent units (a02) and (a03) (constituent unit (a01): constituent unit (a02) and constituent unit (a03)) is 60:40 to 40:

60.

6. The photoresist composition of claim 1, wherein the content of the constituent unit (a02) of the aforementioned polymer compound (A01) is 20 to 50 mol relative to the total (100 mol%) of all constituent units constituting the aforementioned polymer compound (A01).

7. The photoresist composition of claim 1, further comprising an acid-generating agent component (B) that generates acid by exposure (except for the aforementioned compound (D1)).

8. A method for forming a photoresist pattern, comprising: a step of forming a photoresist film on a support using a photoresist composition as claimed in claim 1; a step of exposing the aforementioned photoresist film; and a step of developing the exposed photoresist film to form a photoresist pattern.

9. The photoresist pattern forming method of claim 8, wherein in the step of exposing the aforementioned photoresist film, the aforementioned photoresist film is subjected to liquid immersion exposure.